CN101193932B

CN101193932B - Polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom

Info

Publication number: CN101193932B
Application number: CN2006800205611A
Authority: CN
Inventors: E·D·克劳福德; T·J·佩科里尼; D·S·麦克威廉斯; D·S·波特; G·W·康奈尔
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 2005-06-17
Filing date: 2006-03-30
Publication date: 2012-08-08
Anticipated expiration: 2026-03-30
Also published as: CN101203541A; CN101193721A; CN101203543A; CN101193937A; CN101203540A; CN101203543B; CN101193935A; CN101193939A; CN101193946A; CN101193934A; CN101203542A; CN101193944A; CN101193932A; CN101193943B; CN101193942A; CN101193978A; CN101193668A; CN101193937B; CN101193936B; CN101193936A

Abstract

Described are polyester compositions comprising at least one polyester which comprises terephthalic acid residues, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 1,4-cyclohexanedimethanol, wherein the inherent viscosity and the Tg of the polyester provides for certain polyester properties. The polyesters may be manufactured into articles such as fibers, films, bottles or sheets.

Description

Contain cyclobutanediol and have logarithmic viscosity number and the polymer blend of high glass-transition temperature particular combination and by the goods of its production

The cross reference of related application

The right of priority of application below the application requires according to 35U.S.C. § 119 (e): the U.S. Provisional Application 60/731 that the U.S. Provisional Application of submitting on June 17th, 2005 was submitted on October 28th, 60/691,567,2005; The U.S. Provisional Application 60/731,389 that on October 28th, 454,2005 submitted; The U.S. Provisional Application 60/738 that the U.S. Provisional Application of submitting on November 22nd, 2005 was submitted on November 22nd, 60/739,058,2005; The U.S. Provisional Application 60/750,692 that on December 15th, 869,2005 submitted; The U.S. Provisional Application 60/750 that the U.S. Provisional Application of submitting on December 15th, 2005 was submitted on December 15th, 60/750,693,2005; The U.S. Provisional Application 60/750,547 that on December 15th, 682,2005 submitted; And it is for reference that their full content is introduced this paper.

Invention field

The present invention relates in general to the polymer blend by following component preparation: terephthalic acid, terephthalate or their mixture; 2,2,4,4-tetramethyl--1,3-cyclobutanediol; And 1,4 cyclohexane dimethanol; Said polyester has the particular combination of logarithmic viscosity number and second-order transition temperature (Tg).It is believed that these compsns have the particular combination of following two kinds or more kinds of performances: high impact, high glass-transition temperature (Tg), toughness; For example low ductile-brittle transition temperature, specific logarithmic viscosity number, the good color and the transparency; Low density, chemical-resistant, stability to hydrolysis; And long half-time of crystallization, this makes these polymer blends be easy to be shaped to goods.

Background of invention

Poly terephthalic acid 1,4-cyclohexylidene dimethylene ester (PCT) are a kind of only based on the ester of terephthalic acid or its ester and 1,4 cyclohexane dimethanol, and they are well known in the art, and can obtain from commerce.This polyester can when cooling apace from melt crystallization, thereby be difficult to for example extrude by means commonly known in the art, injection moulding etc. forms amorphous goods.For the crystallization rate of the PCT that slows down, can prepare the copolyesters that contains extra dicarboxylicacid or glycol (for example m-phthalic acid or terepthaloyl moietie).These also are well known in the art by the PCT of terepthaloyl moietie or isophthalate modified, and can obtain from commerce.

A kind of copolyesters that is generally used for producing film, sheet material and moulded parts is from terephthalic acid, 1,4 cyclohexane dimethanol and ethylene glycol.Though these copolyesters can be used in many end-uses, when in batching, comprising enough modification terepthaloyl moietie so that long half-time of crystallization to be provided, they are presented at the for example defective of second-order transition temperature and shock strength aspect of performance.For example; By terephthalic acid, 1; 4-cyclohexanedimethanol and ethylene glycol and have the copolyesters of sufficiently long half-time of crystallization amorphous products can be provided are compared with compsn disclosed herein, and it demonstrates disadvantageous higher ductile-brittle transition temperature and lower second-order transition temperature.

4, the polycarbonate of 4 '-isopropylidene biphenol (bisphenol-a polycarbonate) as the substitute of polyester known in the art, also has been known engineering moulded plastic.Bisphenol-a polycarbonate is transparent high performance plastics, and it has good physicals, for example dimensional stability, high heat resistance and good shock strength.Although bisphenol-a polycarbonate has many good physicalies, its higher melt viscosity causes melt processability poor, and the chemical-resistant of polycarbonate is poor.They also are difficult to thermoforming.

Contain 2,2,4,4-tetramethyl--1, the polymkeric substance of 3-cyclobutanediol also have description in the art.But generally speaking, these polymkeric substance demonstrate high logarithmic viscosity number, high melt viscosity and/or high Tg (second-order transition temperature), make the equipment that in industry, uses be not enough to produce or these materials of post polymerization processing.

Therefore, this area needs to have in a kind of workability on keeping industry standard equipment the polymkeric substance that is selected from following at least a two or more combination of properties: the toughness of polyester, high glass-transition temperature; High impact, stability to hydrolysis, chemical-resistant; Long half-time of crystallization, low ductile-brittle transition temperature, the good color and the transparency; Low density, and/or thermal formability.

Summary of the invention

It is believed that by terephthalic acid or its ester or their mixture and 1,4 cyclohexane dimethanol residue and 2,2; 4, that form and the particular composition that have logarithmic viscosity number and second-order transition temperature particular combination of 4-tetramethyl--1,3-cyclobutanediol residue is superior to known polyester and polycarbonate in the affiliated field at following one or more aspect of performances: high impact; Stability to hydrolysis, toughness, chemical-resistant; The good color and the transparency; Long half-time of crystallization, low ductile-brittle transition temperature, low-gravity and/or thermal formability.It is believed that these compsns are similar with polycarbonate aspect thermotolerance, and still can on standard industry equipment, process.

In one aspect, the present invention relates to a kind of polymer blend, it contains at least a polyester that contains following component:

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

Ii) 0-30 mole %'s has an aromatic dicarboxylic acid residue of 20 carbon atoms at the most; With

Iii) 0-10 mole %'s has an aliphatic dicarboxylic acid residue of 16 carbon atoms at the most; With

(b) diol component, it contains:

I) 2,2,4 of 1-99 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 1-99 mole %,

Wherein dicarboxylic acid component's total mole of % is 100 moles of %, and total mole of % of diol component is 100 moles of %; With

The logarithmic viscosity number of wherein said polyester is 0.35 to less than 0.70dL/g, in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration; With the Tg of wherein said polyester be 110-200 ℃.

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) greater than 2,2,4 of 81 to 99 moles of %, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) 1 to the 1,4 cyclohexane dimethanol residue less than 19 moles of %,

The logarithmic viscosity number of wherein said polyester is 0.35-0.2dL/g, in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration; With the Tg of wherein said polyester be 110-200 ℃.

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 40-85 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 15-60 mole %,

The logarithmic viscosity number of wherein said polyester is 0.35-1.2dL/g, in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration; With the Tg of wherein said polyester be 110-200 ℃.

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 40-85 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 15-60 mole %,

The logarithmic viscosity number of wherein said polyester is 0.35-1.2dL/g, in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration; With the Tg of wherein said polyester be 148-200 ℃.

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 40-80 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 20-60 mole %,

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 40-65 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 35-60 mole %,

The logarithmic viscosity number of wherein said polyester is 0.35-0.75dL/g, in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration; With the Tg of wherein said polyester be 110-200 ℃.

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 40-64.9 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 35-59.9 mole %,

Iii) 0.10 to the glycol residue less than 15 moles of %;

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 40-55 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 45-60 mole %,

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 45-55 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 45-55 mole %,

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 40-65 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 35-60 mole %,

The logarithmic viscosity number of wherein said polyester is 0.35-0.75dL/g, in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration;

The Tg of wherein said polyester be 110-200 ℃ and

Randomly before the polymerization of polymkeric substance or during add one or more branching agents.

In one aspect, the present invention relates to a kind of polymer blend, it contains:

(A) at least a polyester that contains following component:

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 1-99 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) the 1,4 cyclohexane dimethanol residue of 1-99 mole % and

(B) residue of at least a branching agent;

Wherein dicarboxylic acid component's total mole of % is 100 moles of %, and total mole of % of diol component is 100 moles of %;

The logarithmic viscosity number of wherein said polyester is 0.35-1.2dL/g, in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration;

The Tg of wherein said polyester is 110-200 ℃.

(A) at least a polyester that contains following component:

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 40-65 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) the 1,4 cyclohexane dimethanol residue of 35-60 mole % and

(B) residue of at least a branching agent;

The logarithmic viscosity number of wherein said polyester is 0.35-1.2dL/g, in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration; The Tg of wherein said polyester is 110-200 ℃.

(A) at least a polyester that contains following component:

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 40-65 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) the 1,4 cyclohexane dimethanol residue of 35-60 mole % and

(B) residue of at least a branching agent;

The logarithmic viscosity number of wherein said polyester is 0.35-0.75dL/g, in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration; The Tg of wherein said polyester is 110-200 ℃.

(A) at least a polyester that contains following component:

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 1-99 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) the 1,4 cyclohexane dimethanol residue of 1-99 mole % and

(B) at least a thermo-stabilizer or its reaction product;

(A) at least a polyester that contains following component:

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 40-65 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) the 1,4 cyclohexane dimethanol residue of 35-60 mole % and

(B) at least a thermo-stabilizer or its reaction product;

(A) at least a polyester that contains following component:

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 40-65 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) the 1,4 cyclohexane dimethanol residue of 35-60 mole % and

(B) at least a thermo-stabilizer or its reaction product;

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 40-65 mole %, 4-tetramethyl--1,3-cyclobutanediol; With

The ii) 1,4 cyclohexane dimethanol of 35-60 mole %,

The logarithmic viscosity number of wherein said polyester is 0.35-0.75dL/g, in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration; With

The Tg of wherein said polyester is 110-150 ℃.

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 40-65 mole %, 4-tetramethyl--1,3-cyclobutanediol; With

The ii) 1,4 cyclohexane dimethanol of 35-60 mole %,

The Tg of wherein said polyester is 120-135 ℃.

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 1-99 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 1-99 mole %,

Wherein the logarithmic viscosity number of polyester is 0.35-0.75dL/g, in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration; With

Wherein the Tg of polyester be from greater than 148 ℃ until 200 ℃.

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 1-99 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 1-99 mole %,

Wherein the logarithmic viscosity number of polyester is 0.35-1.2dL/g, in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration; With

Wherein the Tg of polyester is 127 ℃-200 ℃.

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 1-80 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 20-99 mole %,

The Tg of wherein said polyester is greater than 124 ℃ to 200 ℃.In other embodiments, Tg can be greater than 125 ℃ to 200 ℃, or greater than 126 ℃ to 200 ℃, or greater than 127 ℃ to 200 ℃.

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) greater than 50 until 2,2,4 of 99 moles of %, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) 1 to the 1,4 cyclohexane dimethanol residue less than 50 moles of %,

Wherein the Tg of polyester is 110 ℃-200 ℃.

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) greater than 50 until 2,2,4 of 80 moles of %, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) 20 to the 1,4 cyclohexane dimethanol residue less than 50 moles of %,

Wherein the Tg of polyester is 110-200 ℃.

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 1-99 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 1-99 mole %,

Wherein the logarithmic viscosity number of polyester is greater than 0.76 until 1.2dL/g, in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration; With

Wherein the Tg of polyester is 110-200 ℃.

In one aspect, said polymer blend contains at least a polycarbonate.

In one aspect, said polymer blend does not contain polycarbonate.

In one aspect, be used for polyester of the present invention and contain the glycol residue less than 15 moles of %, for example 0.01 mole of % is to the glycol residue less than 15 moles of %.

In one aspect, be used for polyester of the present invention and do not contain glycol residue.

In one aspect, be used for polyester of the present invention and contain at least a thermo-stabilizer and/or its reaction product.

In one aspect, be used for polyester of the present invention and do not contain branching agent, or before the polymerization of polyester or during add at least a branching agent.

In one aspect, be used for polyester of the present invention and contain at least a branching agent, and with the addition means or the sequence independence of branching agent.

In one aspect, being used for polyester of the present invention is not by 1, ammediol or 1,4-Ucar 35 or its combined preparation.In yet another aspect, 1, ammediol or 1,4-Ucar 35 or its combination can be used to prepare polyester of the present invention.

In one aspect of the invention, in the specific polyester of the present invention, use suitable-2,2,4; 4-tetramethyl--1, the mole % of 3-cyclobutanediol is greater than 50 moles of % or greater than suitable-2,2,4 of 55 moles of %; 4-tetramethyl--1, the 3-cyclobutanediol, or greater than suitable-2,2 of 70 moles of %; 4,4-tetramethyl--1,3-cyclobutanediol; Wherein suitable-2,2,4,4-tetramethyl--1,3-cyclobutanediol be with anti--2,2,4,4-tetramethyl--1, and total molar percentage of 3-cyclobutanediol equals 100 moles of %.

In one aspect of the invention, in the specific polyester of the present invention, use 2,2,4,4-tetramethyl--1,3-cyclobutanediol isomer the mole % be suitable-2,2 of 30-70 mole %; 4,4-tetramethyl--1,3-cyclobutanediol and 30-70 mole %'s is anti--2,2,4,4-tetramethyl--1,3-cyclobutanediol; Perhaps 40-60 mole %'s is suitable-2,2,4,4-tetramethyl--1, anti--2,2 of 3-cyclobutanediol and 40-60 mole %; 4,4-tetramethyl--1,3-cyclobutanediol, wherein suitable-2,2,4; 4-tetramethyl--1,3-cyclobutanediol be with anti--2,2,4,4-tetramethyl--1, and total molar percentage of 3-cyclobutanediol equals 100 moles of %.

In one aspect; Said polymer blend is used to produce goods of the present invention; Said goods include but not limited to extrude, the goods of calendering and/or moulding, include but not limited to injection-molded item, extruded product, casting extruded product, thermoformed articles, section bar extruded product, melt spinning goods, thermoformed articles, extrusion molding goods, injection blow molding goods, injection drawing blow goods, extrusion-blow molding product and extrude the stretch-blow goods.These goods can include but not limited to film, bottle (including but not limited to infant bottle), container, sheet material and/or fiber.In one aspect; Being used for polymer blend of the present invention can use with the form of various types of films and/or sheet material, includes but not limited to: film of extruding and/or sheet material, the film of calendering and/or sheet material; The film of compression moulding and/or sheet material, the film of solution casting and/or sheet material.The method for preparing film and/or sheet material includes but not limited to extrude, calendering, compression moulding and solution casting.

In addition, in one aspect, use polymer blend of the present invention that drying step before melt and/or the thermoforming is minimized and/or do not need this drying step.

In one aspect, it can be amorphous or hemicrystalline being used for specific polyester of the present invention.In one aspect, be used for specific polyester of the present invention and have lower percent crystallinity.Therefore, be used for specific polyester of the present invention and have essentially amorphous rheology, this representes that said polyester contains unordered basically polymer areas.

The accompanying drawing summary

Fig. 1 shows the soonest figure of the influence of half-time of crystallization of comonomer to modification PCT copolyesters.

Fig. 2 shows the figure of comonomer to the influence of the brittle-ductile transition temperature (Tbd) in the notched izod strength trial (ASTM D256,1/8 inch thick, 10 mil breach).

Fig. 3 shows 2,2,4,4-tetramethyl--1, and the composition of 3-cyclobutanediol is to the figure of the influence of the glass transition transition temperature (Tg) of copolyesters.

Detailed Description Of The Invention

Can understand the present invention better to specific embodiments of the present invention and the detailed description of work embodiment with reference to following.According to the object of the invention, certain embodiments of the present invention are disclosed in " summary of the invention ", and further describe following.Other embodiment of the present invention also is described below.

It is believed that described herein and be used for the unique combination that polyester of the present invention and/or polymer blend have following two or more physicalies: high impact, high glass-transition temperature, chemical-resistant; Stability to hydrolysis, toughness, for example low ductile-brittle transition temperature; The good color and the transparency, low density, long half-time of crystallization; And good processibility, this makes them be easy to be shaped to goods.In some embodiments of the present invention; Polyester has the special performance combination of good impact strength, thermotolerance, chemical-resistant, density; And/or the combination of properties of good impact strength, thermotolerance and processibility; And/or the combination of two or more said performances, this is irrealizable in existing polyester.

The term " polyester " that uses at this paper comprises " copolyesters ", and is interpreted as that expression reacts the synthetic polymer that makes through one or more bifunctional carboxylic acids and/or polyfunctional carboxylic acids with one or more difunctionality oxy-compound and/or multifunctional hydroxy compounds.Usually, the bifunctional carboxylic acid can be a dicarboxylicacid, and the difunctionality oxy-compound can be a divalent alcohol, for example glycol (glycol) and glycol (diol).The term " glycol " that uses in this application includes but not limited to glycol, glycol and/or multifunctional hydroxy compounds, for example branching agent.Perhaps, the bifunctional carboxylic acid can be a hydroxycarboxylic acid, and is for example right-hydroxy-benzoic acid; The difunctionality oxy-compound can be the virtue nuclear that has two hydroxyl substituents, for example quinhydrones.Term " residue " expression of using at this paper is any through carrying out polycondensation with corresponding monomer and/or esterification is introduced into the organic structure in the polymkeric substance.Term " repeating unit " expression of using at this paper has the dicarboxylic acid residue that connects via the ketonic oxygen base key and the organic structure of diol residue.Therefore, for example, dicarboxylic acid residue can be derived from dicarboxylic acid monomer or its corresponding carboxylic acid halides, ester, salt, acid anhydrides or its mixture.In addition, the term " diacid " that uses in this application comprises polyfunctional acid, for example branching agent.So; Any verivate that comprises dicarboxylicacid and dicarboxylicacid in term " dicarboxylicacid " expression of this paper use; Comprise its corresponding carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or its mixture, be used for process with glycol prepared in reaction polyester.Term " terephthalic acid " expression of using at this paper comprises terephthalic acid itself and its residue; And any verivate of terephthalic acid; Comprise its corresponding carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or its mixture, be used for process with glycol prepared in reaction polyester.

In one embodiment, terephthalic acid can be used as raw material.In another embodiment, DMT. Dimethyl p-benzenedicarboxylate is as raw material.In another embodiment, the mixture of terephthalic acid and DMT. Dimethyl p-benzenedicarboxylate can be as raw material and/or as intermediate materials.

Being used for polyester of the present invention usually can be from dicarboxylicacid and glycol according to the basic ratio prepared in reaction that equates, said dicarboxylicacid and glycol are introduced in the polyester polymers as their corresponding residue.So polyester of the present invention can contain basic sour residue (100 moles of %) and glycol (and/or multifunctional hydroxy compounds) residue (100 moles of %) that waits molar ratio, makes total mole of % of repeating unit equal 100 moles of %.So the molar percentage that provides in this manual can be based on the total mole number of sour residue, the total mole number of diol residue or the total mole number of repeating unit.For example, represent that based on the polyester that sour residue total amount meter contains 30 moles of % m-phthalic acids polyester contains 30 moles of % isophthalic acid residues, based on the sour residue meter of 100 moles of %.Therefore, in per 100 moles sour residue, 30 moles isophthalic acid residues is arranged.In another example, contain 30 moles of %2 based on diol residue total amount meter, 2,4,4-tetramethyl--1, the polyester of 3-cyclobutanediol represent that polyester contains 2,2,4 of 30 moles of %, 4-tetramethyl--1,3-cyclobutanediol residue is based on the diol residue meter of 100 moles of %.Therefore, in per 100 moles diol residue, have 30 moles 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.

In another aspect of the present invention, the Tg that is used for the polyester of polymer blend of the present invention includes but not limited to: 85-200 ℃; 85-190 ℃; 85-180 ℃; 85-170 ℃; 85-160 ℃; 85-155 ℃; 85-150 ℃; 85-145 ℃; 85-140 ℃; 85-138 ℃; 85-135 ℃; 85-130 ℃; 85-125 ℃; 85-120 ℃; 85-115 ℃; 85-110 ℃; 85-105 ℃; 85-100 ℃; 85-95 ℃; 85-90 ℃; 90-200 ℃; 90-190 ℃; 90-180 ℃; 90-170 ℃; 90-160 ℃; 90-155 ℃; 90-150 ℃; 90-145 ℃; 90-140 ℃; 90-138 ℃; 90-135 ℃; 90-130 ℃; 90-125 ℃; 90-120 ℃; 90-115 ℃; 90-110 ℃; 90-105 ℃; 90-100 ℃; 90-95 ℃; 95-200 ℃; 95-190 ℃; 95-180 ℃; 95-170 ℃; 95-160 ℃; 95-155 ℃; 95-150 ℃; 95-145 ℃; 95-140 ℃; 95-138 ℃; 95-135 ℃; 95-130 ℃; 95-125 ℃; 95-120 ℃; 95-115 ℃; 95-110 ℃; 95-105 ℃; 95-is less than 105 ℃; 95-100 ℃; 100-200 ℃; 100-190 ℃; 100-180 ℃; 100-170 ℃; 100-160 ℃; 100-155 ℃; 100-150 ℃; 100-145 ℃; 100-140 ℃; 100-138 ℃; 100-135 ℃; 100-130 ℃; 100-125 ℃; 100-120 ℃; 100-115 ℃; 100-110 ℃; 105-200 ℃; 105-190 ℃; 105-180 ℃; 105-170 ℃; 105-160 ℃; 105-155 ℃; 105-150 ℃; 105-145 ℃; 105-140 ℃; 105-138 ℃; 105-135 ℃; 105-130 ℃; 105-125 ℃; 105-120 ℃; 105-115 ℃; 105-110 ℃; Greater than 105-125 ℃; Greater than 105-120 ℃; Greater than 105-115 ℃; Greater than 105-110 ℃; 110-200 ℃; 110-195 ℃; 110-190 ℃; 110-185 ℃; 110-180 ℃; 110-175 ℃; 110-170 ℃; 110-165 ℃; 110-160 ℃; 110-155 ℃; 110-150 ℃; 110-145 ℃; 110-138 ℃; 110-140 ℃; 110-135 ℃; 110-130 ℃; 110-125 ℃; 110-120 ℃; 110-115 ℃; 115-200 ℃; 115-195 ℃; 115-190 ℃; 115-185 ℃; 115-180 ℃; 115-175 ℃; 115-170 ℃; 115-165 ℃ 115-160 ℃; 115-155 ℃; 115-150 ℃; 115-145 ℃; 115-140 ℃; 115-138 ℃; 115-135 ℃; 115-125 ℃; 115-120 ℃; 120-200 ℃; 120-195 ℃; 120-190 ℃; 120-185 ℃ 120-180 ℃; 120-175 ℃ 120-170 ℃; 120-165 ℃; 120-160 ℃; 120-155 ℃; 120-150 ℃; 120-145 ℃; 120-140 ℃; 120-138 ℃; 120-135 ℃; 125-180 ℃; 125-170 ℃; 125-160 ℃; 125-155 ℃; 125-150 ℃; 125-145 ℃; 125-140 ℃; 125-138 ℃; 125-135 ℃; 135-180 ℃; 127-180 ℃; 127-170 ℃; 127-160 ℃; 127-150 ℃; 127-145 ℃; 127-140 ℃; 127-138 ℃; 127-135 ℃; 130-200 ℃; 130-195 ℃; 130-190 ℃; 130-185 ℃; 130-180 ℃; 130-175 ℃; 130-170 ℃; 130-165 ℃ 130-160 ℃; 130-155 ℃; 130-150 ℃; 130-145 ℃; 130-140 ℃; 130-138 ℃; 130-135 ℃; 135-170 ℃; 135-160 ℃; 135-155 ℃; 135-150 ℃; 135-145 ℃; 135-140 ℃; 135-135 ℃; 140-200 ℃; 140-195 ℃; 140-190 ℃; 140-185 ℃; 140-180 ℃; 140-170 ℃; 140-165 ℃; 140-160 ℃; 140-155 ℃; 140-150 ℃; 140-145 ℃; 148-200 ℃; 148-190 ℃; 148-180 ℃; 148-170 ℃; 148-160 ℃; 148-155 ℃; 148-150 ℃; 150-200 ℃; 150-195 ℃; 150-190 ℃; 150-185 ℃; 150-180 ℃; 150-175 ℃; 150-170 ℃; 150-165 ℃; 150-160 ℃; 150-155 ℃; 155-200 ℃; 150-190 ℃; 150-180 ℃; 150-170 ℃; 150-160; 155-190 ℃; 155-180 ℃; 155-170 ℃; 155-165 ℃; Greater than 124 ℃ until 200 ℃; Greater than 125 ℃ until 200 ℃; Greater than 126 ℃ until 200 ℃; Greater than 148 ℃ until 200 ℃.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 1-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-99 mole %1,4-cyclohexanedimethanol; 1-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-99 mole %1,4-cyclohexanedimethanol; 1-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-99 mole %1,4-cyclohexanedimethanol; 1-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-99 mole %1,4-cyclohexanedimethanol; 1-80 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-99 mole %1,4-cyclohexanedimethanol, 1-75 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-99 mole %1,4-cyclohexanedimethanol; 1-70 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-99 mole %1,4-cyclohexanedimethanol; 1-65 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-99 mole %1,4-cyclohexanedimethanol; 1-60 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-99 mole %1,4-cyclohexanedimethanol; 1-55 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-99 mole %1,4-cyclohexanedimethanol; 1-50 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-99 mole %1,4-cyclohexanedimethanol; 1-45 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 55-99 mole %1,4-cyclohexanedimethanol; 1-40 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 60-99 mole %1,4-cyclohexanedimethanol; 1-35 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 65-99 mole %1,4-cyclohexanedimethanol; 1-30 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 70-99 mole %1,4-cyclohexanedimethanol; 1-25 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 75-99 mole %1,4-cyclohexanedimethanol; 1-20 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 80-99 mole %1,4-cyclohexanedimethanol; 1-15 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 85-99 mole %1,4-cyclohexanedimethanol; 1-10 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 90-99 mole %1,4-cyclohexanedimethanol; 1-5 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 95-99 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 5-less than 50 moles of %2,2,4, and 4-tetramethyl--1,3-cyclobutanediol and greater than 50-95 mole %1,4-cyclohexanedimethanol; 5-45 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 55-95 mole %1,4-cyclohexanedimethanol; 5-40 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 60-95 mole %1,4-cyclohexanedimethanol; 5-35 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 65-95 mole %1,4-cyclohexanedimethanol; 5 to less than 35 moles of %2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and greater than 65-95 mole %1,4-cyclohexanedimethanol; 5-30 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 70-95 mole %1,4-cyclohexanedimethanol; 5-25 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 75-95 mole %1,4-cyclohexanedimethanol; 5-20 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 80-95 mole %1,4-cyclohexanedimethanol; 5-15 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 85-95 mole %1,4-cyclohexanedimethanol; 5-10 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 90-95 mole %1,4-cyclohexanedimethanol; Greater than 5 to less than 10 moles of %2,2,4,4-tetramethyl--1, the 3-cyclobutanediol and less than 90 to greater than 95 moles of %1,4-cyclohexanedimethanol; 5.5-9.5 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 94.5-90.5 mole %1,4-cyclohexanedimethanol; 6-9 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 94-91 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 10-100 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 0-90 mole %1,4-cyclohexanedimethanol; 10-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-90 mole %1,4-cyclohexanedimethanol; 10-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-90 mole %1,4-cyclohexanedimethanol; 10-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-90 mole %1,4-cyclohexanedimethanol; 10-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-90 mole %1,4-cyclohexanedimethanol; 10-80 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-90 mole %1,4-cyclohexanedimethanol, 10-75 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-90 mole %1,4-cyclohexanedimethanol; 10-70 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-90 mole %1,4-cyclohexanedimethanol; 10-65 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-90 mole %1,4-cyclohexanedimethanol; 10-60 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-90 mole %1,4-cyclohexanedimethanol; 10-55 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-90 mole %1,4-cyclohexanedimethanol; 10-50 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-90 mole %1,4-cyclohexanedimethanol; 10 to less than 50 moles of %2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and greater than 50-90 mole %1,4-cyclohexanedimethanol; 10-45 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 55-90 mole %1,4-cyclohexanedimethanol; 10-40 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 60-90 mole %1,4-cyclohexanedimethanol; 10-35 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 65-90 mole %1,4-cyclohexanedimethanol; 10-is less than 35 moles of %2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and, 4-cyclohexanedimethanol greater than 65-90%1; 10-30 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 70-90 mole %1,4-cyclohexanedimethanol; 10-25 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 75-90 mole %1,4-cyclohexanedimethanol; 10-20 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 80-90 mole %1,4-cyclohexanedimethanol; 10-15 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 85-90 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 14-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-86 mole %1,4-cyclohexanedimethanol; 14-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-86 mole %1,4-cyclohexanedimethanol; 14-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-86 mole %1,4-cyclohexanedimethanol; 14-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-86 mole %1,4-cyclohexanedimethanol; 14-86 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 14-86 mole %1,4-cyclohexanedimethanol, 14-75 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-86 mole %1,4-cyclohexanedimethanol; 14-70 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-86 mole %1,4-cyclohexanedimethanol; 14-65 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-86 mole %1,4-cyclohexanedimethanol; 14-60 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-86 mole %1,4-cyclohexanedimethanol; 14-55 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-86 mole %1,4-cyclohexanedimethanol; 14-50 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-86 mole %1,4-cyclohexanedimethanol; 14 to less than 50 moles of %2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and greater than 50 to 86 moles of %1,4-cyclohexanedimethanol; 14-45 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 55-86 mole %1,4-cyclohexanedimethanol; 14-40 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 60-86 mole %1,4-cyclohexanedimethanol; 14-35 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 65-86 mole %1,4-cyclohexanedimethanol; 14-30 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 70-86 mole %1,4-cyclohexanedimethanol; 14-24 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 76-86 mole %1,4-cyclohexanedimethanol; 14-25 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 75-86 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 15-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-85 mole %1,4-cyclohexanedimethanol; 15-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-85 mole %1,4-cyclohexanedimethanol; 15-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-85 mole %1,4-cyclohexanedimethanol; 15-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-85 mole %1,4-cyclohexanedimethanol; 15-86 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-86 mole %1,4-cyclohexanedimethanol, 15-75 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-85 mole %1,4-cyclohexanedimethanol; 15-70 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-85 mole %1,4-cyclohexanedimethanol; 15-65 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-85 mole %1,4-cyclohexanedimethanol; 15-60 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-85 mole %1,4-cyclohexanedimethanol; 15-55 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-85 mole %1,4-cyclohexanedimethanol; 15-50 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-85 mole %1,4-cyclohexanedimethanol; 15 to less than 50 moles of %2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and greater than 50 to 85 moles of %1,4-cyclohexanedimethanol; 15-45 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 55-85 mole %1,4-cyclohexanedimethanol; 15-40 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 60-85 mole %1,4-cyclohexanedimethanol; 15-35 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 65-85 mole %1,4-cyclohexanedimethanol; 15-30 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 70-85 mole %1,4-cyclohexanedimethanol; 15-25 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 75-85 mole %1,4-cyclohexanedimethanol; 15-24 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 76-85 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 20-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-80 mole %1,4-cyclohexanedimethanol; 20-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-80 mole %1,4-cyclohexanedimethanol; 20-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-80 mole %1,4-cyclohexanedimethanol; 20-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-80 mole %1,4-cyclohexanedimethanol; 20-80 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-80 mole %1,4-cyclohexanedimethanol, 20-75 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-80 mole %1,4-cyclohexanedimethanol; 20-70 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-80 mole %1,4-cyclohexanedimethanol; 20-65 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-80 mole %1,4-cyclohexanedimethanol; 20-60 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-80 mole %1,4-cyclohexanedimethanol; 20-55 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-80 mole %1,4-cyclohexanedimethanol; 20-50 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-80 mole %1,4-cyclohexanedimethanol; 20 to less than 50 moles of %2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and greater than 50-80 mole %1,4-cyclohexanedimethanol; 20-45 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 55-80 mole %1,4-cyclohexanedimethanol; 20-40 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 60-80 mole %1,4-cyclohexanedimethanol; 20-35 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 65-80 mole %1,4-cyclohexanedimethanol; 20-30 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 70-80 mole %1,4-cyclohexanedimethanol; 20-25 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 75-80 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 25-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-75 mole %1,4-cyclohexanedimethanol; 25-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-75 mole %1,4-cyclohexanedimethanol; 25-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-75 mole %1,4-cyclohexanedimethanol; 25-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-75 mole %1,4-cyclohexanedimethanol; 25-80 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-75 mole %1,4-cyclohexanedimethanol, 25-75 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-75 mole %1,4-cyclohexanedimethanol; 25-70 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-75 mole %1,4-cyclohexanedimethanol; 25-65 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-75 mole %1,4-cyclohexanedimethanol; 25-60 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-75 mole %1,4-cyclohexanedimethanol; 25-55 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-75 mole %1,4-cyclohexanedimethanol; 25-50 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-75 mole %1,4-cyclohexanedimethanol; 25 to less than 50 moles of %2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and greater than 50-75 mole %1,4-cyclohexanedimethanol; 25-45 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 55-75 mole %1,4-cyclohexanedimethanol; 25-40 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 60-75 mole %1,4-cyclohexanedimethanol; 25-35 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 65-75 mole %1,4-cyclohexanedimethanol; 25-30 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 70-75 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 30-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-70 mole %1,4-cyclohexanedimethanol; 30-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-70 mole %1,4-cyclohexanedimethanol; 30-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-70 mole %1,4-cyclohexanedimethanol; 30-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-70 mole %1,4-cyclohexanedimethanol; 30-80 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-70 mole %1,4-cyclohexanedimethanol; 30-75 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-70 mole %1,4-cyclohexanedimethanol; 30-70 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-70 mole %1,4-cyclohexanedimethanol; 30-65 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-70 mole %1,4-cyclohexanedimethanol; 30-60 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-70 mole %1,4-cyclohexanedimethanol; 30-55 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-70 mole %1,4-cyclohexanedimethanol; 30-50 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-70 mole %1,4-cyclohexanedimethanol; 30 to less than 50 moles of %2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and greater than 50 to 70 moles of %1,4-cyclohexanedimethanol; 30-45 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 55-70 mole %1,4-cyclohexanedimethanol; 30-40 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 60-70 mole %1,4-cyclohexanedimethanol; 30-35 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 65-70 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 35-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-65 mole %1,4-cyclohexanedimethanol; 35-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-65 mole %1,4-cyclohexanedimethanol; 35-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-65 mole %1,4-cyclohexanedimethanol; 35-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-65 mole %1,4-cyclohexanedimethanol; 35-80 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-65 mole %1,4-cyclohexanedimethanol, 35-75 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-65 mole %1,4-cyclohexanedimethanol; 35-70 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-65 mole %1,4-cyclohexanedimethanol; 35-65 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-65 mole %1,4-cyclohexanedimethanol; 35-60 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-65 mole %1,4-cyclohexanedimethanol; 35-55 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-65 mole %1,4-cyclohexanedimethanol; 35-50 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-65 mole %1,4-cyclohexanedimethanol; 35 to less than 50 moles of %2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and greater than 50 to 65 moles of %1,4-cyclohexanedimethanol; 35-45 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 55-65 mole %1,4-cyclohexanedimethanol; 35-40 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 60-65 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 40-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-60 mole %1,4-cyclohexanedimethanol; 40-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-60 mole %1,4-cyclohexanedimethanol; 40-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-60 mole %1,4-cyclohexanedimethanol; 40-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-60 mole %1,4-cyclohexanedimethanol; 40-80 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-60 mole %1,4-cyclohexanedimethanol; 40 to less than 80 moles of %2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and greater than 20 to 60 moles of %1,4-cyclohexanedimethanol; 40-75 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-60 mole %1,4-cyclohexanedimethanol; 40-70 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-60 mole %1,4-cyclohexanedimethanol; 40-65 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-60 mole %1,4-cyclohexanedimethanol; 40-60 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-60 mole %1,4-cyclohexanedimethanol; 40-55 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-60 mole %1,4-cyclohexanedimethanol; 40 to less than 50 moles of %2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and greater than 50 to 60 moles of %1,4-cyclohexanedimethanol; 40-50 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-60 mole %1,4-cyclohexanedimethanol; 40-45 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 55-60 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 45-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-55 mole %1,4-cyclohexanedimethanol; 45-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-55 mole %1,4-cyclohexanedimethanol; 45-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-55 mole %1,4-cyclohexanedimethanol; 45-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-55 mole %1,4-cyclohexanedimethanol; 45-80 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-55 mole %1,4-cyclohexanedimethanol, 45-75 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-55 mole %1,4-cyclohexanedimethanol; 45-70 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-55 mole %1,4-cyclohexanedimethanol; 45-65 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-55 mole %1,4-cyclohexanedimethanol; 45-60 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-55 mole %1,4-cyclohexanedimethanol; Greater than 45 to 55 moles of %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45 is to less than 55 moles of %1,4-cyclohexanedimethanol; 45-55 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-55 mole %1,4-cyclohexanedimethanol; 45-50 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-55 mole %1,4-cyclohexanedimethanol; Greater than 45 to 52 moles of %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 48-55 mole %1,4-cyclohexanedimethanol; 46-55 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-54 mole %1,4-cyclohexanedimethanol; 48-52 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 48-52 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: greater than 50 to 99 moles of %2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and 1 is to less than 50 moles of %1,4-cyclohexanedimethanol; Greater than 50 to 90 moles of %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10 is to less than 50 moles of %1,4-cyclohexanedimethanol; Greater than 50 to 85 moles of %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15 is to less than 50 moles of %1,4-cyclohexanedimethanol; Greater than 50 to 80 moles of %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20 be to less than 50 moles of %1, the 4-cyclohexanedimethanol, greater than 50 to 75 moles of %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25 is to less than 50 moles of %1,4-cyclohexanedimethanol; Greater than 50 to 70 moles of %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30 is to less than 50 moles of %1,4-cyclohexanedimethanol; Greater than 50 to 65 moles of %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35 is to less than 50 moles of %1,4-cyclohexanedimethanol; Greater than 50 to 60 moles of %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40 is to less than 50 moles of %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 55-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-45 mole %1,4-cyclohexanedimethanol; 55-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-45 mole %1,4-cyclohexanedimethanol; 55-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-45 mole %1,4-cyclohexanedimethanol; 55-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-45 mole %1,4-cyclohexanedimethanol; 55-80 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-45 mole %1,4-cyclohexanedimethanol, 55-75 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-45 mole %1,4-cyclohexanedimethanol; 55-70 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-45 mole %1,4-cyclohexanedimethanol; 55-65 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-45 mole %1,4-cyclohexanedimethanol; 55-60 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-45 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 60-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-40 mole %1,4-cyclohexanedimethanol; 60-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-40 mole %1,4-cyclohexanedimethanol; 60-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-40 mole %1,4-cyclohexanedimethanol; 60-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-40 mole %1,4-cyclohexanedimethanol; 60-80 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-40 mole %1,4-cyclohexanedimethanol, 60-75 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-40 mole %1,4-cyclohexanedimethanol; 60-70 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-40 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 65-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-35 mole %1,4-cyclohexanedimethanol; 65-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-35 mole %1,4-cyclohexanedimethanol; 65-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-35 mole %1,4-cyclohexanedimethanol; 65-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-35 mole %1,4-cyclohexanedimethanol; 65-80 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-35 mole %1,4-cyclohexanedimethanol, 65-75 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-35 mole %1,4-cyclohexanedimethanol; 65-70 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-35 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 70-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-30 mole %1,4-cyclohexanedimethanol; 70-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-30 mole %1,4-cyclohexanedimethanol; 70-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-30 mole %1,4-cyclohexanedimethanol; 70-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-30 mole %1,4-cyclohexanedimethanol; 70-80 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-30 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 75-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-25 mole %1,4-cyclohexanedimethanol; 75-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-25 mole %1,4-cyclohexanedimethanol; 75-90 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-25 mole %1,4-cyclohexanedimethanol; 75-85 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-25 mole %1,4-cyclohexanedimethanol.

In others of the present invention, the diol component that is used for polyester of the present invention includes but not limited at least one following scope combination: 80-99 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-20 mole %1,4-cyclohexanedimethanol; 80-95 mole %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-20 mole %1,4-cyclohexanedimethanol; 80-90 mole %2,2,4,2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-20 mole %1,4-cyclohexanedimethanol; Greater than 80 to 90 moles of %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10 is to less than 20 moles of %1,4-cyclohexanedimethanol; Greater than 81 to 90 moles of %2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10 is to less than 19 moles of %1,4-cyclohexanedimethanol.

Except above-mentioned glycol, the polyester that is used for polymer blend of the present invention also can be by 1, ammediol, 1,4-butyleneglycol or the preparation of its mixture.Think by 1; Ammediol, 1, the present composition of 4-butyleneglycol or the preparation of its mixture can have at least one Tg scope described here, the logarithmic viscosity number scope that at least one is described here and/or glycol or two acid ranges that at least one is described here.Select in addition or as another kind of, by 1, ammediol, 1, the polyester of 4-butyleneglycol or the preparation of its mixture also can be prepared by the 1,4 cyclohexane dimethanol of at least one following consumption: 0.1-99 mole %; 0.1-95 mole %; 0.1-90 mole %; 0.1-85 mole %; 0.1-80 mole %; 0.1-75 mole %; 0.1-70 mole %; 0.1-60 mole %; 0.1-50 mole %; 0.1-40 mole %; 0.1-35 mole %; 0.1-30 mole %; 0.1-25 mole %; 0.1-20 mole %; 0.1-15 mole %; 0.1-10 mole %; 0.1-5 mole %; 1-99 mole %; 1-95 mole %; 1-90 mole %; 1-85 mole %; 1-80 mole %; 1-70 mole %; 1-60 mole %; 1-50 mole %; 1-40 mole %; 1-35 mole %; 1-30 mole %; 1-25 mole %; 1-20 mole %; 1-15 mole %; 1-10 mole %; 1-5 mole %; 5-99 mole %; 5-95 mole %; 5-90 mole %; 5-85 mole %; 5-80 mole %; 5-75 mole %; 5-70 mole %; 5-60 mole %; 5-50 mole %; 5-40 mole %; 5-35 mole %; 5-30 mole %; 5-25 mole %; 5-20 mole %; 5-15 mole %; 5-10 mole %; 10-99 mole %; 10-95 mole %; 10-90 mole %; 10-85 mole %; 10-80 mole %; 10-75 mole %; 10-70 mole %; 10-60 mole %; 10-50 mole %; 10-40 mole %; 10-35 mole %; 10-30 mole %; 10-25 mole %; 10-20 mole %; 10-15 mole %; 20-99 mole %; 20-95 mole %; 20-90 mole %; 20-85 mole %; 20-80 mole %; 20-75 mole %; 20-70 mole %; 20-60 mole %; 20-50 mole %; 20-40 mole %; 20-35 mole %; 20-30 mole %; 20-25 mole %.

For specific embodiments of the present invention, polyester may be displayed in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in any following logarithmic viscosity number of 25 ℃ of mensuration: 0.35-is less than 0.70dL/g; 0.35-0.68dL/g; 0.35-less than 0.68dL/g; 0.35-0.65dL/g.; 0.40-0.70dL/g; 0.40 extremely less than 0.70dL/g; 0.40-0.68dL/g; 0.40 extremely less than 0.68dL/g; 0.40-0.65dL/g; 0.45 extremely less than 0.70dL/g; 0.45-0.68dL/g; 0.45 extremely less than 0.68dL/g; 0.45-0.65dL/g; 0.50 extremely less than 0.70dL/g; 0.50-0.68dL/g; 0.50 extremely less than 0.68dL/g; 0.50-0.67dL/g; 0.50-0.66dL/g; 0.50-0.65dL/g; 0.55-less than 0.70dL/g; 0.55-0.68dL/g; 0.55 extremely less than 0.68dL/g; 0.55-0.65dL/g; 0.58 extremely less than 0.70dL/g; 0.58-0.68dL/g; 0.58 extremely less than 0.68dL/g; Or 0.58-0.65dL/g.

For the logarithmic viscosity number of polyester of the present invention wherein is 0.35-0.75dL/g or bigger embodiment, and these polyester also may be displayed in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in any following logarithmic viscosity number of 25 ℃ of mensuration: 0.35-is less than 0.75dL/g; 0.35-0.72dL/g; Or 0.35-0.70dl/g.

For specific embodiments of the present invention, polyester may be displayed in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in any following logarithmic viscosity number of 25 ℃ of mensuration: 0.10-1.2dL/g; 0.10-1.1dL/g; 0.10-1dL/g; 0.10 extremely less than 1dL/g; 0.10-0.98dL/g; 0.10-0.95dL/g; 0.10-0.90dL/g; 0.10-0.85dL/g; 0.10-0.80dL/g; 0.10-0.75dL/g; 0.10-less than 0.75dL/g; 0.10-0.72dL/g; 0.10-0.70dL/g; 0.10 extremely less than 0.70dL/g; 0.10-0.68dL/g; 0.10-less than 0.68dL/g; 0.10-0.65dL/g; 0.10-0.6dL/g; 0.10-0.55dL/g; 0.10-0.5dL/g; 0.10-0.4dL/g; 0.10-0.35dL/g; 0.20-1.2dL/g; 0.20-1.1dL/g; 0.20-1dL/g; 0.20 extremely less than 1dL/g; 0.20-0.98dL/g; 0.20-0.95dL/g; 0.20-0.90dL/g; 0.20-0.85dL/g; 0.20-0.80dL/g; 0.20-0.75dL/g; 0.20 extremely less than 0.75dL/g; 0.20-0.72dL/g; 0.20-0.70dL/g; 0.20 extremely less than 0.70dL/g; 0.20-0.68dL/g; 0.20 extremely less than 0.68dL/g; 0.20-0.65dL/g; 0.20-0.6dL/g; 0.20-0.55dL/g; 0.20-0.5dL/g; 0.20-0.4dL/g; And 0.20-0.35dL/g.

For the logarithmic viscosity number of polyester of the present invention wherein is the embodiment of 0.35-1.2dL/g, and these polyester also may be displayed in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in any following logarithmic viscosity number of 25 ℃ of mensuration: 0.35-1.2dL/g; 0.35-1.1dL/g; 0.35-1dL/g; 0.35 extremely less than 1dL/g; 0.35-0.98dL/g; 0.35-0.95dL/g; 0.35-0.9dL/g; 0.35-0.85dL/g; 0.35-0.8dL/g; 0.35-0.75dL/g; 0.35-less than 0.75dL/g; 0.35-0.72dL/g; 0.40-1.2dL/g; 0.40-1.1dL/g; 0.40-1dL/g; 0.40-less than 1dL/g; 0.40-0.98dL/g; 0.40-0.95dL/g; 0.40-0.9dL/g; 0.40-0.85dL/g; 0.40-0.8dL/g; 0.40-0.75dL/g; 0.40 extremely less than 0.75dL/g; 0.40-0.72dL/g; Greater than 0.42 to 1.2dL/g; Greater than 0.42 to 1.1dL/g; Greater than 0.42 to 1dL/g; Greater than 0.42 to less than 1dL/g; Greater than 0.42-0.98dL/g; Greater than 0.42-0.95dL/g; Greater than 0.42 to 0.9dL/g; Greater than 0.42 to 0.85dL/g; Greater than 0.42 to 0.80dL/g; Greater than 0.42 to 0.75dL/g; Greater than 0.42 to less than 0.75dL/g; 0.42-0.70dL/g; 0.42 extremely less than 0.70dL/g; Greater than 0.42 to 0.72dL/g; Greater than 0.42 to 0.70dL/g; Greater than 0.42 to 0.68dL/g; Greater than 0.42 to less than 0.68dL/g; 0.42-0.68dL/g; Greater than 0.42 to 0.65dL/g; 0.45-1.2dL/g; 0.45-1.1dL/g; 0.45-1dL/g; 0.45-0.98dL/g; 0.45-0.95dL/g; 0.45-0.9dL/g; 0.45-0.85dL/g; 0.45-0.80dL/g; 0.45-0.75dL/g; 0.45 extremely less than 0.75dL/g; 0.45-0.72dL/g; 0.45-0.70dL/g; 0.50-1.2dL/g; 0.50-1.1dL/g; 0.50-1dL/g; 0.50 extremely less than 1dL/g; 0.50-0.98dL/g; 0.50-0.95dL/g; 0.50-0.9dL/g; 0.50-0.85dL/g; 0.50-0.80dL/g.; 0.50-0.75dL/g; 0.50 extremely less than 0.75dL/g; 0.50-0.72dL/g; 0.50-0.70dL/g; 0.55-1.2dL/g; 0.55-1.1dL/g; 0.55-1dL/g; 0.55 extremely less than 1dL/g; 0.55-0.98dL/g; 0.55-0.95dL/g; 0.55-0.9dL/g; 0.55-0.85dL/g; 0.55-0.80dL/g; 0.55-0.75dL/g; 0.55-less than 0.75dL/g; 0.55-0.72dL/g; 0.55-0.70dL/g; 0.58-1.2dL/g; 0.58-1.1dL/g; 0.58-1dL/g; 0.58 extremely less than 1dL/g; 0.58-0.98dL/g; 0.58-0.95dL/g; 0.58-0.9dL/g; 0.58-0.85dL/g; 0.58-0.80dL/g; 0.58-0.75dL/g; 0.58 extremely less than 0.75dL/g; 0.58-0.72dL/g; 0.58-0.70dL/g; 0.60-1.2dL/g; 0.60-1.1dL/g; 0.60-1dL/g; 0.60 extremely less than 1dL/g; 0.60-0.98dL/g; 0.60-0.95dL/g; 0.60-0.90dL/g; 0.60-0.85dL/g; 0.60-0.80dL/g; 0.60-0.75dL/g; 0.60 extremely less than 0.75dL/g; 0.60-0.72dL/g; 0.60-0.70dL/g; 0.60 extremely less than 0.70dL/g; 0.60-0.68dL/g; 0.60 extremely less than 0.68dL/g; 0.60-0.65dL/g; 0.65-1.2dL/g; 0.65-1.1dL/g; 0.65-1dL/g; 0.65 extremely less than 1dL/g; 0.65-0.98dL/g; 0.65-0.95dL/g; 0.65-0.90dL/g; 0.65-0.85dL/g; 0.65-0.80dL/g; 0.65-0.75dL/g; 0.65-less than 0.75dL/g; 0.65-0.72dL/g; 0.65-0.70dL/g; 0.65 extremely less than 0.70dL/g; 0.68-1.2dL/g; 0.68-1.1dL/g; 0.68-1dL/g; 0.68-less than 1dL/g; 0.68-0.98dL/g; 0.68-0.95dL/g; 0.68-0.90dL/g; 0.68-0.85dL/g; 0.68-0.80dL/g; 0.68-0.75dL/g; 0.68 extremely less than 0.75dL/g; 0.68-0.72dL/g; Greater than 0.70dL/g to 1.2dL/g; Greater than 0.76dL/g to 1.2dL/g; Greater than 0.76dL/g to 1.1dL/g; Greater than 0.76dL/g to 1dL/g; Greater than 0.76dL/g to less than 1dL/g; Greater than 0.76dL/g to 0.98dL/g; Greater than 0.76dL/g to 0.95dL/g; Greater than 0.76dL/g to 0.90dL/g; Greater than 0.80dL/g to 1.2dL/g; Greater than 0.80dL/g to 1.1dL/g; Greater than 0.80dL/g to 1dL/g; Greater than 0.80dL/g to less than 1dL/g; Greater than 0.80dL/g to 1.2dL/g; Greater than 0.80dL/g to 0.98dL/g; Greater than 0.80dL/g to 0.95dL/g; Greater than 0.80dL/g to 0.90dL/g.

Think compsn of the present invention can have at least one the disclosed logarithmic viscosity number scope of this paper with at least one in the disclosed compositing monomer scope of this paper, except as otherwise noted.Also think compsn of the present invention can have at least one the disclosed Tg scope of this paper with at least one in the disclosed compositing monomer scope of this paper, except as otherwise noted.Also think compsn of the present invention can have at least one in the disclosed Tg scope of this paper, at least one is in the disclosed logarithmic viscosity number scope of this paper and at least one is in the disclosed compositing monomer scope of this paper, except as otherwise noted.

For required polyester, suitable/anti-2,2,4,4-tetramethyl--1, the mol ratio of 3-cyclobutanediol can change from pure form or its mixture separately.In certain embodiments, cis and/or trans 2,2,4,4-tetramethyl--1, the molar percentage of 3-cyclobutanediol are greater than 50 moles of % cis and trans less than 50 moles of %; Or greater than 55 moles of % cis and trans less than 45 moles of %; Or 30-70 mole % cis and 70-30% are trans; Or 40-60 mole % cis and 60-40 mole % are trans; Or 50-70 mole % is trans and the 50-30% cis; Or 50-70 mole % cis and 50-30% are trans; Or 60-70 mole % cis and 30-40 mole % are trans; Or greater than 70 moles of % cis and trans less than 30 moles of %; Cis-wherein with trans-2,2,4,4-tetramethyl--1, total molar percentage of 3-cyclobutanediol equals 100 moles of %.The mol ratio of cis/trans 1,4 cyclohexane dimethanol can change in the scope of 50/50-0/100, for example 40/60-20/80.

In certain embodiments, the mixture of terephthalic acid, its ester (for example DMT. Dimethyl p-benzenedicarboxylate) or terephthalic acid and its ester occupies the most of of the dicarboxylic acid component that forms polyester of the present invention or all.In certain embodiments, the terephthalic acid residue can with at least 70 moles of %, for example at least 80 moles of %, at least 90 moles of %, at least 95 moles of %, at least 99 moles of % or even the concentration of 100 moles of % occupy the dicarboxylic acid component's who forms a polyester of the present invention part or all.In certain embodiments, can use the terephthalic acid of higher amount to have polyester than high impact with preparation.For disclosed purpose, term " terephthalic acid " and " DMT. Dimethyl p-benzenedicarboxylate " can exchange use here.In one embodiment, DMT. Dimethyl p-benzenedicarboxylate be used to prepare polyester of the present invention the dicarboxylic acid component partly or entirely.In all embodiments, can use 70-100 mole % or 80-100 mole % or 90-100 mole % or 99-100 mole % or even terephthalic acid and/or DMT. Dimethyl p-benzenedicarboxylate and/or its mixture of 100 moles of %.

Except the terephthalic acid residue, the dicarboxylic acid component who is used for polyester of the present invention can be contained at the most 30 moles of %, 20 moles of %, 10 moles of %, 5 moles of % or one or more modified aromatic dicarboxylicacid of 1 mole of % at the most at the most at the most at the most.Another embodiment contains the modified aromatic dicarboxylicacid of 0 mole of %.Therefore; If exist; Think that the amount of one or more modified aromatic dicarboxylicacid can be the scope between any above-mentioned endpoint value, comprise for example 0.01-30 mole %, 0.01-20 mole %, 0.01-10 mole %, 0.01-5 mole % and 0.01-1 mole %.In one embodiment, can be used for modified aromatic dicarboxylicacid of the present invention and include but not limited to have those of 20 carbon atoms at the most, it can be linear, right-orientation or symmetric.The example that can be used for modified aromatic dicarboxylicacid of the present invention includes but not limited to m-phthalic acid, 4,4'-diphenyldicarboxylic acids, 1, and 4-, 1,5-, 2,6-, 2,7-naphthalic acid be with anti--4,4 '-Stilbene dioctyl phthalate, and their ester.In one embodiment, the modified aromatic dicarboxylicacid is a m-phthalic acid.

Be used for the carboxyl acid component of polyester of the present invention can be further with 10 moles of % at the most, as 5 moles of % at the most or at the most one or more of 1 mole of % contain the aliphatic dicarboxylic acid modification of 2-16 carbon atom, for example propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid and dodecyl dioctyl phthalate.Some embodiment also can contain 0.01 mole of % or more, like 0.1 mole of % or more, 1 mole of % or more, 5 moles of % or more or 10 moles of % or more one or more modification aliphatic dicarboxylic acids.Another embodiment contains the modification aliphatic dicarboxylic acid of 0 mole of %.Therefore,, think that the amount of one or more modification aliphatic dicarboxylic acids can be the scope between any above-mentioned endpoint value, comprise for example 0.01-15 mole % and 0.1-10 mole % if exist.Dicarboxylic acid component's total mole of % is 100 moles of %.

Can use the ester and other modification dicarboxylicacid or its corresponding esters and/or salt replacement dicarboxylicacid of terephthalic acid.The suitable example of dicarboxylic ester includes but not limited to dimethyl esters, diethyl ester, dipropyl, diisopropyl ester, dibutyl ester and diphenyl.In one embodiment, these esters are selected from following at least a: methyl ester, ethyl ester, propyl diester, isopropyl esters and phenylester.

1,4 cyclohexane dimethanol can be cis, trans or its mixture, and for example suitable/reverse proportionality is 60: 40 to 40: 60.In another embodiment, anti--1,4 cyclohexane dimethanol can exist with the amount of 60-80 mole %.

Be used for polymer blend of the present invention, the diol component of polyester portion can contain 25 moles of % or still less one or more and 2,2,4,4-tetramethyl--1, the modification glycol that 3-cyclobutanediol or 1,4 cyclohexane dimethanol are different; In one embodiment, be used for polyester of the present invention and can contain one or more modification glycol less than 15 moles of %.In another embodiment, be used for polyester of the present invention and can contain 10 moles of % or one or more modification glycol still less.In another embodiment, be used for polyester of the present invention and can contain 5 moles of % or one or more modification glycol still less.In another embodiment, be used for polyester of the present invention and can contain 3 moles of % or one or more modification glycol still less.In another embodiment, be used for the modification glycol that polyester of the present invention can contain 0 mole of %.Some embodiment also can contain 0.01 mole of % or more, like 0.1 mole of % or more, 1 mole of % or more, 5 moles of % or more or 10 moles of % or more one or more modification glycol.Therefore,, think that the amount of one or more modification glycol can be the scope between any above-mentioned endpoint value, comprise for example 0.01-15 mole % and 0.01-10 mole % if exist.

The modification glycol that is used for polyester of the present invention refers to and 2,2,4,4-tetramethyl--1, and 3-cyclobutanediol or 1,4 cyclohexane dimethanol are different and contain the glycol of 2-16 carbon atom.The example of suitable modification glycol includes but not limited to terepthaloyl moietie, glycol ether, 1,2-Ucar 35,1, ammediol, NSC 6366,1,4-butyleneglycol, 1,5-pentanediol, 1,6-pinakon, p-Xylol glycol or their mixture.In one embodiment, the modification glycol is a terepthaloyl moietie.In another embodiment, the modification glycol includes but not limited to 1, ammediol and/or 1,4-butyleneglycol.In another embodiment, the modification glycol does not comprise terepthaloyl moietie.In another embodiment, the modification glycol does not comprise 1, ammediol and 1,4-butyleneglycol.In another embodiment, the modification glycol does not comprise 2.

Polyester and/or the polycarbonate that is used for polymer blend of the present invention can contain respectively residue (being also referred to as branching agent here) or its combination that has the branched monomer of 3 or more carboxyl substituents, hydroxyl substituent or its combination based on one or more of 0-10 mole %, for example 0.01-5 mole %, 0.01-1 mole %, 0.05-5 mole %, 0.05-1 mole % or the 0.1-0.7 mole % of glycol or the total molar percentage meter of diacid residues or 0.1-0.5 mole %.In certain embodiments, branched monomer or branching agent can be before the polymerization of polyester and/or during and/or add afterwards.Being used for polyester of the present invention therefore can be linearity or branching.Polycarbonate also can be linearity or branching.In certain embodiments, branched monomer or branching agent can be before the polymerization of polycarbonate and/or during and/or add afterwards.

The example of branched monomer includes but not limited to polyfunctional acid or polyfunctional alcohol, for example trimellitic acid, trimellitic acid 1,2-anhydride, pyromellitic dianhydride, TriMethylolPropane(TMP), glycerine, tetramethylolmethane, Hydrocerol A, tartrate, 3-hydroxyl pentanedioic acid etc.In one embodiment; The branched monomer residue can contain 0.1-0.7 mole % one or more be selected from the residue below at least a: trimellitic acid 1,2-anhydride, pyromellitic dianhydride, glycerine, sorbyl alcohol, 1; 2; 6-hexanetriol, tetramethylolmethane, trimethylolethane and/or 1,3, the 5-benzenetricarboxylic acid.Can with branched monomer add in the pet reaction mixture or with the polyester blend of enriched material form, for example be described in USP 5,654, in 347 and 5,696,176, for reference with wherein introducing this paper about the disclosure of branched monomer.

Second-order transition temperature (Tg) is to use from the TA DSC 2920 of Thermal Analyst Instrument with 20 ℃/minute determination of scan rate.

Because some used polyester of the present invention has long half-time of crystallization (for example greater than 5 minutes) at 170 ℃; So can article of manufacture, include but not limited to articles injection-moulded, injection blow molding goods, injection drawing blow goods, extruded film, extrusion sheet, extrusion-blow molding product and fiber.Polyester of the present invention can be amorphous or hemicrystalline.In one aspect, some used polyester of the present invention can have lower percent crystallinity.Therefore, some used polyester of the present invention can have essentially amorphous rheology, and the expression polyester contains unordered basically polymer areas.

In one embodiment, the half-time of crystallization of " amorphous " polymkeric substance can 170 ℃ greater than 5 minutes or 170 ℃ greater than 10 minutes 170 ℃ greater than 50 minutes or at 170 ℃ greater than 100 minutes.In one embodiment of the invention, half-time of crystallization is greater than 1000 minutes at 170 ℃.In another embodiment, the half-time of crystallization that is used for polyester of the present invention is greater than 10000 minutes at 170 ℃.Can use the method that well known to a person skilled in the art to detect in the half-time of crystallization that this paper uses.For example, the half-time of crystallization t of polyester _1/2Can be through changing and measure along with the time on the temperature control warm table via the transmittance of laser and photo-detector test sample.This detection can be through making polymkeric substance be exposed to temperature T max, being cooled to required temperature then and carrying out.Then sample is remained on required temperature through warm table, detect transsmissivity simultaneously over time.During beginning, the sample range estimation is transparent, has high transmission rate, and becomes muddy along with the sample crystallization.Half-time of crystallization is the time that transmittance is in the half between initial transmittance and the final transmittance.Tmax is defined as the needed temperature in crystallization phases farmland (if the crystallization phases farmland exists) of fusing sample.Can sample be heated to Tmax before detecting half-time of crystallization, to regulate sample.Absolute Tmax is different for each compsn.For example, can PCT be heated to than 290 ℃ of high temperature with fusion-crystallization phase farmland.

Like the table 1 of embodiment with shown in Figure 1,2,2,4,4-tetramethyl--1, for example terepthaloyl moietie and m-phthalic acid are more effective aspect the increase half-time of crystallization than other comonomer for the 3-cyclobutanediol, promptly polymkeric substance reaches the half the required time of its maximum percent crystallinity.Through reducing the crystallization rate of PCT, promptly increase half-time of crystallization, can produce by means commonly known in the art based on the amorphous goods of the PCT of modification, for example extrude, injection moulding etc.As shown in table 1, these materials show than higher second-order transition temperature of the PCT copolyesters of other modification and lower density.

For some embodiment of the present invention, polyester shows the improvement of toughness and processibility combination.For example, the logarithmic viscosity number that reduces polyester of the present invention can obtain the better melt viscosity of processibility, and the good physical behavior that keeps polyester simultaneously is toughness and thermotolerance for example.

Improve 1; The 4-cyclohexanedimethanol is based on terephthalic acid, terepthaloyl moietie and 1; Content in the copolyesters of 4-cyclohexanedimethanol can improve toughness, and this can be through detecting the brittle-ductile transition temperature measuring according to ASTM D256 in the notched izod strength trial.Think that this improvement through the toughness that is realized with 1,4 cyclohexane dimethanol reduction brittle-ductile transition temperature is because the flexibility of the 1,4 cyclohexane dimethanol in copolyesters and conformation behavior cause.Think and in PCT, introduce 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol can improve toughness through reducing the brittle-ductile transition temperature, like the table 2 of embodiment with shown in Figure 2.

In one embodiment, in the rotation melt rheometer, be less than 30000 pools under 1 radian per second 290 ℃ of melt viscosities that record polyester of the present invention.In another embodiment, in the rotation melt rheometer, be less than 20000 pools under 1 radian per second 290 ℃ of melt viscosities that record polyester of the present invention.

In one embodiment, in the rotation melt rheometer, be less than 15000 pools under 1 radian per second 290 ℃ of melt viscosities that record polyester of the present invention.

In one embodiment, in the rotation melt rheometer, be less than 10000 pools under 1 radian per second 290 ℃ of melt viscosities that record polyester of the present invention.In another embodiment, in the rotation melt rheometer, be less than 6000 pools under 1 radian per second 290 ℃ of melt viscosities that record polyester of the present invention.Viscosity under radian per second is relevant with processibility.Viscosity when typical polymkeric substance detects under its processing temperature under 1 radian per second is less than 10000 pools.Polyester is not usually in the temperature processing that is higher than 290 ℃.Polycarbonate is processed 290 ℃ temperature usually.Polycarbonate viscosity under typical case's 12 melt flow of 1 radian per second is 7000 pools at 290 ℃.

Polyester of the present invention can have one or more following performances.Of ASTM D256, notched izod intensity is the toughness detection method of using always.In one embodiment, in the thick rod of 3.2mm (1/8 inch), are 150J/m (3ft-lb/in) at least 23 ℃ of notched izod intensity that record polyester of the present invention according to ASTM D256 with the breach of 10 mils; In one embodiment, in the thick rod of 3.2mm (1/8 inch), are 400J/m (7.5ft-lb/in) at least 23 ℃ of notched izod intensity that record polyester of the present invention according to ASTM D256 with the breach of 10 mils; In one embodiment, in the thick rod of 3.2mm (1/8 inch), are 1000J/m (18ft-lb/in) at least 23 ℃ of notched izod intensity that record polyester of the present invention according to ASTM D256 with the breach of 10 mils.In one embodiment, in the thick rod of 6.4mm (1/4 inch), are 150J/m (3ft-lb/in) at least 23 ℃ of notched izod intensity that record polyester of the present invention according to ASTM D256 with the breach of 10 mils; In one embodiment, in the thick rod of 6.4mm (1/4 inch), are 400J/m (7.5ft-lb/in) at least 23 ℃ of notched izod intensity that record polyester of the present invention according to ASTM D256 with the breach of 10 mils; In one embodiment, in the thick rod of 6.4mm (1/4 inch), are 1000J/m (18ft-lb/in) at least 23 ℃ of notched izod intensity that record polyester of the present invention according to ASTM D256 with the breach of 10 mils.

In another embodiment, being used for some polyester of the present invention demonstrates according to ASTM D256 at 1/8 inch thick rod with the breach of 10 mils 0 ℃ of notched izod strength ratio that records-5 ℃ of notched izod intensity increases by 3% or 5% or 10% or 15% that record at least at least at least at least.In addition, some other polyester also can demonstrate according to ASTM D256 and in 1/8 inch thick rod, when detecting for 0-30 ℃, remain ± 5% notched izod intensity with the breach of 10 mils.

In another embodiment; With compare in the notched izod intensity of 23 ℃ of detections according to ASTM D256 breach with 10 mils in 1/8 inch thick rod, be used for some polyester of the present invention and demonstrate according to ASTM D256 and be no more than 70% notched izod intensity with breach loss when detecting for 23 ℃ of 10 mils at 1/4 inch thick rod.

In one embodiment, based on breach, be used for polyester of the present invention and show ductile-brittle transition temperature less than 0 ℃ according to ASTM D256 10 mils in 1/8 inch thick rod.

In one embodiment, use the gradient column density, be used for polyester of the present invention and show at least one following density 23 ℃ of detections: 23 ℃ density less than 1.2g/ml; 23 ℃ density less than 1.18g/ml; 23 ℃ density is 0.8-1.3g/ml; 23 ℃ density is 0.80-1.2g/ml; 23 ℃ density is 0.8 to less than 1.2g/ml; 23 ℃ density is 1.0-1.3g/ml; 23 ℃ density is 1.0-1.2g/ml; 23 ℃ density is 1.0-1.1g/ml; 23 ℃ density is 1.13-1.3g/ml; 23 ℃ density is 1.13-1.2g/ml.

In one embodiment, being used for polyester of the present invention can generally be that range estimation is transparent.Term " estimates transparent " here to be defined as when visual observations, do not have appreciable muddiness, mist degree and/or dirt.In another embodiment, when polyester and polycarbonate (including but not limited to bisphenol-a polycarbonate) blend, blend can be that range estimation is transparent.

In another embodiment of the invention, the xanthochromia index (ASTM D-1925) that is used for polyester of the present invention can be less than 50 or less than 20.

In one embodiment, be used for polyester of the present invention and/or polymer blend of the present invention (containing or do not contain toning agent) and can have colour L ^*, a ^*And b ^*, using Hunter LabInc.Reston, the Hunter Lab Ultrascan Spectra Colorimeter that Va. produces measures.The color detection value is the MV of the value that detects to the pellet of polyester or by its injection moulding or the sheet material of extruding or other goods.They are through the L of CIE ^*a ^*b ^*Colour system is measured (Intemational Commission on Illumination) (translating), wherein L ^*The expression lightness dimension, a ^*Represent red/green coordinate, b ^*Expression Huang/blue coordinate.In certain embodiments, the b of polyester of the present invention ^*Value can be-10 to less than 10, L ^*Value can be 50-90.In other embodiments, the b of polyester of the present invention ^*Value can be in one of following scope :-10 to 9;-10 to 8;-10 to 7;-10 to 6;-10 to 5;-10 to 4;-10 to 3;-10 to 2;-5 to 9;-5 to 8;-5 to 7;-5 to 6;-5 to 5;-5 to 4;-5 to 3;-5 to 2; 0 to 9; 0 to 8; 0 to 7; 0 to 6; 0 to 5; 0 to 4; 0 to 3; 0 to 2; 1 to 10; 1 to 9; 1 to 8; 1 to 7; 1 to 6; 1 to 5; 1 to 4; 1 to 3; With 1 to 2.In other embodiments, the L of polyester of the present invention ^*Value can be in one of following scope: 50-60; 50-70; 50-80; 50-90; 60-70; 60-80; 60-90; 70-80; 79-90.

In some embodiments, use polymer blend of the present invention that drying step before melt and/or thermoforming is minimized and/or do not need drying step.

Polyester portion in polymer blend of the present invention can be through the known method preparation of document, for example through the method in homogeneous solution, through the ester exchange method in melt with through the two-phase interface method.Suitable method includes but not limited to make the reaction under the pressure of 100-315 ℃ temperature and 0.1-760mmHg of one or more dicarboxylicacid and one or more glycol to be enough to form the time of polyester.Method about producing polyester can be referring to USP 3,772,405, and it is for reference to introduce this paper about the disclosure of these methods.

On the other hand, the present invention relates to a kind of method of producing polyester.This method comprises:

(I) will contain the monomeric mixture that in any polyester of the present invention, uses in the presence of catalyzer in time that 150-240 ℃ of heating is enough to prepare initial polyester;

(II) will be from the initial polyester of step (I) 240-320 ℃ temperature heating 1-4 hour; With

(III) remove any unreacted glycol.

The catalyzer that is applicable to this method comprises but is not limited to organic zinc compound or organo-tin compound.The use of this catalyzer is well known in the art.Be used for catalyzer of the present invention and for example include but not limited to zinc acetate, three-2 ethyl hexanoic acid butyl tin, oxalic acid two fourth tin and/or dibutyl tin oxides.Other catalyzer can include but not limited to based on those of titanium, zinc, manganese, lithium, germanium and cobalt.The amount of catalyzer can be 10-20000ppm or 10-10000ppm, or 10-5000ppm or 10-1000ppm or 10-500ppm, or 10-300ppm or 10-250ppm, based on catalyst metal with based on the weight meter of final polymkeric substance.This method can be carried out according to intermittence or continuous processing.

Generally, step (I) can be carried out up to 50 weight % or more 2,2,4,4-tetramethyl--1, and the 3-cyclobutanediol reacts.Step (I) can be carried out under normal atmosphere to the pressure of 100psig.Here with the present invention in term " reaction product " expression of the relevant use of catalyst system therefor any with catalyzer and in the preparation polyester product of used monomeric polycondensation or esterification, and the polycondensation between catalyzer and any other additive types or the product of esterification.

Generally, step (II) and step (III) can be carried out simultaneously.These steps can be carried out by means commonly known in the art, for example through reaction mixture being placed 0.002psig to the pressure that is lower than barometric pressure range, or through hot nitrogen being blown over this mixture.

The invention further relates to a kind of polyester product of producing through aforesaid method.

The invention further relates to a kind of blend polymer.This blend comprises:

(a) at least a above-mentioned polyester of 5-95 weight %; With

(b) at least a polymeric constituent of 5-95 weight %.

The suitable example of polymeric constituent include but not limited to nylon, with above-mentioned different polyester, polymeric amide (for example from DuPont ); PS; Polystyrene copolymer; Styrene/acrylonitrile copolymer; The acrylonitrile/butadiene/styrene multipolymer; Polymethylmethacrylate, acrylic copolymer; Polyetherimide, for example

(a kind of polyetherimide) from General Electric; Ppe; For example gather 2; 6-dimethylphenylene ether or polyphenyl ether/styrene blend; NORYL

(a kind of from GeneralElectric gather 2, the blend of 6-dimethylphenylene ether and polystyrene resin) for example; Polyphenylene sulfide; Polyphenylene sulfide/sulfone; Polyester/carbonic ether; Polycarbonate, for example

(a kind of polycarbonate) from General Electric; Polysulfones; Polysulfones ether; The polyetherketone of aromatic dihydroxy compound; Or any above-mentioned mixture of polymers.Said blend can be through conventional processing technology preparation well known in the art, for example melt blending or solution blending.In one embodiment, in polymer blend, there is not polycarbonate.If in polymer blend of the present invention, in blend, use polycarbonate, then this blend can be that range estimation is transparent.But, be used for polymer blend of the present invention and also can get rid of polycarbonate or comprise polycarbonate.

Being used for polycarbonate of the present invention can be according to known program preparation, for example through making dihydroxy aromatic compounds and carbonate precursor (for example phosgene, haloformate or carbonic ether), molecular weight regulator, acid acceptor and catalyst reaction.The method for preparing polycarbonate is well known in the art, for example is described in USP 4,452, and is in 933, for reference with wherein introducing this paper about the content of polycarbonate.

The example of suitable carbonate precursor includes but not limited to carbonyl bromine, carbonyl chlorine or its mixture; Dipheryl carbonate base ester; Carbonic acid two (halogenophenyl) ester, for example carbonic acid two (trichlorophenyl) ester, carbonic acid two (tribromo phenyl) ester etc.; Carbonic acid two (alkyl phenyl) ester, for example carboxylol base ester; Carbonic acid two (naphthyl) ester; Carbonic acid two (chloronaphthyl, methylnaphthyl) ester, or its mixture; Haloformate with dihydric phenol.

The example of suitable molecular weight regulator includes but not limited to phenol, hexalin, methyl alcohol, alkylated phenol, for example octyl phenol, p-tert-butylphenol etc.In one embodiment, molecular weight regulator is phenol or alkylated phenol.

Acid acceptor can be organic acid or examples of inorganic acceptors.The appropriate organic acceptor can be a tertiary amine, includes but not limited to pyridine, triethylamine, xylidine, Tributylamine etc.Examples of inorganic acceptors can be oxyhydroxide, carbonate, supercarbonate or the phosphoric acid salt of basic metal or earth alkali metal.

Operable catalyzer comprises but is not limited to assist usually those of polyreaction of monomer and phosgene.Appropriate catalyst includes but not limited to tertiary amine, for example triethylamine, tripropyl amine, N, accelerine; Quaternary ammonium compound, for example tetraethylammonium bromide, cetyltriethylammonium bromide, four n-heptyl ammonium iodides, four n-propyl bromination ammoniums, tetramethyl ammonium chloride, TMAH, tetrabutylammonium iodide, benzyl trimethyl ammonium chloride; And quaternary phosphonium compound, for example normal-butyl tri-phenyl-phosphorus bromide

and methyltriphenylphospbromide bromide phosphorus

The polycarbonate that is used for polymer blend of the present invention also can be a copolyestercarbonates, for example is disclosed in USP 3,169,121,3,207; 814,4,194,038,4,156; 069,4,430,484,4,465; In 820 and 4,981,898 those, for reference with introducing this paper about the content of copolyestercarbonates in these USPs.

Being used for copolyestercarbonates of the present invention can and/or can prepare from the commerce acquisition by means commonly known in the art.For example, they can be usually mixture reaction acquisition through at least a dihydroxy aromatic compounds and phosgene and at least a diacid chloride (particularly m-phthaloyl chloride, p-phthaloyl chloride or the two).

In addition; The polymer blend and the polymer blend composition that contain polyester of the present invention also can contain based on the 0.01-25 weight % of polymer blend gross weight meter or the conventional additives of 0.01-20 weight % or 0.01-15 weight % or 0.01-10 weight % or 0.01-5 weight %, for example tinting material, dyestuff, releasing agent, fire retardant, softening agent, nucleator, stablizer (including but not limited to UV stablizer, thermo-stabilizer and/or its mixture), filler and impact modifying agent.Be used for the present invention and the commercially available impact modifying agent of typical case well known in the art for example includes but not limited to the ethylene/propene ter-polymers; Functionalised polyolefin for example contains those of methyl acrylate and/or SY-Monomer G; The segmented copolymer impact modifying agent of styrene-based; With various acrylic acid or the like core/shell type impact modifying agents.For example, can be through adding in the body, the UV additive being introduced in the goods of the present invention's production through the coating hard coat or through the coextrusion overcoat.The residue of these additives also is the part of polymer blend of the present invention.

Polyester of the present invention can contain at least a chainextender.Suitable chainextender includes but not limited to multifunctional (including but not limited to difunctionality) isocyanic ester, multi-functional epoxyization thing, comprises for example epoxy group(ing) lacquer resins, and phenoxy resin.In certain embodiments, chainextender can add when polymerization technique finishes or after polymerization technique.If after polymerization technique, add, then chainextender can conversion process for example injection moulding or extrude during through mixing or introducing through adding.The consumption of chainextender can change according to used concrete monomer composition and required physicals, but the about 10 weight % of normally about 0.1-, and the about 5 weight % of preferably about 0.1-are based on the gross weight meter of polyester.

Thermo-stabilizer is to include but not limited to P contained compound at the compound of stabilized polyester during the production of polyester and/or during the post polymerization, includes but not limited to phosphoric acid, phosphorous acid, phosphonic acids, phospho acid, phosphonous acid and their various esters and salt.They may reside in the polymer blend of the present invention.These esters can be alkyl ester, branched alkyl ester, substituted alkyl ester, difunctionality alkyl ester, alkyl oxide, aryl ester and substituted aryl ester.In one embodiment, the ester group number that in concrete P contained compound, exists can be from the 0 admissible maximum number of hydroxy number meter that until being based on used stablizer, exists.Term " thermo-stabilizer " expression comprises its reaction product.The term that here uses " reaction product " with thermo-stabilizer of the present invention be illustrated in thermo-stabilizer and any in producing polyester the polycondensation between the used monomer or the spawn of esterification, and the polycondensation between catalyzer and any other additive types or the spawn of esterification.

Strongthener can be used for compsn of the present invention.Strongthener can include but not limited to carbon monofilament, silicate, mica, clay, talcum, titanium oxide, wollastonite, sheet glass, granulated glass sphere and fiber, polymer fiber and their mixture.In one embodiment, strongthener is a glass, for example fibrous glass yarn, glass and steatitic mixture, glass and micaceous mixture, and the mixture of glass and polymer fiber.

In another embodiment, the invention further relates to the article of manufacture that contains any above-mentioned polyester and blend.

In another embodiment, the invention further relates to the article of manufacture that contains any above-mentioned polyester and blend.Extrude, the goods of calendering and/or moulding, include but not limited to injection-molded item, extruded product, casting extruded product, thermoformed articles, section bar extruded product, melt spinning goods, thermoformed articles, extrusion molding goods, injection blow molding goods, injection drawing blow goods, extrusion-blow molding product and extrude the stretch-blow goods.These goods can include but not limited to film, bottle (including but not limited to infant bottle), container, sheet material and/or fiber.

Polyester of the present invention and/or polyester blend compositions can be used to form fiber, film, moulded parts, container and sheet material.The method that polyester is formed fiber, film, moulded parts, container and sheet material is well known in the art.The example of potential moulded parts includes but not limited to: medical facilities, for example dialysis equipment, medical treatment bag, health material; Commercial food product tableware articles for use, for example food tray, steam plate, glass cylinder and bin, infant bottle, food processor, mixing machine and mixing bowl, apparatus, water bottle, Freshness keeping disc, washing machine front end and vacuum cleaner parts.Other potential moulded parts includes but not limited to ophthalmic lens and mirror holder.For example, this material can be used for producing bottle, includes but not limited to infant bottle, because this material is transparent, toughness, stable on heating, and shows good stability to hydrolysis.

In another embodiment, the invention further relates to the article of manufacture that contains film and/or sheet material, said film and/or sheet material contain above-mentioned polymer blend.

Be used for film of the present invention and/or sheet material and can have any thickness, thickness is obvious to those skilled in the art.In one embodiment, the thickness of film of the present invention is no more than 40 mils.In one embodiment, the thickness of film of the present invention is no more than 35 mils.In one embodiment, the thickness of film of the present invention is no more than 30 mils.In one embodiment, the thickness of film of the present invention is no more than 25 mils.In one embodiment, the thickness of film of the present invention is no more than 20 mils.

In one embodiment, the thickness of sheet material of the present invention is not less than 20 mils.In another embodiment, the thickness of sheet material of the present invention is not less than 25 mils.In another embodiment, the thickness of sheet material of the present invention is not less than 30 mils.In another embodiment, the thickness of sheet material of the present invention is not less than 35 mils.In another embodiment, the thickness of sheet material of the present invention is not less than 40 mils.

The invention further relates to the film and/or the sheet material that contain polymer blend of the present invention.The method that makes polyester form film and/or sheet material is well known in the art.Film of the present invention and/or sheet material include but not limited to film and/or the sheet material extruded, the film of calendering and/or sheet material, the film of compression moulding and/or sheet material, the film of solution casting and/or sheet material.The method of producing film and/or sheet material includes but not limited to extrude, calendering, compression moulding and solution casting.

Example by the potential goods of said film and/or sheet production includes but not limited to the film of uniaxial extension, biaxial stretch-formed film, shrink film (no matter whether being single shaft or biaxial stretch-formed), the goods of liquid crystal display film (including but not limited to diffusion sheet, compensate film and protective membrane), thermoforming sheet, direction board film, outdoor mark, skylight, coating, coating, goods, laminating material, laminated product and/or the many walls film or the sheet material of japanning.

The example of direction board film includes but not limited to business card, film conversion lamination; The attractable point indicating meter; Plane on washing machine or in-mold decoration plate; Plane contact panel on the refrigerator; Flat board on baking oven; The interior trim that is used for automobile; The panel board of automobile; Phone cover; Heating and Ventilation Control indicating meter; The automobile shock dish; Doughnut displacement dish; The control indicating meter or the warning mark that are used for automobile instrument panel; Panel on the household articles, button or image display; Panel on the washing machine, button or image display; Panel on the dishwasher, button or image display; The keyboard of electronics; The keyboard of mobile telephone, PDA (hand-held computer) or telepilot; The image display of electronics; Palmtronic is the indicating meter of phone and PDA for example; The panel and the shell that are used for automobile or standard telephone; Sign on the electronics; With the sign that is used for Cell phone.

Many walls film or sheet material are represented the sheet material extruded as section bar, and it is made up of the multilayer that connects via vertical bar each other.The example of many walls film or sheet material includes but not limited to greenhouse and commercial shelter.

The example of extruded product includes but not limited to be used for the film in direction board, coating, outdoor sign, skylight, is used for the film of resin glass laminating material, and liquid-crystal display (LCD) film, includes but not limited to scatterer sheet material, compensate film and protective membrane.

Abbreviation used herein " wt " expression " weight ".

Following examples further specify and how to prepare and estimate polymer blend of the present invention, only are used to explain the present invention, do not limit the scope of the invention.Except as otherwise noted, umber is a weight part, and temperature is ℃ or room temperature, and pressure is normal atmosphere or near normal atmosphere.

Embodiment

Detection method

The logarithmic viscosity number of polyester be in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration.

Except as otherwise noted, second-order transition temperature (Tg) is to use from the TA DSC 2920 of Thermal Analyst Instrument with 20 ℃/minute determination of scan rate according to ASTM D3418.

The glycol content of compsn and cis/trans ratio are measured through proton NMR spectrum (NMR).All NMR data are recorded on the JEOL Eclipse Plus 600MHz nuclear magnetic resonance spectrometer; Use chloroform-trifluoroacetic acid (70/30 volume) for polymkeric substance; Or, use 60/40 (wt/wt) phenol/tetrachloroethane for oligomeric sample, wherein add the deuterate chloroform with locking.For 2,2,4,4-tetramethyl--1, the ownership of 3-cyclobutanediol resonance peak be through with as 2,2,4 of model (model), 4-tetramethyl--1, the list of 3-cyclobutanediol-relatively carry out with two-benzoic ether.These model compounds are very near the resonant position in polymkeric substance and oligopolymer.

Half-time of crystallization t1/2 is through changing and measure along with the time on the temperature control warm table via the transmittance of laser and photo-detector test sample.This detection can be through making polymkeric substance be exposed to temperature T max, being cooled to required temperature then and carrying out.Then sample is remained on required temperature through warm table, detect transsmissivity simultaneously over time.During beginning, the sample range estimation is transparent, has high transmission rate, and becomes muddy along with the sample crystallization.Half-time of crystallization is the time that transmittance is in the half between initial transmittance and the final transmittance.Tmax is defined as the needed temperature in crystallization phases farmland (if the crystallization phases farmland exists) of fusing sample.Tmax in following examples representes sample heating with in the temperature that detects when regulating sample before half-time of crystallization.Tmax depends on composition, and normally different for various polyester.For example, can PCT be heated to than 290 ℃ of high temperature with fusion-crystallization phase farmland.

Density is to use gradient density tower 23 ℃ of detections.

Here the melt viscosity of report is to use Rheometrics Dynamic Analyzer (RDA II) to detect.Melt viscosity detects under the temperature of being reported under the frequency of 1-400 radian per second as the function of shearing rate.Zero-shear viscosity (η ₀) be the melt viscosity under zero shearing rate, through estimating according to model extrapolation data known in the art.This step is carried out through Rheometrics Dynamic Analyzer (RDA II) software automatically.

With polymkeric substance under 80-100 ℃ temperature in vacuum drying oven dry 24 hours, and injection moulding on Boy 22S mould machine, obtain the flexural bars of 1/8 * 1/2 * 5 inches and 1/4 * 1/2 * 5 inches.These rods are cut into 2.5 inches length, and fall 1/2 inch width with 10 mil notch shocks according to ASTM D256.At 23 ℃ average cantilever-type impact strengths is to confirm from the detected value of 5 samples.

In addition, under all temps, detect 5 samples, thereby measure the brittle-ductile transition temperature with 5 ℃ increments.The brittle-ductile transition temperature is defined as 50% the sample fragility mode destructive temperature with ASTM D 256 explanations.

Here the colour of report is to use Hunter Associatess Lab Inc.Reston, and the Hunter Lab Ultrascan Spectra Colorimeter that Va. produces measures.The MV of the value that the confirming of colour detects to the pellet of polyester or by its injection moulding or the sheet material of extruding or other goods.They are through the L of CIE ^*a ^*b ^*Colour system is measured (International Commission on illumination), wherein L ^*The expression lightness dimension, a ^*Represent red/green coordinate, b ^*Expression Huang/blue coordinate.

In addition, the film of 10 mils uses the Carver press to carry out compression moulding at 240 ℃.

Except as otherwise noted, the suitable/inverse proportion of the 1,4 cyclohexane dimethanol that in following examples, uses is about 30/70, can be in 35/65 to 25/75 scope.Except as otherwise noted, in following examples, use 2,2,4,4-tetramethyl--1, the suitable/inverse proportion of 3-cyclobutanediol is about 50/50.

Abbreviation below in work embodiment and accompanying drawing, using:

Embodiment 1

Present embodiment explanation 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is more effective than terepthaloyl moietie or m-phthalic acid aspect the crystallization rate that reduces PCT.In addition, present embodiment explanation 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is to the benefit of second-order transition temperature and density.

The various copolyesters of preparation are described below.These copolyesters all use the 200ppm dibutyltin oxide as catalyzer, thereby the influence of the concentration during Study on Crystallization during with catalyst type and nucleation minimizes.Suitable/the inverse proportion of 1,4 cyclohexane dimethanol is 31/69, and 2,2,4,4-tetramethyl--1, the suitable/inverse proportion of 3-cyclobutanediol is listed in the table 1.

For the purpose of present embodiment, sample has enough similar logarithmic viscosity number, thereby in crystallization rate detects, can not become variable effectively.

It is in 140-200 ℃ the temperature incremental detection with 10 ℃ that the half-time of crystallization of melt detects, and is listed in the table 1.With the fastest half-time of crystallization of each sample as temperature variant minimum value of half-time of crystallization, usually in about 170-180 ℃ appearance.The fastest half-time of crystallization of sample, be plotted in Fig. 1 as the function of mole % of the comonomer that is used for modification PCT.

Data presentation 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is more effective than terepthaloyl moietie and m-phthalic acid at reduction crystallization rate (that is, increasing half-time of crystallization) aspect.In addition, 2,2,4,4-tetramethyl--1,3-cyclobutanediol can improve Tg and reduce density.

Table 1

Half-time of crystallization (minute)

The surplus of the diol component of polyester is a 1,4 cyclohexane dimethanol in 1 table 1; The dicarboxylic acid component's of polyester surplus is a DMT. Dimethyl p-benzenedicarboxylate in the table 1; If do not describe dicarboxylicacid, then be the DMT. Dimethyl p-benzenedicarboxylate of 100 moles of %.

The 1,4 cyclohexane dimethanol of 2 100 moles of %.

3 from the grinding polyester of embodiment 1G at 240 ℃ of compacting films.The film of gained has the logarithmic viscosity number of 0.575dL/g.

4 from the grinding polyester of embodiment 1H at 240 ℃ of compacting films.The film of gained has the logarithmic viscosity number of 0.652dL/g.

Wherein: A is a m-phthalic acid

B is a terepthaloyl moietie

C is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (suitable/anti-=about 50/50)

D is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (suitable/anti-=about 98/2)

E is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (suitable/anti-=about 5/95)

Like table 1 with shown in Figure 1,2,2,4, for example terepthaloyl moietie and m-phthalic acid are more effective than other comonomer increasing aspect half-time of crystallization (being the half the required time that polymkeric substance reaches its maximum percent crystallinity) for 4-tetramethyl--1,3-cyclobutanediol.Through reducing the crystallization rate (increase half-time of crystallization) of PCT, described here based on 2,2,4,4-tetramethyl--1, the amorphous goods of 3-cyclobutanediol modification PCT can prepare by means commonly known in the art.As shown in table 1, these materials demonstrate than higher second-order transition temperature of other modification PCT copolyesters and lower density.

The preparation of the polyester shown in the table 1 is described below.

Embodiment 1A

Present embodiment has been described target group becomes the preparation of the copolyesters of the 1,4 cyclohexane dimethanol residue of 80 moles of % DMT. Dimethyl p-benzenedicarboxylate residues, 20 moles of % dimethyl isophthalate residues and 100 moles of % (suitable/anti-=28/72).

The mixture of 56.63g DMT. Dimethyl p-benzenedicarboxylate, 55.2g 1,4 cyclohexane dimethanol, 14.16g dimethyl isophthalate and 0.0419g dibutyl tin oxide is put into the 500ml flask that is equipped with nitrogen inlet, metal agitator and short still column.Flask is put into the Wood metal bath that is heated to 210 ℃.In experimentation, stirring velocity is set at 200RPM.210 ℃ of heating 5 minutes, in 30 minutes, make temperature be elevated to 290 ℃ gradually then flask contents.Reaction mixture kept 60 minutes at 290 ℃, in subsequently 5 minutes, applied the pressure of vacuum in flask then gradually and reached 100mmHg.In subsequently 5 minutes, further the pressure in the flask is reduced to 0.3mmHg.0.3mmHg pressure keep 90 minutes altogether to remove excessive unreacted glycol.The polymkeric substance of obtained to have high melt viscosity, range estimation is transparent and colourless, its second-order transition temperature is 87.5 ℃, logarithmic viscosity number is 0.63dL/g.This polymkeric substance of NMR analysis revealed comprises 1,4 cyclohexane dimethanol residue and 20.2 moles of % dimethyl isophthalate residues of 100 moles of %.

Embodiment 1B

Present embodiment has been described target group becomes the preparation of the copolyesters of the 1,4 cyclohexane dimethanol residue of 100 moles of % DMT. Dimethyl p-benzenedicarboxylate residues, 20 moles of % glycol residues and 80 moles of % (suitable/anti-=32/68).

The mixture of 77.68g DMT. Dimethyl p-benzenedicarboxylate, 50.77g 1,4 cyclohexane dimethanol, 27.81g terepthaloyl moietie and 0.0433g dibutyl tin oxide is put into the 500ml flask that is equipped with nitrogen inlet, metal agitator and short still column.Flask is put into the Wood metal bath that is heated to 200 ℃.In experimentation, stirring velocity is set at 200RPM.200 ℃ of heating 60 minutes, in 5 minutes, make temperature be elevated to 210 ℃ gradually then flask contents.Reaction mixture kept 120 minutes at 210 ℃, arrived until 280 ℃ at 30 minutes internal heating then.In case reach 280 ℃, in subsequently 5 minutes, apply the pressure of vacuum in flask gradually and reach 100mmHg.In subsequently 10 minutes, further the pressure in the flask is reduced to 0.3mmHg.0.3mmHg pressure keep 90 minutes altogether to remove excessive unreacted glycol.The polymkeric substance of obtained to have high melt viscosity, range estimation is transparent and colourless, its second-order transition temperature is 87.7 ℃, logarithmic viscosity number is 0.71dL/g.This polymkeric substance of NMR analysis revealed comprises 19.8 moles of % glycol residues.

Embodiment 1C

Present embodiment has been described target group becomes 100 moles of % DMT. Dimethyl p-benzenedicarboxylate residues, 20 moles of %2, and 2,4,4-tetramethyl--1, the preparation of the copolyesters of the 1,4 cyclohexane dimethanol residue of 3-cyclobutanediol residue and 80 moles of % (suitable/anti-=31/69).

With 77.68g DMT. Dimethyl p-benzenedicarboxylate, 48.46g 1; 4-cyclohexanedimethanol, 17.86g 2,2,4; 4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyl tin oxide are put into the 500ml flask that is equipped with nitrogen inlet, metal agitator and short still column.Mode according to similar with embodiment 1A prepares polyester.The polymkeric substance of obtained to have high melt viscosity, range estimation is transparent and colourless, its second-order transition temperature is 100.5 ℃, logarithmic viscosity number is 0.73dL/g.This polymkeric substance of NMR analysis revealed comprise 80.5 moles of % 1,4 cyclohexane dimethanol residue and 19.5 moles of % 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 1D

Present embodiment has been described target group becomes the preparation of the copolyesters of the 1,4 cyclohexane dimethanol residue of 80 moles of % DMT. Dimethyl p-benzenedicarboxylate residues, 40 moles of % dimethyl isophthalate residues and 100 moles of % (suitable/anti-=28/72).

The mixture of 42.83g DMT. Dimethyl p-benzenedicarboxylate, 55.26g 1,4 cyclohexane dimethanol, 28.45g dimethyl isophthalate and 0.0419g dibutyl tin oxide is put into the 500ml flask that is equipped with nitrogen inlet, metal agitator and short still column.Flask is put into the Wood metal bath that is heated to 210 ℃.In experimentation, stirring velocity is set at 200RPM.210 ℃ of heating 5 minutes, in 30 minutes, make temperature be elevated to 290 ℃ gradually then flask contents.Reaction mixture kept 60 minutes at 290 ℃, in subsequently 5 minutes, applied the pressure of vacuum in flask then gradually and reached 100mmHg.In subsequently 5 minutes, further the pressure in the flask is reduced to 0.3mmHg.0.3mmHg pressure keep 90 minutes altogether to remove excessive unreacted glycol.The polymkeric substance of obtained to have high melt viscosity, range estimation is transparent and colourless, its second-order transition temperature is 81.2 ℃, logarithmic viscosity number is 0.67dL/g.This polymkeric substance of NMR analysis revealed comprises 1,4 cyclohexane dimethanol residue and 40.2 moles of % dimethyl isophthalate residues of 100 moles of %.

Embodiment 1E

Present embodiment has been described target group becomes the preparation of the copolyesters of the 1,4 cyclohexane dimethanol residue of 100 moles of % DMT. Dimethyl p-benzenedicarboxylate residues, 40 moles of % glycol residues and 60 moles of % (suitable/anti-=31/69).

The mixture of 81.3g DMT. Dimethyl p-benzenedicarboxylate, 42.85g 1,4 cyclohexane dimethanol, 34.44g terepthaloyl moietie and 0.0419g dibutyl tin oxide is put into the 500ml flask that is equipped with nitrogen inlet, metal agitator and short still column.Flask is put into the Wood metal bath that is heated to 200 ℃.In experimentation, stirring velocity is set at 200RPM.200 ℃ of heating 60 minutes, in 5 minutes, make temperature be elevated to 210 ℃ gradually then flask contents.Reaction mixture kept 120 minutes at 210 ℃, arrived until 280 ℃ at 30 minutes internal heating then.In case reach 280 ℃, in subsequently 5 minutes, apply the pressure of vacuum in flask gradually and reach 100mmHg.In subsequently 10 minutes, further the pressure in the flask is reduced to 0.3mmHg.0.3mmHg pressure keep 90 minutes altogether to remove excessive unreacted glycol.The polymkeric substance of obtained to have high melt viscosity, range estimation is transparent and colourless, its second-order transition temperature is 82.1 ℃, logarithmic viscosity number is 0.64dL/g.This polymkeric substance of NMR analysis revealed comprises 34.5 moles of % glycol residues.

Embodiment 1F

Present embodiment has been described target group becomes 100 moles of % DMT. Dimethyl p-benzenedicarboxylate residues, 40 moles of %2, and 2,4,4-tetramethyl--1, the preparation of the copolyesters of the 1,4 cyclohexane dimethanol residue of 3-cyclobutanediol residue and 60 moles of % (suitable/anti-=31/69).

With 77.4g DMT. Dimethyl p-benzenedicarboxylate, 36.9g 1; 4-cyclohexanedimethanol, 32.5g2,2,4; 4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyl tin oxide are put into the 500ml flask that is equipped with nitrogen inlet, metal agitator and short still column.Flask is put into the Wood metal bath that is heated to 210 ℃.In experimentation, stirring velocity is set at 200RPM.210 ℃ of heating 3 minutes, in 30 minutes, make temperature be elevated to 260 ℃ gradually then flask contents.Reaction mixture kept 120 minutes at 260 ℃, arrived until 290 ℃ at 30 minutes internal heating then.In case reach 290 ℃, in subsequently 5 minutes, apply the pressure of vacuum in flask gradually and reach 100mmHg.In subsequently 5 minutes, further the pressure in the flask is reduced to 0.3mmHg.0.3mmHg pressure keep 90 minutes altogether to remove excessive unreacted glycol.The polymkeric substance of obtained to have high melt viscosity, range estimation is transparent and colourless, its second-order transition temperature is 122 ℃, logarithmic viscosity number is 0.65dL/g.This polymkeric substance of NMR analysis revealed comprise 59.9 moles of % 1,4 cyclohexane dimethanol residue and 40.1 moles of % 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 1G

Present embodiment has been described target group becomes 100 moles of % DMT. Dimethyl p-benzenedicarboxylate residues, 20 moles of %2; 2,4,4-tetramethyl--1; The preparation of the copolyesters of the 1,4 cyclohexane dimethanol residue (suitable/anti-=31/69) of 3-cyclobutanediol residue (suitable/anti-=98/2) and 80 moles of %.

With 77.68g DMT. Dimethyl p-benzenedicarboxylate, 48.46g 1; 4-cyclohexanedimethanol, 20.77g 2,2,4; 4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyl tin oxide are put into the 500ml flask that is equipped with nitrogen inlet, metal agitator and short still column.Flask is put into the Wood metal bath that is heated to 210 ℃.In experimentation, stirring velocity is set at 200RPM.210 ℃ of heating 3 minutes, in 30 minutes, make temperature be elevated to 260 ℃ gradually then flask contents.Reaction mixture kept 120 minutes at 260 ℃, arrived until 290 ℃ at 30 minutes internal heating then.In case reach 290 ℃, in subsequently 5 minutes, apply the pressure of vacuum in flask gradually and reach 100mmHg, and stirring velocity also is reduced to 100RPM.In subsequently 5 minutes, further the pressure in the flask is reduced to 0.3mmHg, and stirring velocity also is reduced to 50RPM.0.3mmHg pressure keep 60 minutes altogether to remove excessive unreacted glycol.The polymkeric substance of obtained to have high melt viscosity, range estimation is transparent and colourless, its second-order transition temperature is 103 ℃, logarithmic viscosity number is 0.65dL/g.This polymkeric substance of NMR analysis revealed comprise 85.7 moles of % 1,4 cyclohexane dimethanol residue and 14.3 moles of % 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 1H

Present embodiment has been described target group becomes 100 moles of % DMT. Dimethyl p-benzenedicarboxylate residues, 20 moles of %2; 2,4,4-tetramethyl--1; The preparation of the copolyesters of the 1,4 cyclohexane dimethanol residue (suitable/anti-=31/69) of 3-cyclobutanediol residue (suitable/anti-=5/95) and 80 moles of %.

With 77.68g DMT. Dimethyl p-benzenedicarboxylate, 48.46g 1; 4-cyclohexanedimethanol, 20.77g 2,2,4; 4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyl tin oxide are put into the 500ml flask that is equipped with nitrogen inlet, metal agitator and short still column.Flask is put into the Wood metal bath that is heated to 210 ℃.When the experiment beginning, stirring velocity is set at 200RPM.210 ℃ of heating 3 minutes, in 30 minutes, make temperature be elevated to 260 ℃ gradually then flask contents.Reaction mixture kept 120 minutes at 260 ℃, arrived until 290 ℃ at 30 minutes internal heating then.In case reach 290 ℃, in subsequently 5 minutes, apply the pressure of vacuum in flask gradually and reach 100mmHg, and stirring velocity also is reduced to 100RPM.In subsequently 5 minutes, further the pressure in the flask is reduced to a setting point of 0.3mmHg, and stirring velocity also is reduced to 50RPM.This pressure keeps 60 minutes altogether to remove excessive unreacted glycol.It should be noted that vacuum system fails to reach above-mentioned a setting point, but produce enough vacuum with obtain to have high melt viscosity, the transparent and colourless polymkeric substance of range estimation, its second-order transition temperature is 99 ℃, logarithmic viscosity number is 0.73dL/g.This polymkeric substance of NMR analysis revealed comprise 85 moles of % 1,4 cyclohexane dimethanol residue and 15 moles of % 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 2

Present embodiment explanation 2,2,4,4-tetramethyl--1,3-cyclobutanediol can improve the toughness of PCT type copolyesters (polyester that contains terephthalic acid and 1,4 cyclohexane dimethanol).

Be described below preparation based on 2,2,4,4-tetramethyl--1, the copolyesters of 3-cyclobutanediol.For all samples, the suitable/inverse proportion of 1,4 cyclohexane dimethanol is about 31/69.Copolyesters based on terepthaloyl moietie and 1,4 cyclohexane dimethanol is the polyester that is purchased.The copolyesters of embodiment 2A (Eastar PCTG 5445) obtains from Eastman Chemical Co..The copolyesters of embodiment 2B obtains with trade(brand)name Spectar from Eastman Chemical Co..Embodiment 2C and 2D prepare according to the described operation of embodiment 1A with pilot scale (each 15-1b batch naturally), and have logarithmic viscosity number shown in the table 2 and second-order transition temperature.Embodiment 2C is with the preparation of the target tin content (dibutyl tin oxide) of 300ppm.Final product contains the tin of 295ppm.The colour of the polyester of embodiment 2C is L ^*=77.11, a ^*=-1.50, b ^*=5.79.Embodiment 2D is with the preparation of the target tin content (dibutyl tin oxide) of 300ppm.Final product contains the tin of 307ppm.The colour of the polyester of embodiment 2D is L ^*=66.72, a ^*=-1.22, b ^*=16.28.

Material is injection molded into rod, beats breach subsequently and be used for socle girder (Izod) detection.Notched izod intensity obtains as the function of temperature, also is listed in the table 2.

For given sample, cantilever-type impact strength is the main transformation of experience in short TR.For example, based on the cantilever-type impact strength of the copolyesters of 38 moles of % terepthaloyl moietie in this transformation of 15-20 ℃ of experience.This transition temperature is relevant with the variation of failure mode: fragility at a lower temperature/low-yield destruction and the toughness/high-energy destruction under comparatively high temps.Transition temperature is expressed as the brittle-ductile transition temperature T _Bd, be to weigh the flexible means.T _BdBe listed in the table 2, and the mole % to comonomer maps in Fig. 2.

Data show and the T that causes PCT _BdThe terepthaloyl moietie that improves is compared, and in PCT, adds 2,2,4,4-tetramethyl--1, and the 3-cyclobutanediol can reduce T _BdWith improvement toughness.

Table 2

Notched izod ability (ft-lb/in)

1 the surplus of diol component of polyester in table is a 1,4 cyclohexane dimethanol.All polymkeric substance are from the DMT. Dimethyl p-benzenedicarboxylate preparation of 100 moles of %.

NA=does not obtain

Wherein B is a terepthaloyl moietie

C is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (suitable/anti-=50/50)

Embodiment 3

Present embodiment explanation 2,2,4,4-tetramethyl--1,3-cyclobutanediol can improve the toughness of PCT type copolyesters (polyester that contains terephthalic acid and 1,4 cyclohexane dimethanol).The polyester of preparation contains greater than 25 to less than 2,2,4 of 40 moles of % in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.

Be described below preparation based on DMT. Dimethyl p-benzenedicarboxylate, 2,2,4,4-tetramethyl--1, the copolyesters of 3-cyclobutanediol and 1,4 cyclohexane dimethanol (suitable/anti-=31/69), it has composition shown in the following table and performance.The surplus of the diol component of the polyester in following table is 1,4 cyclohexane dimethanol (suitable/anti-=31/69) until 100 moles of %.

Material is injection molded into 3.2mm and the thick rod of 6.4mm, beats breach subsequently and be used for the socle girder detection.Notched izod intensity is listed in the following table 23 ℃ of acquisitions.Detect density, Tg and the half-time of crystallization of molded bar.Melt viscosity at 290 ℃ of detection pellets.

Table 3

The various performances that are used for specific polyester of the present invention gather

NA=does not obtain

Embodiment 3A

With 1 of the DMT. Dimethyl p-benzenedicarboxylate of 21.24lb (49.71g/mol), 11.82lb (37.28g/mol); 2 of 4-cyclohexanedimethanol and 6.90lb (21.77g/mol); 2; 4, the reaction in the presence of catalyzer three (2 ethyl hexanoic acid) butyl tin of 200ppm together of 4-tetramethyl--1,3-cyclobutanediol.This is reflected under the nitrogen purging and in 18 gallons the stainless steel pressure container that is equipped with condensation tower, vacuum system and HELICONE type whisking appliance, carries out.Under the stirring of 25RPM, the temperature of reaction mixture is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture 250 ℃ with the down maintenance 2 hours of 20psig pressure.With 3psig/ minute speed pressure is reduced to 0psig then.The temperature of reaction mixture is elevated to 270 ℃ then, and pressure is reduced to 90mmHg.270 ℃ with 90mmHg down maintenance after 1 hour agitator speed is reduced to 15RPM, the temperature of reaction mixture is elevated to 290 ℃, pressure is reduced to less than 1mmHg.Reaction mixture 290 ℃ and less than 1mmHg pressure under keep stretching and no longer increase (50 minutes) up to energy to whisking appliance.Use nitrogen that the pressure of pressurized vessel is elevated to 1 normal atmosphere then.The fused polymkeric substance is extruded from pressurized vessel then.The refrigerative extruded polymer is ground to passes through the 6mm sieve.The logarithmic viscosity number of polymkeric substance is 0.714dL/g, and Tg is 113 ℃.This polymkeric substance of NMR analysis revealed comprise 73.3 moles of % 1,4 cyclohexane dimethanol residue and 26.7 moles of % 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 3B

The polyester of embodiment 3B is according to preparing with the said similar operation of embodiment 3A.The composition and the performance of these polyester are listed in the table 3.

Embodiment 4

Present embodiment explanation 2,2,4,4-tetramethyl--1,3-cyclobutanediol can improve the toughness of PCT type copolyesters (polyester that contains terephthalic acid and 1,4 cyclohexane dimethanol).The polyester of preparation contains 40 moles of % or more 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue in the present embodiment.

Be described below preparation based on DMT. Dimethyl p-benzenedicarboxylate, 2,2,4,4-tetramethyl--1, the copolyesters of 3-cyclobutanediol and 1,4 cyclohexane dimethanol (suitable/anti-=31/69), it has composition shown in the table 4 and performance.The surplus to 100 of the diol component of the polyester in table 4 a mole % is 1,4 cyclohexane dimethanol (suitable/anti-=31/69).

Material is injection molded into 3.2mm and the thick rod of 6.4mm, beats breach subsequently and be used for the socle girder detection.Notched izod intensity is listed in the table 4 23 ℃ of acquisitions.Detect density, Tg and the half-time of crystallization of molded bar.Melt viscosity at 290 ℃ of detection pellets.

Table 4

NA=does not obtain

Embodiment 4A

With 1 of the DMT. Dimethyl p-benzenedicarboxylate of 21.24lb (49.71g/mol), 8.84lb (27.88g/mol); 2 of 4-cyclohexanedimethanol and 10.08lb (31.77g/mol); 2; 4, the reaction in the presence of catalyzer three (2 ethyl hexanoic acid) butyl tin of 200ppm together of 4-tetramethyl--1,3-cyclobutanediol.This is reflected under the nitrogen purging and in 18 gallons the stainless steel pressure container that is equipped with condensation tower, vacuum system and HELICONE type whisking appliance, carries out.Under the stirring of 25RPM, the temperature of reaction mixture is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture 250 ℃ with the down maintenance 2 hours of 20psig pressure.With 3psig/ minute speed pressure is reduced to 0psig then.Agitator speed is reduced to 15RPM, and the temperature of reaction mixture is elevated to 290 ℃ then, and pressure is reduced to 2mmHg.Reaction mixture keeps down up to the no longer increase (80 minutes) that stretches of the energy to whisking appliance with 2mmHg pressure at 290 ℃.Use nitrogen that the pressure of pressurized vessel is elevated to 1 normal atmosphere then.The fused polymkeric substance is extruded from pressurized vessel then.The refrigerative extruded polymer is ground to passes through the 6mm sieve.The logarithmic viscosity number of polymkeric substance is 0.657dL/g, and Tg is 119 ℃.This polymkeric substance of NMR analysis revealed comprise 56.3 moles of % 1,4 cyclohexane dimethanol residue and 43.7 moles of % 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polymkeric substance is: L ^*=75.04, a ^*=-1.82, b ^*=6.72.

Embodiment 4B to 4D

The polyester of embodiment 4B to 4D is according to preparing with the said similar operation of embodiment 4A.The composition of these polyester and performance are listed in the following table 4.

Embodiment 4E

With 1 of the DMT. Dimethyl p-benzenedicarboxylate of 21.24lb (49.71g/mol), 6.43lb (20.28g/mol); 2 of 4-cyclohexanedimethanol and 12.49lb (39.37g/mol); 2; 4, the reaction in the presence of catalyzer three (2 ethyl hexanoic acid) butyl tin of 200ppm together of 4-tetramethyl--1,3-cyclobutanediol.This is reflected under the nitrogen purging and in 18 gallons the stainless steel pressure container that is equipped with condensation tower, vacuum system and HELICONE type whisking appliance, carries out.Under the stirring of 25RPM, the temperature of reaction mixture is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture 250 ℃ with the down maintenance 2 hours of 20psig pressure.With 3psig/ minute speed pressure is reduced to 0psig then.Then agitator speed is reduced to 15RPM, the temperature of reaction mixture is elevated to 290 ℃ then, and pressure is reduced to 2mmHg.Reaction mixture keeps down up to the no longer increase (50 minutes) that stretches of the energy to whisking appliance at 290 ℃ of pressure with＜1mmHg.Use nitrogen that the pressure of pressurized vessel is elevated to 1 normal atmosphere then.The fused polymkeric substance is extruded from pressurized vessel then.The refrigerative extruded polymer is ground to passes through the 6mm sieve.The logarithmic viscosity number of polymkeric substance is 0.604dL/g, and Tg is 139 ℃.This polymkeric substance of NMR analysis revealed comprise 40.8 moles of % 1,4 cyclohexane dimethanol residue and 59.2 moles of % 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polymkeric substance is: L ^*=80.48, a ^*=-1.30, b ^*=6.82.

Embodiment 4F

With 1 of the DMT. Dimethyl p-benzenedicarboxylate of 21.241b (49.71g/mol), 8.84lb (27.88g/mol); 2 of 4-cyclohexanedimethanol and 10.08lb (31.77g/mol); 2; 4, the reaction in the presence of catalyzer three (2 ethyl hexanoic acid) butyl tin of 200ppm together of 4-tetramethyl--1,3-cyclobutanediol.This is reflected under the nitrogen purging and in 18 gallons the stainless steel pressure container that is equipped with condensation tower, vacuum system and HELICONE type whisking appliance, carries out.Under the stirring of 25RPM, the temperature of reaction mixture is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture 250 ℃ with the down maintenance 2 hours of 20psig pressure.With 3psig/ minute speed pressure is reduced to 0psig then.The temperature of reaction mixture is elevated to 270 ℃ then, and pressure is reduced to 90mmHg.270 ℃ keep 1 hour with 90mmHg after, agitator speed is reduced to 15RPM, pressure is reduced to 4mmHg.When reaction mixture reaches 290 ℃ when the 4mmHg, use nitrogen that the pressure of pressurized vessel is elevated to 1 normal atmosphere immediately.The fused polymkeric substance is extruded from pressurized vessel then.The refrigerative extruded polymer is ground to passes through the 6mm sieve.The logarithmic viscosity number of polymkeric substance is 0.475dL/g, and Tg is 121 ℃.This polymkeric substance of NMR analysis revealed comprise 55.5 moles of % 1,4 cyclohexane dimethanol residue and 44.5 moles of % 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue is formed.The colour of polymkeric substance is: L ^*=85.63, a ^*=-0.88, b ^*=4.34.

Embodiment 5-Comparative Examples

The data rows of the contrast material of present embodiment is in table 5.PC is the Makrolon 2608 from Bayer, and it is the diphenyl carbonate residue of 100 moles of % dihydroxyphenyl propane residues and 100 moles of % that its nominal is formed.The nominal melt flow of Makrolon 2608 is 20g/10 minute, uses the 1.2kg weight measurement down at 300 ℃.PET is the Eastar 9921 from Eastman Chemical Company, and it is the cyclohexanedimethanol (CHDM) of 100 moles of % terephthalic acids, 3.5 moles of % and the terepthaloyl moietie of 96.5 moles of % that its nominal is formed.PETG is the Eastar 6763 from Eastman ChemicalCompany, and it is the cyclohexanedimethanol (CHDM) of 100 moles of % terephthalic acids, 31 moles of % and the terepthaloyl moietie of 69 moles of % that its nominal is formed.PCTG is the Eastar DN001 from EastmanChemical Company, and it is the cyclohexanedimethanol (CHDM) of 100 moles of % terephthalic acids, 62 moles of % and the terepthaloyl moietie of 38 moles of % that its nominal is formed.PCTA is the Eastar AN001 from Eastman Chemical Company, and it is the m-phthalic acid of 65 moles of % terephthalic acids, 35 moles of % and the cyclohexanedimethanol (CHDM) of 100 moles of % that its nominal is formed.Polysulfones is the Udel 1700 from Solvay, 4 of the dihydroxyphenyl propane residue that its nominal composition is 100 moles of % and 100 moles of %, 4-dichloro semi-annular jade pendant acyl group sulfone residue.The nominal melt flow of Udel1700 is 6.5g/10 minute, uses the 2.16kg weight measurement down at 343 ℃.SAN is the Lustran 31 from Lanxess, and it is the vinylbenzene of 76 moles of % and the vinyl cyanide of 24 moles of % that its nominal is formed.The nominal melt flow of Lustran 31 is 7.5g/10 minute, uses the 3.8kg weight measurement down at 230 ℃.Compare with all other resins, embodiments of the invention show the toughness improved the thick rod of 6.4mm.

Table 5

The various performances of particular business polymkeric substance gather

NA=does not obtain

Embodiment 6

The present embodiment explanation is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl--1, and the consumption of 3-cyclobutanediol is to the influence of the second-order transition temperature of polyester.

Embodiment 6A

The polyester of present embodiment is through carrying out transesterify and polycondensation prepares in the stage of separating.The transesterify experiment is being carried out in heating type (CTR) reactor drum continuously.CTR is the glass reactor of 3000ml, is equipped with single shaft to drive paddle agitator, is covered by the electrically heated overcoat, and is equipped with the filling reflux condensation mode post of heating.In reactor drum, pack into 777g (4 moles) DMT. Dimethyl p-benzenedicarboxylate, 230g (1.6 moles) 2; 2; 4; 4-tetramethyl--1, the cyclohexanedimethanol of 3-cyclobutanediol, 460.8g (3.2 moles) and three-2 ethyl hexanoic acid butyl tin of 1.12g (make the tin of 200ppm is arranged in final polymkeric substance).With the heating jacket manual regulation to 100% output rating.The collection of a setting point and data is promoted through the Camile process control system.In case the reactant fusion just begins to stir and slowly be increased to 250rpm.The temperature of reactor drum progressively raise along with working time.The weight of the methyl alcohol of collecting is equaled a record through the sky.When the effusion of methyl alcohol stops or stopped reaction during predetermined low temperature level at 260 ℃.Under nitrogen purging, take out oligopolymer, and cool to room temperature.Use the liquid nitrogen freezing oligopolymer, and be broken into the fritter that is small enough to weighing adding 500ml round-bottomed flask.

In polycondensation, in the about 150g oligopolymer adding 500ml round-bottomed flask with as above preparation.This flask is equipped with stainless steel whisking appliance and polymkeric substance head.Glassware is set on the polymeric device of half mole number, and beginning Camile order.In case the oligopolymer fusion just is placed on the full up position in the round-bottomed flask with whisking appliance.Temperature/pressure/the stir speed (S.S.) by the Camile software control of these embodiment is listed in the following table, in proper order except as otherwise noted.

The Camile order of embodiment 6A

The polymkeric substance of gained takes out from flask, uses the hydraulic cutter cutting, and grinds to form the screen size of 6mm.The logarithmic viscosity number of every kind of polymer samples that ground in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration, levels of catalysts (Sn) detects through x-XRF X spectrum, colour (L ^*, a ^*, b ^*) detect through transmitted spectrum.The composition of polymkeric substance passes through ¹H NMR obtains.Use the thermostability and the melt viscosity of RheometricsMechanical Spectrometer (RMS-800) test sample.

Following table shows the experimental data of present embodiment polyester.Fig. 3 also shows the dependency of Tg to composition and logarithmic viscosity number.These data show for the constant logarithmic viscosity number, improve 2,2,4,4-tetramethyl--1, and the consumption of 3-cyclobutanediol can improve second-order transition temperature with almost linear mode

Table 6

Second-order transition temperature, logarithmic viscosity number and composition

NA=does not obtain

Embodiment 7

The present embodiment explanation is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl--1, and the consumption of 3-cyclobutanediol is to the influence of the second-order transition temperature of polyester.The polyester of preparation contains greater than 25 to less than 2,2,4 of 40 moles of % in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.

With DMT. Dimethyl p-benzenedicarboxylate, 1,4 cyclohexane dimethanol and 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol adds in single neck round-bottomed flask of 500ml.To 2,2,4,4-tetramethyl--1, the NMR of 3-cyclobutanediol raw material are analyzed and are shown that suitable/inverse proportion is 53/47.The polyester of present embodiment prepares with glycol/sour ratio of 1.2/1, and is wherein all excessive in 2,2,4,4-tetramethyl--1,3-cyclobutanediol.The dibutyl tin oxide that adds capacity is to obtain the tin of 300ppm in final polymkeric substance.Flask is under the 0.2SCFC nitrogen purging with vacuum drop capabilities.Flask is immersed in the Belmont metal bath at 200 ℃, and after the reactant fusion, stir in 200RPM.After about 2.5 hours, temperature is elevated to 210 ℃, and these conditions were kept 2 hours again.Temperature is elevated to 285 ℃ (in about 25 minutes), and in 5 minutes, pressure is reduced to 0.3mmHg.Along with viscosity increases and reduce stirring velocity, use the minimum stirring of 15RPM.Change the total polymerization time to reach the target logarithmic viscosity number.After accomplishing polymerization, the Belmont metal bath of loweing, and make polymkeric substance be cooled to be lower than its second-order transition temperature.After about 30 minutes, flask is immersed Belmont metal bath (at this 30 minutes waiting periods, temperature has been elevated to 295 ℃) once more, and heated polymerizable thing material is up to from glass flask, taking out.Under medium level, stirring polymer material cools off up to polymkeric substance.Take out polymkeric substance from flask, and be ground to and pass through the 3mm sieve.Changing this operation is described below with preparation and has the copolyesters that 32 moles of % targets are formed.

Logarithmic viscosity number such as above-mentioned " detection method " said detection.The composition of polyester is through being explained in above-mentioned detection method part ¹H NMR measures.Second-order transition temperature uses after quenching 20 ℃/minute speed control second-heating to detect through DSC.

Following table shows the experimental data of present embodiment polyester.Fig. 3 also shows the dependency of Tg to composition and logarithmic viscosity number.These data show for the constant logarithmic viscosity number, improve 2,2,4,4-tetramethyl--1, and the consumption of 3-cyclobutanediol can improve second-order transition temperature with almost linear mode.

Table 7

The relation of second-order transition temperature and logarithmic viscosity number and composition

NA=does not obtain

Embodiment 8

The present embodiment explanation is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl--1, and the consumption of 3-cyclobutanediol is to the influence of the second-order transition temperature of polyester.The polyester of preparation contains 40 moles of % or more 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue in the present embodiment.

Embodiment A-AC

These polyester are through carrying out transesterify and polycondensation prepares in the stage of separating.The transesterify experiment is being carried out in heating type (CTR) reactor drum continuously.CTR is the glass reactor of 3000ml, is equipped with single shaft to drive paddle agitator, is covered by the electrically heated overcoat, and is equipped with the filling reflux condensation mode post of heating.In reactor drum, pack into 777g DMT. Dimethyl p-benzenedicarboxylate, 375g 2,2,4,4-tetramethyl--1, three-2 ethyl hexanoic acid butyl tin of the cyclohexanedimethanol of 3-cyclobutanediol, 317g and 1.12g (make the tin of 200ppm is arranged in final polymkeric substance).With the heating jacket manual regulation to 100% output rating.The collection of a setting point and data is promoted through the Camile process control system.In case the reactant fusion just begins to stir and slowly be increased to 250rpm.The temperature of reactor drum progressively raise along with working time.The weight of the methyl alcohol of collecting is equaled a record through the sky.When the effusion of methyl alcohol stops or stopped reaction during predetermined low temperature level at 260 ℃.Under nitrogen purging, take out oligopolymer, and cool to room temperature.Use the liquid nitrogen freezing oligopolymer, and be broken into the fritter that is small enough to weighing adding 500ml round-bottomed flask.

In polycondensation, in the 150g oligopolymer adding 500ml round-bottomed flask with as above preparation.This flask is equipped with stainless steel whisking appliance and polymkeric substance head.Glassware is set on the polymeric device of half mole number, and beginning Camile order.In case the oligopolymer fusion just is placed on the full up position in the round-bottomed flask with whisking appliance.Temperature/pressure/the stir speed (S.S.) by the Camile software control of these embodiment is listed in the following table, in proper order except as otherwise noted.

The Camile order of polycondensation

The Camile order of embodiment A, C, R, Y, AB, AC

For Embodiment B, D, F, use with last epiphase with order, the time that different is in the stage 7 is 80 minutes.For embodiment G and J, use with last epiphase with order, the time that different is in the stage 7 is 50 minutes.For embodiment L, use with last epiphase with order, the time that different is in the stage 7 is 140 minutes.

The Camile order of embodiment E

For example I, use with last epiphase with order, the vacuum that different is in stage 6 and 7 is 8 to hold in the palm.For embodiment O, use with last epiphase with order, the vacuum that different is in stage 6 and 7 is 6 to hold in the palm.For embodiment P, use with last epiphase with order, the vacuum that different is in stage 6 and 7 is 4 to hold in the palm.For embodiment Q, use with last epiphase with order, the vacuum that different is in stage 6 and 7 is 5 to hold in the palm.

The Camile order of embodiment H

For embodiment U and AA, use with last epiphase with order, the vacuum that different is in stage 6 and 7 is 6 to hold in the palm.For EXAMPLE V and X, use with last epiphase with order, the vacuum that different is in stage 6 and 7 is 6 to hold in the palm and stir speed (S.S.) is 15rpm.For embodiment Z, use with last epiphase with order, the stir speed (S.S.) that different is in stage 6 and 7 is 15rpm.

The Camile order of embodiment K

For embodiment M, use with last epiphase with order, the vacuum that different is in stage 6 and 7 is 8 to hold in the palm.For embodiment N, use with last epiphase with order, the vacuum that different is in stage 6 and 7 is 7 to hold in the palm.

The Camile order of embodiment S and T

The polymkeric substance of gained takes out from flask, uses the hydraulic cutter cutting, and grinds to form the screen size of 6mm.The logarithmic viscosity number of every kind of polymer samples that ground in the phenol/tetrachloroethane of 60/40 (w/w) under the concentration of 0.5g/100ml in 25 ℃ of mensuration, levels of catalysts (Sn) detects through x-XRF X spectrum, colour (L ^*, a ^*, b ^*) detect through transmitted spectrum.The composition of polymkeric substance obtains through 1H NMR.Use the thermostability and the melt viscosity of Rheometrics Mechanical Spectrometer (RMS-800) test sample.

Embodiment A D-AK and AS

As above for the polyester of said these embodiment of preparation of embodiment A-Z, the target tin content of different the is final polymkeric substance among embodiment A D-AK and the AS is 150ppm.Following table has been explained the order of passing through the temperature/pressure/stir speed (S.S.) of Camile software control among these embodiment.

The Camile order of embodiment A D, AF and AH

For embodiment A D, whisking appliance is adjusted to 25rpm, and in the stage 7, stopped 95 minutes.

The Camile order of embodiment A E

For embodiment A K, use with last epiphase with order, the time that different is in the stage 7 is 75 minutes.

The Camile order of embodiment A G

The Camile order of embodiment A I

The Camile order of embodiment A J

Embodiment A L-AR

With DMT. Dimethyl p-benzenedicarboxylate, 1,4 cyclohexane dimethanol and 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol adds in single neck round-bottomed flask of 500ml.The polyester of present embodiment prepares with glycol/sour ratio of 1.2/1, and is wherein all excessive in 2,2,4,4-tetramethyl--1,3-cyclobutanediol.The tributyltin oxide catalyst that adds capacity is to obtain the tin of 300ppm in final polymkeric substance.Flask is under the 0.2SCFC nitrogen purging with vacuum drop capabilities.Flask is immersed in the Belmont metal bath at 200 ℃, and after the reactant fusion, stir in 200RPM.After about 2.5 hours, temperature is elevated to 210 ℃, and these conditions were kept 2 hours again.Temperature is elevated to 285 ℃ (in about 25 minutes), and in 5 minutes, pressure is reduced to 0.3mmHg.Along with viscosity increases and reduce stirring velocity, use the minimum stirring of 15RPM.Change the total polymerization time to reach the target logarithmic viscosity number.After accomplishing polymerization, the Belmont metal bath of loweing, and make polymkeric substance be cooled to be lower than its second-order transition temperature.After about 30 minutes, flask is immersed Belmont metal bath (at this 30 minutes waiting periods, temperature has been elevated to 295 ℃) once more, and heated polymerizable thing material is up to from glass flask, taking out.Under medium level, stirring polymer material cools off up to polymkeric substance.Take out polymkeric substance from flask, and be ground to and pass through the 3mm sieve.Changing this operation is described below with preparation and has the copolyesters that 45 moles of % targets are formed.

Following table shows the experimental data of present embodiment polyester.These data show for the constant logarithmic viscosity number, improve 2,2,4,4-tetramethyl--1, and the consumption of 3-cyclobutanediol can improve second-order transition temperature with almost linear mode.Fig. 3 also shows the dependency of Tg to composition and logarithmic viscosity number.

Table 8

NA=does not obtain

Embodiment 9

Present embodiment explanation 2,2,4,4-tetramethyl--1, the dominant position of 3-cyclobutanediol isomer type (suitable or trans) is to the influence of polyester second-order transition temperature.

With DMT. Dimethyl p-benzenedicarboxylate, 1,4 cyclohexane dimethanol and 2,2,4,4-tetramethyl--1, the weighing of 3-cyclobutanediol adds in single neck round-bottomed flask of 500ml.The polyester of present embodiment prepares with glycol/sour ratio of 1.2/1, and is wherein all excessive in 2,2,4,4-tetramethyl--1,3-cyclobutanediol.The tributyltin oxide catalyst that adds capacity is to obtain the tin of 300ppm in final polymkeric substance.Flask is under the 0.2SCFC nitrogen purging with vacuum drop capabilities.Flask is immersed in the Belmont metal bath at 200 ℃, and after the reactant fusion, stir in 200RPM.After about 2.5 hours, temperature is elevated to 210 ℃, and these conditions were kept 2 hours again.Temperature is elevated to 285 ℃ (in about 25 minutes), and in 5 minutes, pressure is reduced to 0.3mmHg.Along with viscosity increases and reduce stirring velocity, use the minimum stirring of 15RPM.Change the total polymerization time to reach the target logarithmic viscosity number.After accomplishing polymerization, the Belmont metal bath of loweing, and make polymkeric substance be cooled to be lower than its second-order transition temperature.After about 30 minutes, flask is immersed Belmont metal bath (at this 30 minutes waiting periods, temperature has been elevated to 295 ℃) once more, and heated polymerizable thing material is up to from glass flask, taking out.Under medium level, stirring polymer material cools off up to polymkeric substance.Take out polymkeric substance from flask, and be ground to and pass through the 3mm sieve.Changing this operation is described below with preparation and has the copolyesters that 45 moles of % targets are formed.

Following table shows the experimental data of present embodiment polyester.These data show for the constant logarithmic viscosity number, cis 2,2,4, and 4-tetramethyl--1, the 3-cyclobutanediol is trans 2,2,4 improving validity aspect the second-order transition temperature, 4-tetramethyl--1, about twice of 3-cyclobutanediol.

Table 9

2,2,4,4-tetramethyl--1, the suitable/trans composition of 3-cyclobutanediol is to the influence of Tg

NA=does not obtain

Embodiment 10

Present embodiment has been described and has been contained 100 moles of % DMT. Dimethyl p-benzenedicarboxylate residues, 55 moles of %1,4-cyclohexanedimethanol residue and 45 moles of %2,2,4,4-tetramethyl--1, the preparation of the copolyesters of 3-cyclobutanediol residue.

With 97.10g (0.5mol) DMT. Dimethyl p-benzenedicarboxylate, 52.46g (0.36mol) 1; 4-cyclohexanedimethanol, 34.07g (0.24mol) 2; 2; 4,4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.0863g (300ppm) dibutyl tin oxide are put into the 500ml flask that is equipped with nitrogen inlet, metal agitator and short still column.Flask is put into the Wood metal bath that is heated to 200 ℃.Flask contents 200 ℃ of heating 1 hour, is elevated to 210 ℃ then.Reaction mixture kept 2 hours at 210 ℃, then at 30 minutes internal heating to 290 ℃.In case reach 290 ℃, in subsequently 3-5 minute, apply the vacuum of 0.01psig gradually.Make whole vacuum (0.01psig) keep about 45 minutes altogether to remove excessive unreacted glycol.The polymkeric substance of obtained to have high melt viscosity, range estimation is transparent and colourless, its second-order transition temperature is 125 ℃, logarithmic viscosity number is 0.64dL/g.

Embodiment 11-Comparative Examples

Present embodiment is explained based on 100%2,2,4,4-tetramethyl--1, and the polyester of 3-cyclobutanediol has half-time of crystallization slowly.

Only based on terephthalic acid and 2,2,4,4-tetramethyl--1, the polyester of 3-cyclobutanediol according to the preparation of the foregoing description 1A similar methods, and have the performance shown in the table 10.This polyester has the dibutyl tin oxide of 300ppm.2,2,4,4-tetramethyl--1, the anti-/ suitable ratio of 3-cyclobutanediol is 65/35.

At 320 ℃ of polymkeric substance compacting films from grinding.Detecting half-time of crystallization from melt is to carry out at 220-250 ℃ the temperature increment with 10 ℃, and is reported in the table 10.With the fastest half-time of crystallization of sample as the half-time of crystallization minimum value relevant with temperature.The fastest half-time of crystallization of this polyester is about 1300 minutes.To be worth and have only comparing of extremely short half-time of crystallization (less than 1 minute) based on the polyester (PCT) of terephthalic acid and 1,4 cyclohexane dimethanol (being not used in the comonomer of modification), as shown in Figure 1.

Table 10

Half-time of crystallization (minute)

Wherein: F is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (anti-/ suitable=65/35)

Embodiment 12-Comparative Examples

Use 3.5 inches single screw extrusion machine productions to contain the sheet material of polyester, said polyester made have 100 moles of % terephthalic acid residues, 80 moles of %1,4-cyclohexanedimethanol and 20 moles of %2; 2; 4,4-tetramethyl--1, the target of 3-cyclobutanediol residue is formed.Sheet material is extruded continuously, be corrected to the thickness of 177 mils, then various sheet materials shearings are reached dimensional requirement.On a sheet material, detect logarithmic viscosity number and second-order transition temperature.The logarithmic viscosity number that records sheet material is 0.69dL/g.The second-order transition temperature that records sheet material is 106 ℃.Then sheet material is regulated fortnights down 50% relative humidity and 60 ℃.Using the Brown thermoforming machine subsequently is in 2.5: 1 the former to stretch ratio with sheet heat forming.Thermoforming baking oven for heating device is set at 70/60/60% output, only uses top firing.In baking oven, keep the various times to measure the influence of sheet temperature sheet material to part quality, as shown in the table.Part quality stretches through volume, the calculating that detects the thermoforming parts and visual observations thermoforming parts are confirmed.Stretching is through calculating divided by the maximum part volume (embodiment G) that in this group experiment, reaches with piece volumes.Any foaming in the parts of visual observations thermoforming, the foaming degree evaluation is not for having (N), low (L) or high (H).These second-order transition temperatures of following result proof are that 106 ℃ thermoplastic sheets can thermoforming under following condition, and this shows as these sheet materials and has at least 95% stretching, do not bubble, and before thermoforming dry sheet material in advance not.

Embodiment 13-Comparative Examples

Use 3.5 inches single screw extrusion machine productions to contain the sheet material of polyester, said polyester made have 100 moles of % terephthalic acid residues, 80 moles of %1,4-cyclohexanedimethanol and 20 moles of %2; 2; 4,4-tetramethyl--1, the target of 3-cyclobutanediol residue is formed.Sheet material is extruded continuously, be corrected to the thickness of 177 mils, then various sheet materials shearings are reached dimensional requirement.On a sheet material, detect logarithmic viscosity number and second-order transition temperature.The logarithmic viscosity number that records sheet material is 0.69dL/g.The second-order transition temperature that records sheet material is 106 ℃.Then sheet material is regulated fortnights down 100% relative humidity and 25 ℃.Using the Brown thermoforming machine subsequently is in 2.5: 1 the former to stretch ratio with sheet heat forming.Thermoforming baking oven for heating device is set at 60/40/40% output, only uses top firing.In baking oven, keep the various times to measure the influence of sheet temperature sheet material to part quality, as shown in the table.Part quality stretches through volume, the calculating that detects the thermoforming parts and visual observations thermoforming parts are confirmed.Stretching is through calculating divided by the maximum part volume (embodiment G) that in this group experiment, reaches with piece volumes.Any foaming in the parts of visual observations thermoforming, the foaming degree evaluation is not for having (N), low (L) or high (H).These second-order transition temperatures of following result proof are that 106 ℃ thermoplastic sheets can thermoforming under following condition, and this shows as these sheet materials and has at least 95% stretching, do not bubble, and before thermoforming dry sheet material in advance not.

Embodiment 14-Comparative Examples

Use 3.5 inches sheet materials that single screw extrusion machine production is made up of Kelvx 201.Kelvx is that a kind of 69.85%PCTG of containing is (from the Eastar of Eastman Chemcial Co.; Have 100 moles of % terephthalic acid residues, 62 moles of %1,4-cyclohexanedimethanol and 38 moles of % glycol residues), the blend of 30%PC (bisphenol-a polycarbonate) and 0.15%Weston 619 (stablizer that Crompton Corporation sells).Sheet material is extruded continuously, be corrected to the thickness of 177 mils, then various sheet materials shearings are reached dimensional requirement.On a sheet material, detect second-order transition temperature, recording is 100 ℃.Then sheet material is regulated fortnights down 50% relative humidity and 60 ℃.Using the Brown thermoforming machine subsequently is in 2.5: 1 the former to stretch ratio with sheet heat forming.Thermoforming baking oven for heating device is set at 70/60/60% output, only uses top firing.In baking oven, keep the various times to measure the influence of sheet temperature sheet material to part quality, as shown in the table.Part quality stretches through volume, the calculating that detects the thermoforming parts and visual observations thermoforming parts are confirmed.Stretching is through calculating divided by the maximum part volume (embodiment E) that in this group experiment, reaches with piece volumes.Any foaming in the parts of visual observations thermoforming, the foaming degree evaluation is not for having (N), low (L) or high (H).These second-order transition temperatures of following result proof are that 100 ℃ thermoplastic sheets can thermoforming under following condition, and this shows as these sheet materials and has at least 95% stretching, do not bubble, and before thermoforming dry sheet material in advance not.

Embodiment 15-Comparative Examples

Use 3.5 inches sheet materials that single screw extrusion machine production is made up of Kelvx 201.Sheet material is extruded continuously, be corrected to the thickness of 177 mils, then various sheet materials shearings are reached dimensional requirement.On a sheet material, detect second-order transition temperature, recording is 100 ℃.Then sheet material is regulated fortnights down 100% relative humidity and 25 ℃.Using the Brown thermoforming machine subsequently is in 2.5: 1 the former to stretch ratio with sheet heat forming.Thermoforming baking oven for heating device is set at 60/40/40% output, only uses top firing.In baking oven, keep the various times to measure the influence of sheet temperature sheet material to part quality, as shown in the table.Part quality stretches through volume, the calculating that detects the thermoforming parts and visual observations thermoforming parts are confirmed.Stretching is through calculating divided by the maximum part volume (embodiment H) that in this group experiment, reaches with piece volumes.Any foaming in the parts of visual observations thermoforming, the foaming degree evaluation is not for having (N), low (L) or high (H).These second-order transition temperatures of following result proof are that 100 ℃ thermoplastic sheets can thermoforming under following condition, and this shows as these sheet materials and has at least 95% stretching, do not bubble, and before thermoforming dry sheet material in advance not.

NR=is record not

Embodiment 16-Comparative Examples

The sheet material that uses 3.5 inches single screw extrusion machine productions to form by PCTG 25976 (the 1,4 cyclohexane dimethanol residue of 100 moles of % terephthalic acid residues, 62 moles of % and the glycol residue of 38 moles of %).Sheet material is extruded continuously, be corrected to the thickness of 118 mils, then various sheet materials shearings are reached dimensional requirement.On a sheet material, detect second-order transition temperature, recording is 87 ℃.Then sheet material is regulated the four stars phases down 50% relative humidity and 60 ℃.Recording water-content is 0.17 weight %.Using the Brown thermoforming machine subsequently is in 2.5: 1 the former to stretch ratio with sheet heat forming.Thermoforming baking oven for heating device is set at 70/60/60% output, only uses top firing.In baking oven, keep the various times to measure the influence of sheet temperature sheet material to part quality, as shown in the table.Part quality stretches through volume, the calculating that detects the thermoforming parts and visual observations thermoforming parts are confirmed.Stretching is through calculating divided by the maximum part volume (embodiment A) that in this group experiment, reaches with piece volumes.Any foaming in the parts of visual observations thermoforming, the foaming degree evaluation is not for having (N), low (L) or high (H).These second-order transition temperatures of following result proof are that 87 ℃ thermoplastic sheets can thermoforming under following condition, and this shows as these sheet materials and has the stretching greater than 95%, do not bubble, and before thermoforming dry sheet material in advance not.

Embodiment 17-Comparative Examples

Use 1.25 inches single screw extrusion machine productions by the Teijin L-1250 polycarbonate (a kind of bisphenol-a polycarbonate) of 20 weight % but, the PCTG 25976 of 79.85 weight % and the miscible blends that 0.15 weight %Weston 619 forms.The sheet material that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Sheet material is extruded continuously, be corrected to the thickness of 118 mils, then various sheet materials shearings are reached dimensional requirement.On a sheet material, detect second-order transition temperature, recording is 94 ℃.Then sheet material is regulated the four stars phases down 50% relative humidity and 60 ℃.Recording water-content is 0.25 weight %.Using the Brown thermoforming machine subsequently is in 2.5: 1 the former to stretch ratio with sheet heat forming.Thermoforming baking oven for heating device is set at 70/60/60% output, only uses top firing.In baking oven, keep the various times to measure the influence of sheet temperature sheet material to part quality, as shown in the table.Part quality stretches through volume, the calculating that detects the thermoforming parts and visual observations thermoforming parts are confirmed.Stretching is through calculating divided by the maximum part volume (embodiment A) that in this group experiment, reaches with piece volumes.Any foaming in the parts of visual observations thermoforming, the foaming degree evaluation is not for having (N), low (L) or high (H).These second-order transition temperatures of following result proof are that 94 ℃ thermoplastic sheets can thermoforming under following condition, and this shows as these sheet materials and has the stretching greater than 95%, do not bubble, and before thermoforming dry sheet material in advance not.

Embodiment 18-Comparative Examples

But use 1.25 inches single screw extrusion machine productions by the Teijin L-1250 polycarbonate of 30 weight %, the PCTG 25976 of 69.85 weight % and the miscible blends that 0.15 weight %Weston 619 forms.The sheet material that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Sheet material is extruded continuously, be corrected to the thickness of 118 mils, then various sheet materials shearings are reached dimensional requirement.On a sheet material, detect second-order transition temperature, recording is 99 ℃.Then sheet material is regulated the four stars phases down 50% relative humidity and 60 ℃.Recording water-content is 0.25 weight %.Using the Brown thermoforming machine subsequently is in 2.5: 1 the former to stretch ratio with sheet heat forming.Thermoforming baking oven for heating device is set at 70/60/60% output, only uses top firing.In baking oven, keep the various times to measure the influence of sheet temperature sheet material to part quality, as shown in the table.Part quality stretches through volume, the calculating that detects the thermoforming parts and visual observations thermoforming parts are confirmed.Stretching is through calculating divided by the maximum part volume (embodiment A) that in this group experiment, reaches with piece volumes.Any foaming in the parts of visual observations thermoforming, the foaming degree evaluation is not for having (N), low (L) or high (H).These second-order transition temperatures of following result proof are that 99 ℃ thermoplastic sheets can thermoforming under following condition, and this shows as these sheet materials and has the stretching greater than 95%, do not bubble, and before thermoforming dry sheet material in advance not.

NA=does not obtain.Null value representes not form because sheet material does not get into mould sheet material (seemingly because too cold).

Embodiment 19-Comparative Examples

But use 1.25 inches single screw extrusion machine productions by the Teijin L-1250 polycarbonate of 40 weight %, the PCTG 25976 of 59.85 weight % and the miscible blends that 0.15 weight %Weston 619 forms.The sheet material that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Sheet material is extruded continuously, be corrected to the thickness of 118 mils, then various sheet materials shearings are reached dimensional requirement.On a sheet material, detect second-order transition temperature, recording is 105 ℃.Then sheet material is regulated the four stars phases down 50% relative humidity and 60 ℃.Recording water-content is 0.265 weight %.Using the Brown thermoforming machine subsequently is in 2.5: 1 the former to stretch ratio with sheet heat forming.Thermoforming baking oven for heating device is set at 70/60/60% output, only uses top firing.In baking oven, keep the various times to measure the influence of sheet temperature sheet material to part quality, as shown in the table.Part quality stretches through volume, the calculating that detects the thermoforming parts and visual observations thermoforming parts are confirmed.Stretching is through calculating divided by the maximum part volume (embodiment 8A-8E) that in this group experiment, reaches with piece volumes.Any foaming in the parts of visual observations thermoforming, the foaming degree evaluation is not for having (N), low (L) or high (H).These second-order transition temperatures of following result proof are that 105 ℃ thermoplastic sheets can thermoforming under following condition, and this shows as these sheet materials and has the stretching greater than 95%, do not bubble, and before thermoforming dry sheet material in advance not.

Embodiment 20-Comparative Examples

But use 1.25 inches single screw extrusion machine productions by the Teijin L-1250 polycarbonate of 50 weight %, the PCTG 25976 of 49.85 weight % and the miscible blends that 0.15 weight %Weston 619 forms.Sheet material is extruded continuously, be corrected to the thickness of 118 mils, then various sheet materials shearings are reached dimensional requirement.On a sheet material, detect second-order transition temperature, recording is 111 ℃.Then sheet material is regulated the four stars phases down 50% relative humidity and 60 ℃.Recording water-content is 0.225 weight %.Using the Brown thermoforming machine subsequently is in 2.5: 1 the former to stretch ratio with sheet heat forming.Thermoforming baking oven for heating device is set at 70/60/60% output, only uses top firing.In baking oven, keep the various times to measure the influence of sheet temperature sheet material to part quality, as shown in the table.Part quality stretches through volume, the calculating that detects the thermoforming parts and visual observations thermoforming parts are confirmed.Stretching through with piece volumes divided by the maximum part volume (embodiment A-D) calculate that in this group experiment, reaches.Any foaming in the parts of visual observations thermoforming, the foaming degree evaluation is not for having (N), low (L) or high (H).These second-order transition temperatures of following result proof are that 111 ℃ thermoplastic sheets can thermoforming under following condition, and this shows as these sheet materials and has the stretching greater than 95%, do not bubble, and before thermoforming dry sheet material in advance not.

Embodiment 21-Comparative Examples

But use 1.25 inches single screw extrusion machine productions by the Teijin L-1250 polycarbonate of 60 weight %, the PCTG 25976 of 39.85 weight % and the miscible blends that 0.15 weight %Weston 619 forms.The sheet material that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Sheet material is extruded continuously, be corrected to the thickness of 118 mils, then various sheet materials shearings are reached dimensional requirement.On a sheet material, detect second-order transition temperature, recording is 117 ℃.Then sheet material is regulated the four stars phases down 50% relative humidity and 60 ℃.Recording water-content is 0.215 weight %.Using the Brown thermoforming machine subsequently is in 2.5: 1 the former to stretch ratio with sheet heat forming.Thermoforming baking oven for heating device is set at 70/60/60% output, only uses top firing.In baking oven, keep the various times to measure the influence of sheet temperature sheet material to part quality, as shown in the table.Part quality stretches through volume, the calculating that detects the thermoforming parts and visual observations thermoforming parts are confirmed.Stretching is through calculating divided by the maximum part volume (embodiment A) that in this group experiment, reaches with piece volumes.Any foaming in the parts of visual observations thermoforming, the foaming degree evaluation is not for having (N), low (L) or high (H).These second-order transition temperatures of following result proof be 117 ℃ thermoplastic sheets can be under following condition can not thermoforming, this shows as can not produce under the situation that before thermoforming, does not have dry sheet material in advance has greater than 95% stretching and does not have blistered sheet material.

Embodiment 22-Comparative Examples

But use 1.25 inches single screw extrusion machine productions by the Teijin L-1250 polycarbonate of 65 weight %, the PCTG 25976 of 34.85 weight % and the miscible blends that 0.15 weight %Weston 619 forms.The sheet material that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Sheet material is extruded continuously, be corrected to the thickness of 118 mils, then various sheet materials shearings are reached dimensional requirement.On a sheet material, detect second-order transition temperature, recording is 120 ℃.Then sheet material is regulated the four stars phases down 50% relative humidity and 60 ℃.Recording water-content is 0.23 weight %.Using the Brown thermoforming machine subsequently is in 2.5: 1 the former to stretch ratio with sheet heat forming.Thermoforming baking oven for heating device is set at 70/60/60% output, only uses top firing.In baking oven, keep the various times to measure the influence of sheet temperature sheet material to part quality, as shown in the table.Part quality stretches through volume, the calculating that detects the thermoforming parts and visual observations thermoforming parts are confirmed.Stretching is through calculating divided by the maximum part volume (embodiment A) that in this group experiment, reaches with piece volumes.Any foaming in the parts of visual observations thermoforming, the foaming degree evaluation is not for having (N), low (L) or high (H).These second-order transition temperatures of following result proof be 120 ℃ thermoplastic sheets can be under following condition can not thermoforming, this shows as can not produce under the situation that before thermoforming, does not have dry sheet material in advance has greater than 95% stretching and does not have blistered sheet material.

Embodiment 23-Comparative Examples

But use 1.25 inches single screw extrusion machine productions by the Teijin L-1250 polycarbonate of 70 weight %, the PCTG 25976 of 29.85 weight % and the miscible blends that 0.15 weight %Weston 619 forms.The sheet material that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Sheet material is extruded continuously, be corrected to the thickness of 118 mils, then various sheet materials shearings are reached dimensional requirement.On a sheet material, detect second-order transition temperature, recording is 123 ℃.Then sheet material is regulated the four stars phases down 50% relative humidity and 60 ℃.Recording water-content is 0.205 weight %.Using the Brown thermoforming machine subsequently is in 2.5: 1 the former to stretch ratio with sheet heat forming.Thermoforming baking oven for heating device is set at 70/60/60% output, only uses top firing.In baking oven, keep the various times to measure the influence of sheet temperature sheet material to part quality, as shown in the table.Part quality stretches through volume, the calculating that detects the thermoforming parts and visual observations thermoforming parts are confirmed.Stretching is through calculating divided by the maximum part volume (embodiment A and B) that in this group experiment, reaches with piece volumes.Any foaming in the parts of visual observations thermoforming, the foaming degree evaluation is not for having (N), low (L) or high (H).These second-order transition temperatures of following result proof be 123 ℃ thermoplastic sheets can be under following condition can not thermoforming, this shows as can not produce under the situation that before thermoforming, does not have dry sheet material in advance has greater than 95% stretching and does not have blistered sheet material.

Embodiment 24-Comparative Examples

Use 3.5 inches sheet materials that single screw extrusion machine production is made up of Teijin L-1250 polycarbonate.Sheet material is extruded continuously, be corrected to the thickness of 118 mils, then various sheet materials shearings are reached dimensional requirement.On a sheet material, detect second-order transition temperature, recording is 149 ℃.Then sheet material is regulated the four stars phases down 50% relative humidity and 60 ℃.Recording water-content is 0.16 weight %.Using the Brown thermoforming machine subsequently is in 2.5: 1 the former to stretch ratio with sheet heat forming.Thermoforming baking oven for heating device is set at 70/60/60% output, only uses top firing.In baking oven, keep the various times to measure the influence of sheet temperature sheet material to part quality, as shown in the table.Part quality stretches through volume, the calculating that detects the thermoforming parts and visual observations thermoforming parts are confirmed.Stretching is through calculating divided by the maximum part volume (embodiment A) that in this group experiment, reaches with piece volumes.Any foaming in the parts of visual observations thermoforming, the foaming degree evaluation is not for having (N), low (L) or high (H).These second-order transition temperatures of following result proof be 149 ℃ thermoplastic sheets can be under following condition can not thermoforming, this shows as can not produce under the situation that before thermoforming, does not have dry sheet material in advance has greater than 95% stretching and does not have blistered sheet material.

Relatively obviously visible from the data of above-mentioned related work embodiment, to compare with commercial polyesters, polyester of the present invention provides the remarkable advantage aspect second-order transition temperature, density, slow crystallization rate, melt viscosity and toughness.

Describe the present invention in detail, but it should be understood that and in purport of the present invention and scope, to change and to improve with reference to embodiment disclosed herein.

Claims

1. polymer blend, it contains at least a polyester that contains following component:

(a) dicarboxylic acid component, it contains:

I) terephthalic acid residue of 70-100 mole %;

(b) diol component, it contains:

I) 2,2,4 of 1-99 mole %, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 1-99 mole %,

The logarithmic viscosity number of wherein said polyester is 0.50 to 0.68dL/g, w/w be in phenol/tetrachloroethane of 60/40 under the concentration at 0.5g/100ml in 25 ℃ of mensuration; The Tg of wherein said polyester is 110-200 ℃.

2. compsn as claimed in claim 1, the logarithmic viscosity number of wherein said polyester is 0.55-0.68dL/g.

3. compsn as claimed in claim 1, wherein said polyester contains the residue of at least a branching agent that is useful on polyester.

4. compsn as claimed in claim 1, wherein said polyester contain the residue that has the branched monomer of 3 or more carboxyl substituents, hydroxyl substituent or its combination based on one or more of the 0-10 mole % of glycol or the total molar percentage meter of diacid residues.

5. compsn as claimed in claim 1, wherein said polymer blend contains at least a thermo-stabilizer.

6. polymer blend as claimed in claim 5, wherein said thermo-stabilizer comprise at least a following any ester or the P contained compound of salt that contain: phosphoric acid, phosphorous acid, phosphonic acids, phospho acid, phosphonous acid.

7. polymer blend as claimed in claim 6, wherein said P contained compound comprise alkyl, alkylether radicals, aryl or substituted aryl.

8. polymer blend as claimed in claim 7, wherein said P contained compound comprise branched-alkyl, substituted alkyl or difunctionality alkyl.

9. compsn as claimed in claim 1, wherein in 1/8 inch thick rod, recording said polyester with 10 mil breach according to ASTM D256 is 7.5ft-lbs/in at least 23 ℃ notched izod intensity.

10. compsn as claimed in claim 1, wherein said polyester contains the residue of at least a catalyzer, said catalyst pack sn-containing compound.

11. article of manufacture that comprises the said polymer blend of claim 1.

A 12. film or sheet material that comprises the said polymer blend of claim 1.

13. liquid crystal display film that comprises the said polymer blend of claim 1.

14. liquid crystal display film as claimed in claim 13, it comprises scatterer sheet material, compensate film or protective membrane.

15. goods as claimed in claim 11, wherein said article of manufacture through extrusion-blown modling, extrude stretch-blow, injection moulding or injection drawing blow forms.

16. film as claimed in claim 12 or sheet material, wherein said film or sheet material are through extruding or rolling formation.

17. injection-molded item that comprises the said polymer blend of claim 1.

18. goods as claimed in claim 11, it comprises one of following: medical facilities, commercial food product tableware articles for use, infant bottle, food processor, mixing machine and mixing bowl, water bottle, washing machine front end and vacuum cleaner parts, ophthalmic lens and mirror holder.

19. goods as claimed in claim 18, wherein said medical facilities comprise medical bag, health material, dialysis equipment.

20. goods as claimed in claim 18, wherein said commercial food product tableware articles for use comprise at least a in apparatus, Freshness keeping disc, food tray, steam plate and the bin.

21. an infant bottle comprises like each described polymer blend in the claim 1,4 and 9.

22. a blend, it comprises:

(a) at least a polyester of 5-95 weight % like claim 1 definition; With

(b) at least a polymeric constituent of 5-95 weight %.

23. blend as claimed in claim 22, wherein said at least a polymeric constituent is selected from following at least a: with the different polyester of the said polyester of claim 1; Polymeric amide; PS; Polystyrene copolymer; Styrene/acrylonitrile copolymer; The acrylonitrile/butadiene/styrene multipolymer; Polymethylmethacrylate, acrylic copolymer; Polyetherimide; Ppe; Or polyphenyl ether/styrene blend; Polyphenylene sulfide; Polyphenylene sulfide/sulfone; Polyester/carbonic ether; Polycarbonate; Polysulfones; Polysulfones ether; And the polyetherketone of aromatic dihydroxy compound.

24. blend as claimed in claim 23, wherein polymeric amide is a nylon, or ppe is for gathering 2, the 6-dimethylphenylene ether.

25. polymer blend as claimed in claim 1, wherein said polyester is being less than 20000 pools under 1 radian per second, in the rotation melt rheometer, 290 ℃ of melt viscosities that record.

26. like claim 1 or 25 described polymer blends, it does not comprise polycarbonate.