CN100386361C - Method of synthesizing non fiber use modified copolyester using ethylene glycol titanium catalysis - Google Patents
Method of synthesizing non fiber use modified copolyester using ethylene glycol titanium catalysis Download PDFInfo
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- CN100386361C CN100386361C CNB2005101278049A CN200510127804A CN100386361C CN 100386361 C CN100386361 C CN 100386361C CN B2005101278049 A CNB2005101278049 A CN B2005101278049A CN 200510127804 A CN200510127804 A CN 200510127804A CN 100386361 C CN100386361 C CN 100386361C
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Abstract
The present invention belongs to the field of modified copolyester, which particularly relates to a method for catalyzing and synthesizing modified copolyester for non-fiber use with titanium ethylene glycolate. The method comprises is characterized in that 1, 4-cyclohexanedimethanol(CHDM) is used as a third monomer, and PTA and ethylene glycol (EG) are used as base raw materials; titanium ethylene glycolate used as a polycondensation novel catalyst with hydrolysis resistance is used, and the high activity of the titanium ethylene glycolate is used, which enables polycondensation reaction speed to be enhanced; at the same time, through the selection of the varieties of synergistic catalysts and the regulation of optimal addition, the content of metal ions in polymers is reduced; finally, copolyester products having the advantages of middle tone and good transparence are prepared, and the intrinsic viscosity of the copolyester products is from 0.65 to 0.85 dl/g.
Description
Technical field
The invention belongs to the modified copolyester field, particularly the spent glycol titanium catalysis synthesizing non fiber method of modified copolyester.
Background technology
In the engineering plastics field, low-crystallinity or amorphism polyethylene terephthalate resin have been used to make plastic prods such as sheet material, sheet material and film.Polyethylene terephthalate belongs to the hemicrystalline superpolymer, under common processing conditions, can make product produce certain degree of crystallinity, and this point is very disadvantageous for plastics such as preparation polyester transparent sheet materials.Therefore, adopting the 3rd monomer to carry out modification by copolymerization, thereby the macromolecular regularity of polyethylene terephthalate is damaged, prepare the modified copolyester of noncrystalline or low-crystallinity, is an important channel that obtains the clear sheet polyester material.
U.S. Pat P5385773 (Eastman Chemical Company) discloses by dimethyl terephthalate (DMT) (DMT), ethylene glycol (EG) and 1,4-cyclohexanedimethanol (CHDM) is a reaction monomers, the synthetic method for preparing the 1,4 cyclohexane dimethanol modified copolyester.In preparation process, adopt zinc acetate, manganese acetate, titanium isopropylate and germanium oxide as catalyst for reaction, triethyl phosphate is as the stablizer of reaction, the conjugated polyester resin that has obtained having the better transparency through the rhythmic reaction process of transesterify and polycondensation.
U.S. Pat P5681918 (Eastman Chemical Company) has reported by pure terephthalic acid (PTA), ethylene glycol (EG) and 1,4-cyclohexanedimethanol (CHDM) is a basic raw material, the mol ratio 69/31 of control EG and CHDM, dibasic alcohol (EG+CHDM) is 1.4～1.7 (excessive part is EG) with the mol ratio of diprotic acid (TPA), adopt direct esterification technology, as catalyst for reaction, the mineral dye Cobaltous diacetate is as the toning agent of copolyesters product with tetra isopropyl titanium.Through the conjugated polyester resin that has obtained having the better transparency after the polycondensation.The intrinsic viscosity of copolyesters [η] scope is: 0.6～0.8dL/g.
The organic compound of U.S. Pat P6342579 (SK Chemical Company) employing titanium or titania-silica coprecipitate are as catalysts, phosphoric acid or organic phosphoric acid are stablizer, pure terephthalic acid (PTA), ethylene glycol (EG) and 1,4-cyclohexanedimethanol (CHDM) is a reactant, adopt direct esterification technology, prepared transparent good 1,4-cyclohexanedimethanol modification polyethylene terephthalate resin, its intrinsic viscosity [η] scope is: 0.7～0.85dL/g.
Summary of the invention
A purpose of the present invention provides the method for a kind of spent glycol titanium catalysis synthesizing non fiber with modified copolyester, adopt novel polycondensation catalyst system, polymerization rate is improved, and makes the intrinsic viscosity transparency all can satisfy the requirement of production polyester transparent sheet material.
Another object of the present invention provides the preparation method with di-carboxylic acid component and diol component modified copolyester.
The difference of the present invention and prior art has been to adopt a kind of polycondensation catalyst titanium ethylene glycolate of novel hydrolysis, utilize its high reactivity, condensation polymerization speed is improved, by to the kind selection of synergistic catalyst and the adjustment of optimal addn, reduced the content of metal ion in polymkeric substance simultaneously.Finally prepare have neutralc tint, limiting viscosity height, the good copolyesters product of the transparency.
Spent glycol titanium catalysis synthesizing non fiber of the present invention may further comprise the steps with the method for modified copolyester:
(1). esterification
With terephthalic acid and dibasic alcohol with mol ratio be 1: 1.05～2.2 ratio directly add or be prepared into slurry after join in the reactor, at 0.1～0.4MPa nitrogen pressure, and carry out esterification under 230～265 ℃ of conditions, generate terephthalic acid and mix diol ester or its oligopolymer;
(2). polycondensation
More than 250 ℃, the reactor that step (1) is equipped with the mixed diol ester of terephthalic acid or its oligopolymer constantly vacuumizes, in 20～30 minutes, making the pressure in the still is 10～150Pa, constantly distillate by product ethylene glycol and 1 in this process, the 4-cyclohexanedimethanol, the control reaction is warm eventually at 280～290 ℃, make reactive system return to normal pressure with nitrogen then, obtain polymer melt, polymer melt is carried out the Cast Strip pelletizing, obtain limiting viscosity in 0.65～0.85dl/g and the good modified copolyester section of form and aspect;
Add titanium ethylene glycolate in the esterification stage, play synergistic zn cpds and germanium compound catalyzer and cobalt compound toning agent; The organic compound stablizer that adds phosphorus in polycondensation phase.
The addition of described titanium ethylene glycolate is to be 3～30ppm with the content of titanium in the modified copolyester gross weight, and being preferably 5～15ppm is benchmark.
The addition of described zn cpds is to be 60～160ppm with the content of zinc in the modified copolyester gross weight, and being preferably 65～120ppm is benchmark.
The addition of described germanium compound is to be 80～180ppm with the content of germanium in the modified copolyester gross weight, and being preferably 100～150ppm is benchmark.
The addition of described cobalt compound is to be 10～80ppm with the content of cobalt in the modified copolyester gross weight, and being preferably 20～60ppm is benchmark.
The addition of described phosphorus compound is to be 10～70ppm with phosphorus at the middle content of modified copolyester gross weight, and being preferably 20～60ppm is benchmark.
Described diol component contains 10～95% moles ethylene glycol and 5～90% moles 1,4 cyclohexane dimethanol, and wherein 1,4 cyclohexane dimethanol can be cis or trans isomer, or two kinds of mixture of isomers.
Described zn cpds is selected from a kind of in zinc acetate, zinc nitrate, the zinc lactate etc.; Described germanium compound is a germanium oxide etc.
Described cobalt compound is selected from a kind of in Cobaltous diacetate tetrahydrate, cobaltous phosphate, the Xiao Suangu etc.
The organic compound of described phosphorus is selected from a kind of in trialkylphosphate, Triphenyl phosphate or the phosphoric acid etc.
The present invention is with 1,4-cyclohexanedimethanol (CHDM) is the 3rd monomer, pure terephthalic acid (PTA), ethylene glycol (EG) is basic raw material, and it is high and have a modified copolyester product that use in the engineering plastics field that is applicable to of good transparency to have prepared intrinsic viscosity.Main innovate point of the present invention is to use novel polymerization catalyst system, thereby makes the speed of polycondensation obtain significantly improving.Meanwhile, compare with traditional polycondensation catalyst tetrabutyl titanate, the use of new catalyst titanium ethylene glycolate has reduced the content of metallic impurity in the copolyesters product, makes the transparency of product obtain certain improvement.
The resulting modified copolyester product of the present invention is carried out performance test by GB/T14189-93, and the gained result is as follows: intrinsic viscosity 0.65-0.85dl/g, the b value is between-2～3.The modified copolyester section that the present invention obtains can be used for the production of polyester engineering plastics such as transparent polyester sheet material, sheet material; Can carry out blend with polycarbonate (PC) in the production process, partly or entirely substitute PC, thereby the cost of this series products is reduced significantly.This is for improving the conventional polyester value-added content of product, and changing the situation that present like product all depends on import has crucial meaning.
Embodiment
The following examples are to set forth rather than limit category of the present invention.Except as otherwise noted, all umber and percentage ratio all are that weight with modified copolyester is benchmark among the embodiment.
Embodiment 1:
At one nitrogen inlet is housed, add 996 gram pure terephthalic acids (PTA) in the 5L stainless steel cauldron of condensation product outlet and agitator, 372 gram ethylene glycol (EG) and 345.6 grams 1,4-cyclohexanedimethanol (CHDM), the zinc acetate that is equivalent to 78ppm zinc, the germanium dioxide of the Cobaltous diacetate of 30ppm cobalt and 110ppm germanium, arrive 0.3MPa with nitrogen pressure then, keep constant voltage, temperature rise to 250 ℃ in the reactor, when the amount that distillates water byproduct in the question response still reaches theoretical aquifer yield, the still internal pressure reverts to normal pressure, in still, add titanium ethylene glycolate that is equivalent to the 5ppm titanium and the trimethyl phosphite 99 that is equivalent to 60ppm phosphorus then, vacuumize the pressure that makes in the polymeric kettle and in 20 minutes, be reduced to 100Pa, reaction is 95 minutes under this pressure, react whole temperature control at 280～290 ℃, make reactive system return to normal pressure with nitrogen then, polymer melt obtains water white product after the pelletizing of Cast Strip.Intrinsic viscosity [η] and form and aspect b value test result are as shown in table 1.
Comparative example 1
Comparative example 1 relative embodiment 1 changes the kind and the add-on of catalyzer under the constant prerequisite of other condition, obtained contrast and experiment, and is as shown in table 1.The result shows: the selected catalyst glycol titanium of the present invention will obviously be better than traditional polycondensation catalyst tetrabutyl titanate.
Table 1 embodiment 1 and comparative example 1 reaction conditions and product performance
| Routine number | Catalyzer | Add-on (ppm) | Reaction times (min) | Intrinsic viscosity (dL/g) | Form and aspect (b value) |
| Embodiment 1 | C-1 | 5 | 95 | 0.775 | 0.65 |
| Comparative example 1 | C-2 | 12 | 114 | 0.726 | 2.04 |
Annotate: C-1: titanium ethylene glycolate
C-2: tetrabutyl titanate
Embodiment 2:
At one nitrogen inlet is housed, in the 5L stainless steel cauldron of condensation product outlet and agitator, add 996 gram pure terephthalic acids (PTA), 372 gram ethylene glycol (EG) and 345.6 grams 1,4-cyclohexanedimethanol (CHDM), the zinc acetate that is equivalent to 78ppm zinc, the germanium dioxide of the Cobaltous diacetate of 30ppm cobalt and 110ppm germanium, arrive 0.3MPa with nitrogen pressure then, keep constant voltage, temperature rise to 250 ℃ in the reactor, when the distilled water byproduct reaches theoretical amount in the question response still, the still internal pressure reverts to normal pressure, adds titanium ethylene glycolate that is equivalent to the 12ppm titanium and the trimethyl phosphite 99 that is equivalent to 60ppm phosphorus in still, vacuumizes, make pressure in 20 minutes, be reduced to 100Pa, kept this vacuum tightness 55 minutes, and reacted whole temperature control, eliminate vacuum to normal pressure with nitrogen then at 280～290 ℃, obtain colourless and transparent polyester strip, pelletizing.Intrinsic viscosity and b value test result are as shown in table 2.
Comparative example 2
Comparative example 2 relative embodiment 2 change the add-on of titanium ethylene glycolate under the constant prerequisite of other condition, obtained contrast and experiment.The result shows: by the adjustment to the titanium ethylene glycolate amount, the add-on that improves titanium ethylene glycolate can make polycondensation reaction time obviously descend, the may command reaction times.
Table 2 embodiment 2 and comparative example 2 reaction conditionss and product performance
| Routine number | Catalyzer | Add-on (ppm) | Reaction times (min) | Intrinsic viscosity (dL/g) | Form and aspect (b value) |
| Embodiment 2 | C-3 | 12 | 55 | 0.796 | 1.65 |
| Comparative example 2 | C-4 | 8 | 65 | 0.812 | 0.81 |
Annotate: C-3: titanium ethylene glycolate
C-4: titanium ethylene glycolate
Embodiment 3:
At one nitrogen inlet is housed, in the 5L stainless steel cauldron of condensation product outlet and agitator, add 996 gram pure terephthalic acids (PTA), 435 gram ethylene glycol (EG) and 86.4 grams 1,4-cyclohexanedimethanol (CHDM), the zinc nitrate that is equivalent to 90ppm zinc, the cobaltous phosphate of 37ppm cobalt, the titanium ethylene glycolate of the germanium dioxide of 132ppm germanium and 5ppm titanium, arrive 0.3MPa with nitrogen pressure then, keep constant voltage, temperature rise to 250 ℃ in the reactor, when the distilled water byproduct reaches theoretical amount in the question response still, the still internal pressure reverts to normal pressure, adds the trimethyl phosphite 99 that is equivalent to 30ppm phosphorus in still, vacuumizes, make pressure in 30 minutes, be reduced to 100Pa, kept this vacuum tightness 80 minutes, and reacted whole temperature control, eliminate vacuum to normal pressure with nitrogen then at 280～290 ℃, obtain colourless and transparent polyester strip, pelletizing.Intrinsic viscosity is 0.726dl/g, b value 1.97.
Embodiment 4:
At one nitrogen inlet is housed, in the 5L stainless steel cauldron of condensation product outlet and agitator, add 996 gram pure terephthalic acids (PTA), 475 gram ethylene glycol (EG) and 259.2 grams 1,4-cyclohexanedimethanol (CHDM), the zinc nitrate that is equivalent to 120ppm zinc, the Xiao Suangu of 48ppm cobalt, the titanium ethylene glycolate of the germanium dioxide of 173ppm germanium and 5ppm titanium, arrive 0.3MPa with nitrogen pressure then, keep constant voltage, temperature rise to 250 ℃ in the reactor, when the distilled water byproduct reaches theoretical amount in the question response still, the still internal pressure reverts to normal pressure, adds the trimethyl phosphite 99 that is equivalent to 30ppm phosphorus in still, vacuumizes, make pressure in 30 minutes, be reduced to 100Pa, kept this vacuum tightness 75 minutes, and reacted whole temperature control, eliminate vacuum to normal pressure with nitrogen then at 280～290 ℃, obtain colourless and transparent polyester strip, pelletizing.Intrinsic viscosity is 0.747dl/g, b value 2.33.
Claims (4)
1. a spent glycol titanium catalysis synthesizing non fiber is with the method for modified copolyester, and it is characterized in that: this method may further comprise the steps:
(1). esterification
With terephthalic acid and dibasic alcohol with mol ratio be 1: 1.05～2.2 ratio directly add or be prepared into slurry after join in the reactor, at 0.1～0.4MPa nitrogen pressure, and carry out esterification under 230～265 ℃ of conditions, generate terephthalic acid and mix diol ester or its oligopolymer;
Add titanium ethylene glycolate in the esterification stage, play synergistic zn cpds and germanium compound catalyzer and cobalt compound toning agent; The organic compound stablizer that adds phosphorus in polycondensation phase;
(2). polycondensation
More than 250 ℃, the reactor that step (1) is equipped with the mixed diol ester of terephthalic acid or its oligopolymer constantly vacuumizes, in 20～30 minutes, making the pressure in the still is 10～150Pa, constantly distillates by product ethylene glycol and 1,4 cyclohexane dimethanol in this process, the control reaction is warm eventually at 280～290 ℃, obtain polymer melt, polymer melt is carried out the Cast Strip pelletizing, obtain the modified copolyester section;
Described diol component contains 10～95% moles ethylene glycol and 5～90% moles 1,4 cyclohexane dimethanol, and wherein 1,4 cyclohexane dimethanol is cis or trans isomer, or two kinds of mixture of isomers;
The addition of described titanium ethylene glycolate is to be that 3～30ppm is a benchmark with the content of titanium in the modified copolyester gross weight;
The addition of described zn cpds is to be that 60～160ppm is a benchmark with the content of zinc in the modified copolyester gross weight;
The addition of described germanium compound is to be that 80～180ppm is a benchmark with the content of germanium in the modified copolyester gross weight;
The addition of described cobalt compound is to be that 10～80ppm is a benchmark with the content of cobalt in the modified copolyester gross weight;
Described zn cpds is selected from a kind of in zinc acetate, zinc nitrate, the zinc lactate;
Described germanium compound is a germanium oxide;
Described cobalt compound is selected from a kind of in Cobaltous diacetate tetrahydrate, cobaltous phosphate, the Xiao Suangu.
2. method according to claim 1 is characterized in that: the limiting viscosity of described modified copolyester section is at 0.65～0.85dl/g.
3. method according to claim 1 is characterized in that: the addition of described phosphorus compound is to be that 10～70ppm is a benchmark with the content of phosphorus in the modified copolyester gross weight.
4. method according to claim 1 is characterized in that: the organic compound of described phosphorus is selected from a kind of in trialkylphosphate, Triphenyl phosphate or the phosphoric acid.
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| CNB2005101278049A CN100386361C (en) | 2005-12-06 | 2005-12-06 | Method of synthesizing non fiber use modified copolyester using ethylene glycol titanium catalysis |
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| CNB2005101278049A CN100386361C (en) | 2005-12-06 | 2005-12-06 | Method of synthesizing non fiber use modified copolyester using ethylene glycol titanium catalysis |
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| CN100386361C true CN100386361C (en) | 2008-05-07 |
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| JP6496245B2 (en) * | 2012-09-24 | 2019-04-03 | エスケー ケミカルズ カンパニー リミテッド | Method for producing polycyclohexylene dimethylene terephthalate resin excellent in color and polycyclohexylene dimethylene terephthalate resin produced thereby |
| CN107216449B (en) * | 2017-07-25 | 2019-04-23 | 合复新材料科技(无锡)有限公司 | A kind of technology of preparing of PCT/PET copolyesters high molecular material |
| CN112608230A (en) * | 2020-11-17 | 2021-04-06 | 银金达(上海)新材料有限公司 | Low-metal-ion PETG material and application thereof |
| CN113185682B (en) * | 2021-04-27 | 2022-08-12 | 中国石油化工股份有限公司 | Modified copolyester and preparation method thereof |
| CN114891189B (en) * | 2022-06-30 | 2023-10-31 | 中国天辰工程有限公司 | Preparation method of low-chroma PETG copolyester |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121727A (en) * | 1993-04-27 | 1996-05-01 | 伊斯曼化学公司 | Copolyester of cyclohexanedimethanol and process for producing such polyester |
| US5681918A (en) * | 1996-02-20 | 1997-10-28 | Eastman Chemical Company | Process for preparing copolyesters of terephthalic acid ethylene glycol and 1 4-cyclohexanedimethanol exhibiting a neutral hue high clarity and increased brightness |
| CN1328072A (en) * | 2001-07-05 | 2001-12-26 | 济南齐鲁化纤集团有限责任公司 | High-activity catalyst and its application in synthesizing polyester |
| US6342579B2 (en) * | 2000-05-17 | 2002-01-29 | Sk Chemical Co., Ltd. | Method for preparing polyester resin copolymerized with 1,4-cyclohexanedimethanol |
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2005
- 2005-12-06 CN CNB2005101278049A patent/CN100386361C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121727A (en) * | 1993-04-27 | 1996-05-01 | 伊斯曼化学公司 | Copolyester of cyclohexanedimethanol and process for producing such polyester |
| US5681918A (en) * | 1996-02-20 | 1997-10-28 | Eastman Chemical Company | Process for preparing copolyesters of terephthalic acid ethylene glycol and 1 4-cyclohexanedimethanol exhibiting a neutral hue high clarity and increased brightness |
| US6342579B2 (en) * | 2000-05-17 | 2002-01-29 | Sk Chemical Co., Ltd. | Method for preparing polyester resin copolymerized with 1,4-cyclohexanedimethanol |
| CN1328072A (en) * | 2001-07-05 | 2001-12-26 | 济南齐鲁化纤集团有限责任公司 | High-activity catalyst and its application in synthesizing polyester |
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