CA2098084A1 - Amorphous, aromatic polyester containing impact modifier - Google Patents

Amorphous, aromatic polyester containing impact modifier

Info

Publication number
CA2098084A1
CA2098084A1 CA002098084A CA2098084A CA2098084A1 CA 2098084 A1 CA2098084 A1 CA 2098084A1 CA 002098084 A CA002098084 A CA 002098084A CA 2098084 A CA2098084 A CA 2098084A CA 2098084 A1 CA2098084 A1 CA 2098084A1
Authority
CA
Canada
Prior art keywords
weight
percent
units derived
monomer
vinyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002098084A
Other languages
French (fr)
Inventor
William G. Carson
Choung-Houng Lai
Edward J. Troy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rohm and Haas Co
Original Assignee
Rohm and Haas Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rohm and Haas Co filed Critical Rohm and Haas Co
Publication of CA2098084A1 publication Critical patent/CA2098084A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/902Core-shell

Abstract

ABSTRACT
Impact modifiers which produce transparent, high notched Izod impact strength blends with amorphous, aromatic polyesters are described. The impact modifiers are core-shell polymers with cores comprised mainly of rubbery polymers of diolefins and vinyl aromatic monomers and shells comprised mainly of styrene copolymers (e.g. styrene and hydroxyalkyl (meth)acrylate).

Description

209~8~
FIELD OF INVENTION
This invention relates to polymer compositions for improving impact strength of clear, amorphous aromatic polyester, processes therein, and improvedpolyester blends, and articles produced therefrom.
BACKGROUND OF THE INVENTION
The present invention concerns an impact modifier composition which significantly improves the notched impact resistance while maintaining clarity of an amorphous aromatic polyester resin (hereafter referred to as polyester). More specifically, the present invention concerns an impact modifier composition which contains a rubbery polymer and a polymer containing a hydroxyl group or another functional group which acts in a similar manner as the hydroxyl group.
Polyesters (e.g., polyethylene terephthalate, polybutylene terephthalate, etc.) exhibit various excellent properties such as resistance to temperature, chemicals, weathering, radiation and burning and also exhibit excellent clarity (in amorphous form), reasonable cost, as well as moldability. Accordingly, polyesters are used for various purposes (e.g., fibers, films, molded and extruded products, etc.) The notched impact resistance of the polyester, however, is less than satisfactory. Plastics such as poly (butylene terephthalate) (PBT) and poly(ethylene terephthalate) (PET) have insufficient notched impact strength, and many attempts have been made to 2 0 improve the impact strength. Many agents have been proposed to improve the impact strength. These are added to resins and subjected to melt-blending. In particular, when a cut (notch) is created in a molded or extruded part, the impact resistance of polyester is poor, and consequently notched impact strength must be further improved for polyester articles.
2 5 Various attempts have been made using conventional fibrous inorganic fillers (e.g., glass fiber, asbestos fiber, etc.) to improve the impact resistance of polyester. Evell when these methods are implemented, however, the impact resistance improvement is less than satisfactory and clarity in amorphous polyesters is adversely affected.
3 0 Various techni-l-les wllerein rubbery polymers or rubber- containing polymers are mixed with polyesters have been developed to improve the impact resistance of polyesters and thermopl.lstic materials. Specifically, certain core-shell polymers comprising a core made of rubbery polymer and a shell, around the core,made of a glass~ polymer are excellent agents for improvement of notched impact 3 5 strength of polvesters ~vhere clarit~ is not an object.

- . ., '- : ' ' ':
-,: - ' ' 2V9808~
When these prior art methods are used, the polyester resin generally exhibits poor compatibility with the shell of the rubber-containing polymer, and therefore impact resistance (especially notched Izod impact resistance) is not fully optimized.
Even when these prior art core-shell modifiers are added to amorphous polyestersS and found to produce ductile, notched breaks, the clarity of amorphous polyester resins is destroyed. An amorphous polyester may contain a small amount of crystallinity, but the level must be low enough so that clarity is not adverselyaffected. Further, although the polyester may be crystallized under certain conditions, in the present invention the molding and cooling conditions are suchl O that crystallization (and loss of clarity) is avoided.
Lane, U.S. Patent 4,034,013 teaches core/shell polymers functionalized with an epoxy group, such as a shell of methyl methacrylate/glycidyl methacrylate, to improve the melt strength of polyesters. Although Lane broadly teaches butadiene-based elastomers with optional minor amounts of styrene in the core and teaches I S styrene as a major component of the outer stage, she does not teach or suggest a solution to preparing an efficient impact modifier which will retain clarity in the amorphous polyester.
Kishimoto et al., Japanese Kokai 54-48850, disclose butadiene-based core/shell polymers with hydroxyalkyl groups in the shell portion as modifiers for crystalline 2 0 polyesters, such as poly(butylene terephthalate), but do not teach the means to modify such core/shell polymers to make them useful as impact modifiers in clear, amorphous polyesters.
The object of the present invention is to provide a composition for improving the impact strength of polyesters, such as PET or PET copolyesters, when 2 S they are processed into clear, tough objects while retaining their amorphous nature.
The composition will provide toughA ductile notched Izod breaks (> 10 ft. Ibs./in., at room temperature) at loadings of 25(7o or less in amorphous polyesters and copolyesters. It is another objective that said composition provide tough ductile notched Izod breaks ~ithout red-lcing the transparency of amorphous polyesters.3 0 Another object is to provide a composition which will also overcome the embrittlemen~ caused bv physical aging which commonly occurs in amorphous aromatic polyesters when conditioned at temperatures approaching glass transition temperature (Tg). A further object is to provide a process for making an impact modifier composition for improving the impact strength of polyester. A still 3 S further object is to provide clear amorphous extrusion/melt shaped or injection molded PET or PET copolyester articles.

- . - . , - - : . . . .
.
-, .

209808~
SUMMARY OF THE INVENTION
In the instant invention, impact strength of amorphous aromatic polyesters is increased substantially by the addition of small amounts of certain core-shell modifiers which disperse very readily in aromatic polyesters and do not detract from clarity. These and other objects as will become apparent from the following disclosure are achieved by the present invention which comprises in one aspect acomposition for improving the impact strength characteristics of aromatic polyesters, such as PET in amorphous form.
The impact modifier composition of this invention is a core-shell polymer with a core comprised mainly of a rubbery core polymer such as a copolymer containing a diolefin, preferably a 1,3-diene, and a shell polymer comprised mainly of a vinyl aromatic monomer such as styrene, and hydroxyalkyl (meth)acrylate or,in the alternative, another functional monomer which acts in a manner similar tothe hydroxyalkyl (meth)acrylate).
Ihere are two general types of impact modifiers meeting this description. In the preferred case, for lowest raw material cost, is a core-shell impact modifier composition comprising:
(A) from about 40 to about 65 parts by weight of a core polymer comprising: fromabout 40 to about 60 percent by weight of units derived from at least one vinyl 2 0 aromatic monomer, from about 60 to about 40 percent by weight of units derived from a 1,3-diene monomer, such as isoprene, 3-chlorobutadiene or butadiene, optionally, up to about 5 percent by weight of at least one cross-linking or graft-linking monomer, and optionally up to about 1070 by weight of units derived from at least one copolymerizable vinyl or vinylidene 2 5 monomer;
(B) from about 35 to about 60 parts by weight of a shell polymer comprising: from about 2 to about 40 percent by weight of units derived from a hydroxyalkyl (meth)acrylate, and from about 60 to about 9~ percent by weight of a vinyl aromatic monomer; and up to about 25 percent by weight of one or more 3 0 copolvmerizable vinyl or vinylidene monomers. Intermediate shells may also be present.
The second tvpe utilizes a ~inyl aromatic monomer of high refractive index chosen from the class of polybromoaromatic monomers and polycyclic aromatic monomers Sucll monomers include dibromostyrene, tribromostyrene, 3 :~ tetrabromostyrelle, monometllyldibromostyrene, vinyl naphthalene, isopropenyl naphthalene, and the like. Because these monomers are more effective in raising .
., :

2~98~8~
refractive index, they may be used in lesser amounts, allowing more diolefin to be present in the core polymer or a higher amount of core in the core/shell polymer.
In this instance, the invention encompasses a core-shell impact modifier composition comprising:
S (C) from about 40 to about 90 parts by weight of a core polymer comprising: from about 20 to about ~0 percent by weight of units derived from at least one vinyl aromatic monomer of high refractive index, from about 40 to about 80 percent by weight of units derived from a 1,3-diene monomer, such as isoprene, 3-chlorobutadiene or butadiene, optionally from about 0.05 to about 5 percent by l O weight of a cross-lir,king monomer; and optionally up to about 10qo by weight of units derived from a copolymerizable vinyl or vinylidene monomer.
(D) from about 10 to about 60 parts by weight of a shell polymer comprising: from about 2 to about 40 parts by weight derived from a hydroxyalkyl (meth)acrylate, and from about 60 to about 98 percent by weight of a vinyl l S aromatic monomer; and up to about 25 percent by weight of one or more copolymerizable vinvl or vinylidene monomers.
In the present invention, the hydroxyalkyl (meth)acrylate may be replaced by a monomer chosen from at least one of the group consisting of epoxyalkyl (meth)acrylates, (meth)acrylonitriie, cyanoalkyl (meth)acrylates, cyanoalkoxyalkyl 2 0 (meth)acrylates, monomers containing an allyl group and a hydroxyl group, and vinylaromatic monomers containing at least one hydroxyl group, preferably non-phenolic.
A further variation of the impact modifier structure is to form a three-stage polymer with a hard-core comprising at least 80 percent of units derived from at2 S least one vinyl aromatic monomer. This hard-core may have units derived from a diene monomer, such as butadiene, or from other copolymerizable vinyl or .
vinylidene monomers. The hard-core may contain up to about 5 percent by weight of units derived from at least one graft-linking or cross-linking monomer. The hard-core may be from about 10 to about 50 weight percent of the total impact 3 0 modifier. The hard-core technology, based on U.S. Patents 3,793,402 and 3,971,835, offers a means to add a vinyl aromatic monomer to adjust the refractive index upwards without requiring that monomer to be copolymerized with the diene monomer and thus adversely affect the rubbery characteristics of the copolymer.
Another aspect of the invention is the blending of the impact modifier 3 S compositiotl with at least one aromatic polyester and/or copolyester at a weight ratio of about 99/1 to about 70/30 of polyester/impact modifier, the polyester remaining , - - .' .

209808~
amorphous. A still further aspect of the invention comprises molded parts, bottles, sheet, films, pipes, foams, containers, profiles, or other articles prepared in accordance vith the above-mentioned compositions and blends.
DETAILED DESCRIPTION OF THE INVENTION
It has been found that certain core-shell impact modifiers produce clear, and unexpectedly tough blends with amorphous aromatic polyesters. These modifiers produce a large increase in impact strength, while maintaining excellent opticalclarity of the polyesters. These modifiers have cores composed principally of rubbery polymers, such as copolymers of diolefins with vinyl aromatic monomers, l 0 such as copolymers of butadiene with styrene, and shells composed principally of vinyl aromatic copolymers (e.g. styrene/hydroxyalkyl (meth)acrylate copolymers).For example, the vinyl aromatic core-shell impact modifiers (i.e. "modifiers") which give this unexpected result contain shells derived from copolymers of vinyl aromatic monomers with certain hydroxyalkyl (meth)acrylates, for example, l S hydroxyethyl (meth)acrylate (HEMA), hydroxypropyl (meth)acrylate (HPMA), 4-hydroxybutyl acrylate, ethyl alpha-hydro>;ymethylacrylate, or hydroxyethyl acrylate (HEA), or other copolymerizable monomers containing one or more hydroxyl groups, such as allyl cellosolve, allyl carbinol, methylvinyl carbinol, allyl alcohol, methallyl alcohol, and the like. Also included are other monomers which function2 0 in a similar manner, for example, glycidyl methacrylate (GMA), 3,4-epoxybutyl - acrylate, acrylonitrile, methacrylonitrile, beta-cyanoethyl methacrylate, beta-cyanoethyl acrylate, cyanoalkoxyalkyl (meth)acrylates, such as omega-cyano-ethoxyethyl acrylate, or omega-cyanoethoxyethyl methacrylate, (meth)acrylamides,such as methacrylamide or acrylamide, N-monoalkyl (meth)acrylamides, such as N-2 5 methylacrylamide or N-t-butylacrylamide or N-ethyl (meth)acrylamide, or vinyl monomers containing an aromatic ring and an hydroxyl group, preferably non-phenolic, such as vinylphenol, para-vinylbenzyl alcohol, meta-vinylphenethyl alcohol, and the like. Styrene homopolymer and other styrene copolymers and terpolymers, such as styrene/methyl methacrylate are very much less effective;
3 0 The monomer concentrations in the cores and shells of the modifier composition are adjusted to provide a refractive index (RI) to match that of thepolyesters ~vith ~vhich they are blended (i.e. about 1.55 to about 1.58). This produces a clear blend under processing conditions ~vhich will maintain the polyester in its amorphous form. Almost all rubbery polymers (e.g. core polymers) have RI's well 3 S below tnis range. Therefore it is necessary that the rubber phase concentration of the impact modifier composition be kept relatively low and the other components of s . .

.

2 0 ~ ~ O ~ Ll the modifier be used to brirlg the RI into the desired range. However, the impact strength obtainable with a given concentration of any core-shell impact modifiertends to vary directly with the amount of rubber polymer in the modifier. This means that high RI modifiers having low rubber contents have to be exceptionallyS efficient to produce good toughening.
From a practical standpoint the most desirable monomer to produce rubbery polymer for this application is butadiene whose homopolymer has a RI=1.52. It has the best combination of RI, cost, stability, and processability. For the same reasons, styrene is the most desirable component for the rest of the modifier. However, even 10 if butadiene and styrene were the only components of the modifier, a butadiene/styrene ratio ranging from about 50/50 to 20/80 would be required for the modifier RI to be in the 1.55 to 1.58 range needed for matching the RI's of amorphous, aromatic polyesters. One skilled in the art of impact modification would expect a 50'~0 concentration of butadiene to be very low for good core-shell l S impact modifier efficiency. The results found herein for modification of polyesters with such functionalized "rubber-poor" modifiers are surprisingly good.
In response to the need to match RI's of amorphous aromatic polyesters and simultaneously have excellent impact modifier efficiency, it was unexpectedly discovered that when low concentrations of certain hydroxyalkyl (meth)acrylates are 2 0 copolymerized with aromatic vinyl monomers to form the shell polymer of core-shell impact modifiers having RI's in the 1.55 to 1.58 range, very high notched Izod impact strengths are obtained with amorphous polyesters at 3070 or lower modifier loadings, and preferably at from about 5 to about 20/;7o loadings. Substitution of the hydroxyalkyl methacrylate with other functional monomers promoting 2 5 compatibility of the shell with the polvester will give similar results in impact improvement and maintenance of clarity.
The requirement for a "rubber-poor" modifier can be relaxed somewhat if the vinyl aromatic monnmer is changed from styrene, vinyl toluene, para-methylstyrene, monochlorostyrene and the like to one of high refractive index, viz., 3 0 the polybrominated vinyl aromatics or the po!ycyclic vinyl aromatics.
The core polymer in the impact modifier composition is a rubbery polymer and generally comprises a copolymer of butadiene and a vinyl aromatic monomer.
The rubbery polvmer may include diene rubber copolymers (e.g., butadiene-styrenecopolymer, butadiene-styrene-(meth)acrylate terpolymers, butadiene-styrene-3 5 acrylonitrile terpolymers, isoprene-styrene copolymers, etc.). Of the afore-mentioned rubbery polymers, those which can be produced as a latex are especially 2~D9808~
desirable. In particular, a butadiene-vinyl aromatic copolymer latex obtained as a result of emulsion polymerization is preferred. In the core polymer, a partiallycrosslinked polymer can also be employed if crosslinking is moderate. Further, at least one of a cross- or graft- linking monomer, otherwise described as a multi-5 functional unsaturated monomer, can also be employed. Such monomers includedivinylbenzene, diallyl maleate, butylene glycol diacrylate, allyl methacrylate, and the like.
The ratio of comonomers in the core depends on the desired core-shell ratio and hardness of the rubber phase. The ratio range of butadiene to the vinyl 1 0 aromatic in the core polymer is 70/30 to 40/60 (parts by weight). If the quantity added is below~ 40 parts by weight butadiene, it is difficult to improve the impact resistance. If the quantity added exceeds 70 parts by weight butadiene on the other hand, it is difficult to obtain a high enough RI modifier to match that of the polyester, unless the vinyl aromatic monomer is of high refractive index and 15 selected from the polybrominated or polycyclic monomers described above.
Optionally, a small concentration, from about 0.01 up to about 5, and preferablyfrom about 0.1 up to about 2 percent, by weight of a crosslinking monomer, such as divinyl benzene or butylene glycol dimethacrylate is included, and optionally about 0.01 to about 5 percent by ~veight of a graftlinking monomer for tying the core and 2 0 shell together, such as allyl maleate may be included in the rubbery core polymer.
Further examples of crosslinking monomers include alkanepolyol polyacrylates or polymethacrylates such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, oligoethylene glycol diacrylate, oligoethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, 2 5 trimethylolpropane triacrylate or trimethylolpropane trimethacrylate, and unsaturated carbo:;ylic acid allyl esters such as allyl acrylate, allyl methacrylate or diallyl maleate.
As the she]l polymer of the impact modifier composition, a hydroxyl-group-containing monomer is preferred to be employed. When a hydroxyl group is 3 0 introduced to the shell polymer, a ~ inyl monomer containing an active double-bond segment and a hydroxyl group (hereafter referred to as hydroxyl-group-containing monomer) is copolymerized t~ith another copolymerizable vinyl monomer. Examplés of the aforementioned hydroxyl-group-containing monomers include hydroxyalkyl (meth)acrylate or alpha-hydroxymethylacrylate esters, such as 3 5 hydroxyethyl (meth)acrylate, hydroxypropvl (meth)acrylate, or ethyl hvdro:;ymetllylacrvl.lte, allyl deri~atives of hydroxyl-group containing compounds, 209~08~
such as allyl cellosolve, allyl carbinol, methylvinyl carbinol, allyl alcohol, methallyl alcohol, and the like, vinyiphenol, para-vinylbenzyl alcohol, meta-vinylphenethyl alcohol, and the like.
Although the hydroxyalkyl (meth)acrylate monomers are preferred for reasons of safety in handling (over the nitrile-containing monomers) or availability (over other monomers taught herein), other monomers which function in a similar manner may be employed, for example, glycidyl methacrylate (GMA), 3,4-epoxybutyl acrylate, acrylonitrile, methacrylonitrile, beta-cyanoethyl methacrylate, beta-cyanoethyl acrylate, cyanoalkoxyalkyl (meth)acrylates, such as omega-cyanoethoxyethyl acrylate, or omega- cyanoethoxyethyl methacrylate, (meth)acrylamide, or N-monoalkyl (meth)acrylamide and the like.
Vinyl monomers to be copolymerized with the aforementioned hydroxyl-group-containing monomers include vinyl aromatic monomers such as styrene, alpha-methyl styrene, para-methyl styrene, chlorostyrene, vinyl toluene, dibromostyrene, tribromostyrene, vinyl naphthalene, isopropenyl naphthalene, andthe like. The hydroxyl-group-containing monomers and vinyl aromatic monomers may be used either singly or in combination of two or more.
In the shell polymer, the ratio bet~veen the hydroxyl- group-containing monomer (e.g. HEMA, HPMA) or a monomer which performs in a similar manner 2 0 (e.g. MAN, AN, or GMA), and the other copolymerizable vinyl monomers (e.g.
styrene, tribromostyrene) ranges from 2/98 to 40/60 parts by weight, and preferably 3/97 to 30/70 parts by weight. Below 2 parts, the performance is not improved over the vinyl aromatic homopolymer shell, and above that level, side reactions, such as crosslinking, may occur, with adverse effects on dispersion.
2 5 Optionally, one or more additional monomers may be added to the shell to adjust the RI. This additional monomer is preferably an alkyl (meth)acrylate (such as C1-C4 alkyl (meth) acrylate, and the like), but it can be any monomer which copolvmerizes with the other two monomers used in the core polymer and produces a terpolymer whicll permits the RI of the modifier to match that of the3 0 polyesters with which it is blended.
The additional monomer may include one or more of any of the following monomers: acrylonitrile, methacrylonitrile, methyl acrylatej ethyl acrylate, propyl acrylate, butvl acrylate, 2-ethylhe~;vl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate and the like.
3 5 In the impact modifier composition, the ratio of the core polymer to the shell polymer ran;~eC from about 90/10 to about 40/60, and preferably especially when 2~9808~
styrene is the vinyl aromatic monomer from about 60/40 to about 40/60 (parts by weight). The resultant composition preferably has a particle size range of about 75 to about 300 nm., more preferably from about 140 nm. to about 230 nm., and a Rl range of about 1.55 to about 1.58.
When the impact modifier composition containing 40-90 parts by weight of the aforementioned rubbery core polymer and 60-10 parts by weight of the shell hydroxyl-group-containing polymer (total: 100 parts by weight) is manufactured, conventional methods for manufacturing ordinary rubber-modified polymers (e.g., ABS resin, impact resistant polystyrene, etc.) may be effectively employed. These l 0 impact modifiers may be prepared by emulsion polymerization. The preferred procedure is emulsion polyrnerization using soaps, initiators and processing conditions normally used for making MBS polymers, that is, impact modifiers based on butadiene-styrene rubbers with one or more stages of styrene or methyl methacrylate polymers. Isolation from the emulsion can be achieved by standard l 5 procedures such as spray drying or coagulation. For example, a polymer latex characterized by an appropriate particle size and degree of conversion is produced by means of emulsion polymerization (e.g. copolymerizing a hydroxyl-group-containing monomer with another copolymerizable vinyl monomer in the presence of a polymerized rubber latex).
2 0 Further, the polymer can be prepared by a method wherein a core polymer is uniformly graft-polymerized with a hydroxyl-group-containing monomer and another copolymerizable vinyl monomer constituting the shell polymer, but also by a method wherein the core polymer is partially graft-polymerized with the vinyl monomer and/or hydroxyl-group-containing monomer, wherein a copolymer, such 2 5 as that described in U.S. Patent Application Serial No. 755,701, filed September 18, 1991 for which two of the present inventors are inventors and which also is assigned to the same assignee as the present application, is produced by copolymerizing the remainder of the vinyl monomer and/or hydroxyl-group-containing monomer and the two are finally mixed. In such a case, an impact 3 0 modifier composition which provides an extremely high impact resistance can be obtained if the following composition is employed. For example: 50-80 parts by weight (solid content) of the rubbery polymer latex are emulsion graft-polymerized witll 50-20 parts by weight of hydroxyl-group-free vinyl monomer. Next, a hydroxyl-group-containing monomer is separatelv emulsion-polymerized with a vinyl 3 5 monomer identical to that used for the aforementioned emulsion graft polymerization or a different vinyl monomer which yields a copolymer with a high 209808~
affinity with said graft polymer. The resulting core polymer latex and the side-chain hydroxyl-group-containing shell polymer latex are then mixed in latex form prior to isolation. The advantage to this method is that higher molecular weight polymer can be produced in the absence of the butadiene-containing rubber, and the higher S molecular weight component may be more effective in improving rheological properties, such as blow molding. Further, such allows for intimate mixing prior to blending with the polyester.
Thus, when the impact modifier composition is manufactured, general free radical polymerization techniques (e.g., emulsion polymerization, solution l O polymerization, and suspension polymerization) may be employed so long as the resulting impact modifier composition is characterized by a core-shell structurewherein hydroxyl groups are preserved.
The impact modifier composition may be isolated from the reaction medium by any of several known processes. For example, when prepared in emulsion, the l S composition may be isolated by coagulation, including coagulation in an extruder from which the water is removed as a liquid, or by spray-drying. Additives such as thermal stabilizers and anti-oxidants may be added to the composition prior to, .
during or after, isolation.
It is important that no crystallization promoter is present in the composition 2 0 since this invention is directed to compositions suitable for producing amorphous, non-crystalline articles. If substantial crystallization occurs in the process, the resultant articles become opaque and brittle. In some cases, such as with pipe, foam and profile extrusion, a small degree of crystallinity may be acceptable and can be achieved by control of the cooling cycle. However, in most cases it is preferred to 2 5 prepare amorphous articles on standard injection molding and extrusion equipment. The type of articles to be produced, whether it be molded parts, bottles, films, foams, pipes, tubing, sheet or profiles, will govern the auxiliary equipment to be employed. For instance, to produce bottles, extrusion blow molding equipment is necessary. To produce film, blown film equipment is necessary.
3 0 The amorphous, aromatic polyesters, such as PET, and copolyesters, such as Eastman PETG (i.e., (poly)ethylene-co-1,4- cyclohexanedimethylene terephthalate), of this in~ention include poly (C1 to C6 alkylene terephthalates), alkylene naphthalelle dicarbo::ylates, such as poly(ethylene naphthalene-2,6- dicarboxylate), and aromatic amorphous polyester which contains units derived from at least one 3 5 aliphatic diol or cycloaliphatic diol or combinations of aliphatic diols and cycloaliphatic diols and one or more aromatic dibasic acids. Examples include l O

2~sgoga polyethylene terephthalate (PET), polypentylene terephthalate, and the like, or an aromatic copolyester which contains units derived from two glycols (e.g., ethylene glycol, and cyclohexanedimethanol) or from two dibasic acids (e.g. terephthalic acid and isophthalic acid). Such polyesters may be obtained by polycondensing polyol components (e.g., ethylene glycol) with dicarboxylic acid components (e.g., terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.), as well as mixtures consisting of two or more polyesters.
The modifiers and polyesters may be combined by melt blending in an extruder. The polyesters should be dried to 0.037c moisture content. A mix of the two components can be directly extruded or molded or the components can be combined in an initial blending step and the pellets from this blend can then bemolded after drying to a 0.037O moisture content. The concentration of modifier in these polyester blends can range from about 1 to about 30% by weight and preferably from about 5 to about 20'7o by ~veight. The blends can be extruded or molded into l S clear parts which have very high notched impact strength, and exhibit ductile type failures and physical aging resistance. The required modifier concentration willdepend on factors such as the molecular weight of the polyester, the impact strength desired, and the temperature at which the final object is utilized. Below 1`7o modifier concentration, no significant effect is seen.
2 0 Blends should contain amorphous aromatic polyester or copolyester which has an intrinsic viscosity of greater than or equal to 0.7 dl/g. for best properties of molding and processing, but for some uses, lower molecular weight polyesters maybe employed. ( PET or PETG may decrease in intrinsic viscosity after melt processing; the values in the specification refer to the polyester as supplied, prior to 2 S processing). Articles such as containers, bottles, foam, or hollow parts may be extrusion blo-v molded, extruded or injection molded from polyester blends described herein.
Blending can be accomplished by melt extrusion in an extruder at temperatures of about 193C. to about 288C., preferably about 204C. to about 265C.
3 0 For example, a high work, t-vo stage scre-v which has a length/diameter ratio of about 24/1, and a compression ratio of about 3.0 to 3.5 gives a very adequate dispersion of the modifier in the polyester. A dwell time in the extruder of 1 to 5 minutes is ade~luate to insure complete mixing or dispersion under most conditions but of course lower and higher dwell times can certainly be used. Preferably the3 5 strancis produced by extruder blending are pelletized and dried to a moishlre content of less than 0.03 percent before molding.
I l : ' ' 20980~
The ingredients used to make the composition of the invention are dispersed uniformly and it has been found that melt blending the ingredients, by using such equipment as a melt extruder (e.g., single screw extruders or twin screw extruders) in a separate step prior to molding is desirable. The blended product may be pelletized 5 (i.e., the extruded strand is quenched and cut), dried and used for subsequent molding purposes.
Other additives known in the art may be included in the composition at about 1 to about 30~0 by weight. These other aclditives may include antioxidants, flame retardants, reinforcing agents such as glass fiber, asbestos fiber and flake, 10 mineral fillers, stabilizers, nucleating agents, ultraviolet light stabilizers, heat and light stabilizers, lubricants, dyes, pigments, toners, mold release agents, fillers, such as glass beads and talc, and the like. Minor amounts of other polymers (i.e. about 1 to about 10 percent by weight) can also be incorporated in the present composition, such as polyamides or polycarbonates. Most of these additives will adversely affect I S clarity. The additives listed above such as antioxidants, thermal stabilizers, fillers, pigments and flame retardant additives may be used in the composition of this invention provided they do not exert any adverse effect on the impact strength or clarity. It is preferred not to have glass fiber reinforcement in clear article applications or any additive which would decrease transparency. It is highly 2 0 preferred that clear articles are produced.
The polyesters must be thoroughly dried prior to melt processing to minimize the rapid hydrolytic degradation known to occur at processing temperatures and to reduce molecular weight. The modifiers of the present invention are much less sencitive to hydrolytic degradation than the polyesters.2 5 Higher than necessary melt temperatures should be avoided during processing to keep the impact strength as high as possible. Melt cooling should be carried out as rapidly as possible to prevent polyester crystallization and the loss of clarity.
Aromatic amnrphous polyesters are quite sensitive to embrittlement from physical aging, but this limitation is overcome by the modifiers herein (see Table II).
3 0 Therefore, polyester blends will now be able to compete successfully with pnlycarbonate, cellulosics, impact modified polyvinyl chloride, and the like for a broad range of applications where high clarity and toughness are needed in the absence of exceptional heat resistance.
The preferred pnly(alkylene terephthalates) are polyethylene terephthalate 3 5 (PET) and copolyesters of PET. Blends with other polyesters are also suitable. For 2~084 example, blends of two or more polyesters may also be used, with polyester blends which have poly (ethylene terephthalate) being preferred.
EXAMPLES
The following examples and comparative examples are presented to illustrate 5 the invention, but the invention should not be limited by these examples. All parts and percentages are by weight unless otherwise indicated, and the following abbreviations are employed in the examples and throughout the text:
BA = butyl acrylate 10 EA = ethyl acrylate ST = s tyrene HEMA = hydroxy ethyl methacrylate MMA = methyl methacrylate MAA = methacrylic acid 15 HPMA = hydroxy propyl methacrylate GMA = glycidyl methacrylate PET = poly(ethylene terephthalate) PBT = poly(butylene terephthalate) BD = butadiene 2 0 DVB = divinyl benzene BZMA = benzyl methacrylate AN= acrylonitrile MAN= methacrylonitrile 2 5 APPARATUCi and GENERAL PROCEDURE
Standard ASTM test specimen molds are employed. Refractive indexes are determined according to ASTM-D-524, light transmission and haze according to ASTM-D-1003, and notched Izod impact strength according to ASTM-D-256. The modifiers are prepared by emulsion polymerization of butadiene with styrene and 3 0 about 0.65to divinyl benzene. After this step was complete, styrene with HEMA or anotl-er comonomer is added to the emulsion and polymerized to form a shell stage on the butadiene rich core stage. The core-shell impact modifier polymer is thenisolated from the emulsion by spra~ drying.
The impact mo(iifiers described herein have particle sizes in the 180-240 nm 3 5 range. The modifier is combined with aromatic polyester resins by melt blending in an extruder. Strands of the blends are quenched in a water bath as they leave the extruder to prevent polyester crystallization. Blends in which the RI's of the modifier and polyester are equal form clear strands. Pellets cut from the strands are injection molded into test specimens under conditions which prevent polyester l 3 2~0~
crystallization. The test specimens are then evaluated for physical properties. It should be noted that notched Izod impact strengths greater than about 10 ft.lbs/in.
(ca. 540 J/m) usually exhibit ductile rather than brittle breaks. Also all the 1/8" (3.2 mm.) molded plaques prepared with modified PETG are transparent so that distant 5 objects could be clearly seen through them even though the measured haze vaiues ranged from about 7 to about 457O.
These results in Table I clearly show the effectiveness of modifiers with styrene/HEMA shells vs. shells with styrene, or styrene and other monomers. In 1/8" (3.2 mm.) thick samples, ductile failures (desirable) were observed at modifier 1 0 loadings as low as 105~o and in three cases at a temperature of 10C (20% loading).
Also some blends produced 1/4" (6.4 mm.) thick samples which gave ductile breaks.
Unmodified polycarbonate, generally conceded to be the toughest clear polymer, exhibits only brittle breaks at 1/4" (6.4 mm.) thickness.
The modifiers in the Tables are prepared by emulsion polymerization. The l 5 impact modifiers are blended with polyester in a 1 inch, 24/1 length/diameter ratio, single screw extruder at the concentrations (i.e. modifier loading (%)) listed in Table I. Impact strength is determined by ASTM-D- 256. Table I describes the effect ofdifferent impact modifiers ( butadiene/styrene//styrene/HEMA ) on the impact strength of a commercial copolyester resin, Eastman's PETG 6763, with a 0.74 dl/g 2 0 intrinsic viscosity (IV) (ASTM D- 4603), and another commercial copolyester,Eastman's Tenite 13339, with a 1.05 dl/g IV (ASTM D-4603). Many of the impact modifiers have RI's approximating those of the polyesters or copolyesters so that clear strands ~vere extruded. Exact RI matches can be achieved by slightly adjusting the impact modifier Compositions witll HPMA or GMA replacing HEMA may be 2 5 employed with similar results.
Table I lists the compositions of a series of core-shell impact modifiers with RI's of about 1.565 except for Example 11 (lower) and Example 15 (higher). Modifiers are melt blended at the concentrations listed in the table with Eastman's PETG 6763, a non-crystallizable PET copolyester in ~vhich part of the ethylene glycol (EG) 3 0 component is replaced vith cvclohe:;ane dimethanol (CHDM), having a RI = 1.565.
These blends and unmodified PETG are molded into 1/8" and 1/4" (3.2 mm. and 6.4 mm.) thick notched Izod impact test (ASTM-D-256) specimens and into 2" x 3" x 1 /8" (50.8 x 76.2 x 3.2 mm.) plaques. The impact test results are determined by ASTM
D-256 on 1 /8' and on 1/4" (3.2 mm. and 6.4 mm.) thick bars. Values for transparency 3 5 and haze are determined on the 1/8" (3.2 mm.) thick plaques.

:

209808~
Two blends with Modifiers 12 and 15 are prepared with Eastman's Tenite 13339 copolyester. This resin contains less CHDM than PETG and its composition is therefore much closer to that of PET than is PETG. It has an RI of 1.575. Since the modifier of Example 12 blended with it had an RI of only about 1.565, the RI
mismatch caused the plaques to be translucent rather than transparent. The modifier of Example 15 with a RI of 1.575 gives a blend of low haze.
Example 1 A 15g charge of a 107O aqueous solution of acetic acid was added to 5244.4g of deionized water in a stainless steel reactor capable of withstanding 200 psi (1.38 mPa) l 0 pressure. The solution was heated to 80C while stirring and sparging with nitrogen for 30 minutes. The temperature was raised to 85C and 360g of a lO~o aqueous solution of sodium formaldehyde sulphoxylate were added along with a 50g rinse of deionized water. A mixture of 611.4g of styrene (ST) and 30g of divinyl benzene (DVB) were next added along with 2358.6g of butadiene (BD) and 240g of a io%
l 5 aqueous solution of sodium dodecyl benzene sulfonate over a 3 hour period. A
357.5 charge of a 1.4'~c, aqueous solution of t-butyl hydroperoxide (tBHP) was added over a 6 hour period. At the end of this addition, the feed line was rinsed with a sufficient amount of deionized water to obtain an emulsion containing 337O solids.
The emulsion was cooled to room temperature and stored for subsequent use as a 2 0 seed for the following modifier examples.
Example 2 A 18.2g charge of a 1070 aqueous solution of acetic acid was added to 5800g of deionized water in a reactor. This was sparged with nitrogen while it was heated to 95C. When the temperature reached 95C, the nitrogen was turned off and 532.5g 2 5 of the emulsion (solids basis) from Example 1 and 337.3g of a 57O aqueous solution sodium formaldehyde sulpho~;ylate were added to the reactor. About 350g of deionized ~vater was used as a rinse. The reactor was then evacuated to 5" (0.17mdynes/ cm2) of mercury. Next a mixture of 2020.8g of ST and 42.2g of DVB were added at a constant rate to the reactor over a 5 hour period. At the same time 590.2g 3 0 of a lO~o aqueous solution of Dowfax 2A-1 and 2241.3g of BD were added at a constant rate over the same 5 hour period. At the same time, 695.6g of a 1.4qo aqueous solution of tBHP was added over a 7.25 hour period. At the end of the monomer feed, 227g of rinse water were added. At the end of the tBHP feed, the reaction - as held for 30 minutes. After this the reactor was cooled to 62C and 3 5 vented to atmospheric pressure. This completed the preparation of the emulsified core of the modifier.
] S

. . .~

. ~.

2~9808~
The shell of the modifier was prepared by first adding 109.8g of a 5~c aqueous solution of sodium formaldehyde sulphoxylate to the reactor containing the core emulsion. A nitrogen sweep of the reactor was started. A mixture of 2574g of ST
and 390.2g of hydroxyethyl methacrylate (HEMA) was prepared and sparged with nitrogen for 20 min. This mixture was fed to the reactor, maintained at 60C, for 90 minutes along with 288.9g of a 1.470 solution of tBHP. At the end of this feed the reaction was held for 15 minutes and then chased for 4 hours with 183.1g of a 1.4~o aqueous solution of tBHP and 87.9g of a 57O aqueous solution of sodium formaldehyde sulphoxylate. At the end of this chase, a 507O solids emulsion l 0 containing 30.1g of trisnonyl phenyl phosphite, 30.1g of triethylene glycol bis(3-(3'-t-butyl-4'hydroxy- 5'methylphenyl) propionate) (Irganox 245, Ciba Geigy Co.) and 90.3g of dilauryl thiodipropionate was added.
The emulsion was then spray dried. A fine powder having a refractive index (RI) of 1.565 was obtained. This powder was melt blended in a single screw extruder l 5 at an average melt temperature of 240C with Kodar PETG 6763, a PET copolyester supplied by Eastman Chemical Co., which contains cyclohexanedimethanol substituted for part of the ethylene glycol. This copol-yester has an RI of 1.565.
Extruded strands of the blend were pelletized, dried for 8 hours at 60C and injection molded into test specimens. Notched Izod impact tests were run according to ASTM2 0 Procedure D-256 and ligh~ transmission and haze tests were run on 32mm thick test specimens according to ASTM Procedure D-524. Results from these tests and tests run on the following examples are listed in Table I. Some blends were also prepared with Eastman Chemical Co.'s Tenite 13339, a PET resin containing less than 10qo isophthalic acid substituted for terephthalic acid and having an intrinsic viscosity of 1.05 dl/g.
Example 3 This modifier was prepared in the same way as Example 2 except that 2433.6g of ST and 530.5g of HEMA were used to prepare the modifier shell.
Example 4 3 0 This modifier was prepared in the same way as Example 2 except that 2730g of ST and 234g of HEMA were used to prepare the modifier shell.
Example 5 This modifier was the same as Example 2 except that the shell consisted of 2371.2g of ST, 296.4g of HEMA and 296.4g of ethyl acrylate.

l 6 2~9808~
Example 6 This modifier was the same as Example 2 except that hydroxypropyl methacrylate was substituted for the HEMA.
The following four examples compare results obtained with modifiers having the same cores as those in the examples above and RI's about equal to those of the above modifiers but with shells that do not fall within the claims of this application.
Example _ This modifier was the same as the one in Example 2 except that the ST charge used in making the core was 2122.2g and the BD charge for the core was 2373.9g. The l 0 shell consisted of 2552g of ST. No comonomer was used in preparing the shell.
Example ~s This modifier was the same as Example 2 except that the shell was prepared with 2652g of ST, 156g of methyl methacrylate and 156g of ethyl acrylate. No HEMA
was present.
l 5 Example 9 This modifier was the same as Example 2 except that the shell consisted of 2652g ST, 156g of methyl methacrylate and 156g of methacrylic acid. No HEMA was present.
Example 10 2 0 This modifier was the same as Example 2 except that the shell was composed of 1560g of ST and 1404g of benzyl methacrylate.
Example 11 The modifier used in this example was Paraloid EXL3647, an MBS type commercial impact modifier supplied by Rohm and Haas Co. This modifier has a 2 5 RI of 1.525 which is well below the RI's of aromatic polyesters and copolyesters.
Although this modifier produced good notched impact strength, it also produced blends which were opaque.
Example 12 This modifier vas equi~alent in composition to Example 2 but it was 3 0 prepared by a different process. The difference was in the rate of addition of the STtDVB mix and of the BD used in preparing the core. These two components were added according to the following schedule:
First hour ST/DVB12.7g/min. BD 1.2g/min.
Second hour " / " 9.1"/ " " 4.9"/ "
3 5 Third hour " / " 7.0"/ " " 7.1"/ "
Fourth hour " / " 4.2"/ " " 9.8"/ "
Fifth hour " / " 1.4"/ " " 12.7"/ "
l 7 2~sgo~ l~
At the end of this monomer feed, the process and components used were the same as those in Example 2.
Example 13 This modifier was the same as Example 12 except that the shell consisted of 2371.2g of ST, 296.4g of HEMA and 296.4g of ethyl acrylate.
Example_ This modifier had the same overall composition as Example 2 except that the seed polymer contained a high level of ST. This seed polymer was prepared in thesame manner as E~ample 1. After the reactor was charged with 5244.4g of deionized I 0 water and 15g of a 10~/O aqueous solution of acetic acid, it was heated to 90C while stirring and sparging with nitrogen for 30 minutes. When the temperature reached90C, 360g of a 107O aqueous solution of sodium dodecyl benzene sulfonate and 182g of a 5~O aqueous solution of sodium formaldehyde sulphoxylate were added. Next amixture of 2970g of ST and 30g of DVB, a 2358g charge of BD and a 240g charge of a 1 5 lOS~o aqueous solution of sodium dodecyl benze sulfonate were added over 3 hours.
A 367.5g charge a 1.4~O aqueous solution of tBHP was added over 4 hours. At the end of the feed, the lines were rinsed with deionized water to produce a 337O solids emulsion.
The procedure used for the rest of the preparation was the same as that used 2 0 for Example 12 except that the above emulsion was substituted for the Example 1 em-llsion used in Example 12 and the monomer charge for making the core was 182.4g of ST, 44.3g of DVB and 2425.5g of BD. All other components used in both the core and the shell and the procedure used were the same as for Example 12.
Example 15 2 5 This modifier was the same as Example 12 except that the shell consisted of 2027.4g of ST, 296.-}g of HEMA and 640.2g of vinyl naphthalene to give a modifier with a Rl of 1.575.
Example 16 This example shows blends of PETG and of PET and impact modifiers of the 3 0 present invention, which blends show retained impact strength after a heat aging process vhich greally lowers the impact strength of the unmodified polyester.
Polymer A: a PET with less than 57O isophthalic acid, (rl) = 0.90 dl/g; Polymer B =
PETG (Eastman 6763), described in the previous table; Modifier C is the modifier of E~;ample 12, viz., 34.1 Bd/27.3 St/0.6 DVB//33 St/5 HEMA. Samples are molded and3 5 tested as molded and after aging at condition D = 5 days at 60C or condition E = 30 days at 65C. Data are shown in Table 2.

- 2~9~0~L

TABLE 1: IMPACT STRENGTH AND OPTICAL PROPERTIES
OR POLYESTER/ /IMPACT MODIFIER BLENDS
S Notcl~ed Izod Impact Strengtl of Blend (loules/M) Blend Modifier Modifier Modifier 3.2 mm Tllick Specimen 6.4 mm Transparency Ex. No. Polvester Cnnc. (~.) __R I 22C 10C 0C 22C Haze No modifierPETG 6763(1) () 101.469.4 58.7 69.4 86t2 2 .. 20 1.565 1072.91~5.5 80.1 838.178/3() 2 .. 15 1.565 1142.3170.8 37.4 784.7 79/29 2 .. 10 .1.565 1185.0117.4 69.4 138.8 82!15 3 .. 2() 1U94.3133.5 8û.1 181.5 76/44 4 .. 20 i .566 1131.71072.9117.4 998.2 79/34 .. 2(~ 1.564 122.885.4 48.0 85.4 74/51 6 .. 20 1.565 250.990.7 80.1 149.5 80/26 7 .. 2n 1.562 58.7 72/25 8 .. 20 1.564 133.5 76/13 8 .. 3U 1.564 144.1 9 .. 20 1.5~5 69.4 77/~
1() .. 2() 1.564 117.4 79/lU
11 .. 20 1.525 763.3 opaque 12 .. 2() 1.565 1158.31147.71121.0 1056.9 78/31 13 .. 2!) I .5~4 1334.5154.8 96.1 154.8 76/33 14 .. 2() 1387.81121.01121.0 65/lR
No modifierT~niIe 1333~(2) () 26.7 8()/~
- 12 .. 2() 1.565 976.9160.1138.8 224.2translucellt .. .2() 1.575 1()1~.6 76/56 ' I O (1) Eastm.lll Cl~-~mic~l C~ BETcop~-lyester, contaills about 3()'~ cyclollexanedimetllallol substitIlted for etllylelle gl~c(-l, r.i. 1.565.
(2) Eastmall Chemic~l Co. - BET contailling <1()'7, isophtllalic acid. IV = 0.95 dl/g; r.i. = 1.575 ~ ,.

l 9 ,:

.

- ~ .

209808~
Table 2: Phvsical Aging Data Dart Impact, Toules Notched Izod, Toules/m PolvmerAs molded Condition D As molded Condition E
A 45.2 2.9 A/C=85/15 48.1 45.0 B 68.0 43.9 48 42.7 l 0 B/C=85/15 60.1 60.7 1228 1142

Claims (29)

1. A core-shell impact modifier composition comprising:
(A) from about 40 to about 65 parts by weight of a core polymer comprising:
from about 40 to about 60 percent by weight of units derived from a vinyl aromatic monomer, from about 40 to about 60 percent by weight of units derived from at least one 1,3-diene, up to about 10 percent by weight of units derived from at least one copolymerizable vinyl or vinylidene monomer, and up to about 5 percent by weight of at least one graft-linking or cross-linking monomer;
(B) from about 35 to about 60 parts by weight of a shell polymer comprising: from about 2 to about 40 percent by weight of units derived from at least one hydroxyalkyl (meth)acrylate, and from about 60 to about 98 percent by weight of units derived from at least one vinyl aromatic monomer; and up to about 25 percent by weight of units derived from one or more copolymerizable vinyl or vinylidene monomers, the core-shell impact modifier having a refractive index of from about 155 to about 158.
2. A core-shell impact modifier composition comprising:
(A) from about 40 to about 90 parts by weight of a core polymer comprising:
from about 20 to about 60 percent by weight of units derived from a vinyl aromatic monomer selected from polybromo vinyl aromatic monomers and polycyclic vinyl aromatic monomers, from about 40 to about 80 percent by weight of units derived from at least one 1,3-diene, up to about 10 percent by weight of units derived from at least one copolymerizable vinyl or vinylidene monomer, and up to about 5 percent by weight of at least one graft-linking or cross-linking monomer;
(B) from about 10 to about 60 parts by weights of a shell polymer comprising: from about 2 to about 40 percent by weight of units derived from at least one hydroxyalkyl (meth)acrylate, and from about 60 to about 98 percent by weight of units derived from at least one vinyl aromatic monomer; and up to about 25 percent by weight of units derived from one or more copolymerizable vinyl or vinylidene monomers, the core-shell impact modifier having a refractive index of from about 155 to about 158.
3. A core-shell impact modifier composition comprising:
(A) from about 10 to about 50 parts of a core polymer comprising: at least 80 percent of units derived from at least one vinyl aromatic monomer, up to about 20 percent of units derived from at least one other copolymerizable vinyl or vinylidene monomer, up to about 20 percent by weight of units derived from at least one 1,3-diene, and up to about 5 percent by weight of units derived from at least one graft-linking or cross-linking monomer;
(B) from about 40 to about 80 parts by weight of a second-stage polymer comprising: from about 20 to about 60 percent by weight of units derived from a vinyl aromatic monomer, from about 30 to about 70 percent by weight of units derived from at least one 1,3-diene, up to about 10 percent by weight of units derived from at least one copolymerizable vinyl or vinylidene monomer, and up to about 5 percent by weight of units derived from at least one graft-linking or cross-linking monomer;
(C) from about 10 to about 40 parts by weight of a shell polymer comprising: from about 2 to about 40 percent by weight of units derived from at least one hydroxyalkyl (meth)acrylate, from about 60 to about 98 percent by weight of units derived from at least one vinyl aromatic monomer; and up to about 25 percent by weight in the shell of units derived from one or more copolymerizable vinyl or vinylidene monomers, the core-shell impact modifier having a refractive index of from about 1.55 to about 1.58.
4. The composition of Claims 1 or 3 wherein the vinyl aromatic monomer is styrene, para-methyl styrene, alpha-methylstyrene, chlorostyrene, vinyl toluene, bromostyrene, dibromostyrene, tribromostyrene, isopropenyl naphthalene, or vinyl naphthalene and wherein the 1,-3 diene is butadiene.
5. The composition of Claims 1, 2 or 3 wherein the hydroxyalkyl (meth)acrylate is hydroxyethyl (meth)acrylate or hydroxypropyl (meth)acrylate.
6. The composition of Claim 1, 2 or 3 wherein the one or more vinyl or vinylidene monomers are acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, or butyl acrylate.
7. The composition of Claims 1 or 2 wherein the core polymer is butadiene-styrene copolymer, butadiene-styrene-acrylonitrile copolymer, or butadiene-butyl acrylate-styrene copolymer, and wherein the core polymer contains from about 0.01 to about 2 weight percent of units derived from at least one cross-linking or graft-linking monomer.
8. The composition of Claims 1, 2 or 3 wherein the shell polymer comprises from about 60 to about 98 percent of vinyl aromatic monomer and from about 2 to about 40 percent hydroxyalkyl (meth)acrylate.
9. A clear, amorphous blend comprising:
(A) at least one amorphous, aromatic polyester or copolyester having a refractive index of from about 1.55 to about 1.58; and (B) the composition of Claims 1, 2 or 3;
at a weight ratio of about 99/1 to about 70/30.
10. The blend of Claim 9 further containing about 0.1 to about 30% by weight, based on the weight of polyester and impact modifier, of one or more other additives.
11. The blend of Claim 10 further containing about 1 to about 1070 by weight, based on the weight of polyester and impact modifier, of one or more other polymers.
12. The blend of Claim 9 wherein the aromatic polyester is a poly(alkylene terephthalate), poly(alkylene naphthalene dicarboxylate) or an aromatic polyester which contains units derived from at least one aliphatic diol or cycloaliphatic diol and at least one aromatic dibasic acid.
13. The blend of Claim 12 wherein the aromatic polyester is polyethylene terephthalate or an aromatic copolyester which contains units derived from ethylene glycol, cyclohexanedimethanol, terephthalic acid and isophthalic acid.
14. Articles produced from the blend of Claim 9 under conditions which maintain the polyester in an amorphous condition.
15. Articles of Claim 14 which are molded, extruded, or extrusion blow molded into parts, sheets, film, containers, bottles, foam, or hollow parts.
16. A core-shell impact modifier composition comprising:
(A) from about 40 to about 65 parts by weight of a core polymer comprising:
from about 40 to about 60 percent by weight of units derived from a vinyl aromatic monomer, from about 40 to about 60 percent by weight of units derived from at least one 1,3-diene, up to about 10 percent by weight of units derived from at least one copolymerizable vinyl or vinylidene monomer, and up to about 5 percent by weight of at least one graft-linking or cross-linking monomer;
(B) from about 35 to about 60 parts by weight of a shell polymer comprising: from about 2 to about 40 percent by weight of units derived from at least one of units derived from the group consisting of (meth)acrylonitrile, cyanoalkyl (meth)acrylates, cyanoalkoxyalkyl (meth)acrylates, (meth)acrylamide, N-monoalkyl(meth)acrylamide, vinylaromatic monomers containing at least one hydroxyl group, and monomers containing an allyl group and an hydroxyl group, from about 60 to about 98 percent by weight of units derived from at least one vinyl aromatic monomer, and up to about 25 percent by weight of units derived from one or more copolymerizable vinyl or vinylidene monomers, the core-shell impact modifier having a refractive index of from about 1.55 to about 1.58.
17. The composition of Claim 16 wherein the (meth)acrylonitrile is acrylonitrile.
18. The composition of Claim 16 wherein the cyanoalkyl (meth)acrylate is beta-cyanoethyl methacrylate or beta-cyanoethyl acrylate.
19. The composition of Claim 16 wherein the cyanoalkoxyalkyl (meth)acrylate is omega-cyanoethoxyethyl methacrylate or omega-cyanoethoxyethyl acrylate.
20. The composition of Claim 16 wherein the (meth)acrylamide is methacrylamide.
21. The composition of Claim 16 wherein the N-monoalkyl(meth)acrylamide is N-methylacrylamide or N-t- butylmethacrylamide.
22. The composition of Claim 16 wherein the vinylaromatic monomer of the shell polymer is para-vinylbenzyl alcohol.
23. The composition of Claims 16 wherein the vinyl aromatic monomer is styrene, para-methyl styrene, chlorostyrene, vinyl toluene, bromostyrene, dibromostyrene, tribromostyrene, isopropenyl naphthalene, or vinyl naphthalene, and wherein the vinyl or vinylidene monomers are methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, or butyl acrylate.
24. A clear, amorphous blend comprising:
(a) at least one amorphous, aromatic polyester or copolyester having a refractive index of from about 1.55 to about 1.58; and (b) the composition of Claim 16 at a weight ratio of about 99/1 to about 70/30.
25. The blend of Claim 24 further containing about 0.1 to about 30% by weight, based on the weight of polyester and impact modifier, of one or more other additives.
26. The blend of Claim 25 further containing about 1 to about 10% by weight, based on the weight of polyester and impact modifier, of one or more other polymers.
27. The blend of Claim 24 wherein the aromatic polyester is a poly(alkylene terephthalate), poly(alkylene naphthalene dicarboxylate) or an aromatic polyester which contains units derived from at least one aliphatic diol or cycloaliphatic diol and at least one aromatic dibasic acid.
28. The composition of Claim 27 wherein the poly (alkylene terephthalate) is polyethylene terephthalate or an aromatic copolyester which contains units derived from ethylene glycol, cyclohexane dimethanol, terephthalic acid and isophthalic acid.
29. Articles of Claim 16 which are molded, extruded, or extrusion blow molded into parts, sheets, film, containers, bottles, foam, or hollow parts.
CA002098084A 1992-06-19 1993-06-09 Amorphous, aromatic polyester containing impact modifier Abandoned CA2098084A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US90132792A 1992-06-19 1992-06-19
US07/901,327 1992-06-19
US08/032,939 1993-03-17
US08/032,939 US5321056A (en) 1992-06-19 1993-03-17 Amorphous, aromatic polyester containing impact modifier

Publications (1)

Publication Number Publication Date
CA2098084A1 true CA2098084A1 (en) 1993-12-20

Family

ID=26709072

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002098084A Abandoned CA2098084A1 (en) 1992-06-19 1993-06-09 Amorphous, aromatic polyester containing impact modifier

Country Status (8)

Country Link
US (2) US5321056A (en)
EP (1) EP0577281B1 (en)
JP (1) JP3278980B2 (en)
AT (1) ATE205227T1 (en)
CA (1) CA2098084A1 (en)
DE (1) DE69330696T2 (en)
DK (1) DK0577281T3 (en)
ES (1) ES2161226T3 (en)

Families Citing this family (81)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0494534B1 (en) * 1990-12-28 1996-11-27 Polyplastics Co. Ltd. Core-shell polymer
US5798172A (en) * 1994-12-07 1998-08-25 Idemitsu Petrochemical Co., Ltd. Styrenic resin composition and polystyrene oriented film
TW412567B (en) * 1995-07-27 2000-11-21 Toray Industries Polyester composition and its film
US7507471B1 (en) * 1995-10-10 2009-03-24 Isola Usa Corp Reducing dusting of epoxy laminates
DE19630118A1 (en) * 1996-07-25 1998-01-29 Basf Ag Flat wall elements
US6020414A (en) * 1996-10-23 2000-02-01 Hoechst Celanese Corporation Method and compositions for toughening polyester resins
US6395865B2 (en) 1997-12-05 2002-05-28 Continental Pet Technologies Inc Process for making pen/pet blends and transparent articles therefrom
US5902539A (en) * 1996-12-06 1999-05-11 Continental Pet Technologies, Inc. Process for making PEN/PET blends and transparent articles therefrom
US6197878B1 (en) 1997-08-28 2001-03-06 Eastman Chemical Company Diol latex compositions and modified condensation polymers
EP1009774A2 (en) * 1997-08-28 2000-06-21 Eastman Chemical Company Modified condensation polymer
DE69937418T2 (en) * 1998-02-06 2008-07-24 Riken Technos Corp. Resin composition and resin film
JP4644219B2 (en) * 1998-02-06 2011-03-02 リケンテクノス株式会社 Resin sheet
US5959066A (en) * 1998-04-23 1999-09-28 Hna Holdings, Inc. Polyesters including isosorbide as a comonomer and methods for making same
US6025061A (en) * 1998-04-23 2000-02-15 Hna Holdings, Inc. Sheets formed from polyesters including isosorbide
US6063464A (en) * 1998-04-23 2000-05-16 Hna Holdings, Inc. Isosorbide containing polyesters and methods for making same
US6063465A (en) * 1998-04-23 2000-05-16 Hna Holdings, Inc. Polyester container and method for making same
US6126992A (en) * 1998-04-23 2000-10-03 E.I. Dupont De Nemours And Company Optical articles comprising isosorbide polyesters and method for making same
US6140422A (en) 1998-04-23 2000-10-31 E.I. Dupont De Nemours And Company Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers
US5958581A (en) * 1998-04-23 1999-09-28 Hna Holdings, Inc. Polyester film and methods for making same
US6063495A (en) * 1998-04-23 2000-05-16 Hna Holdings, Inc. Polyester fiber and methods for making same
US6130290A (en) * 1998-04-29 2000-10-10 Rohm And Haas Company Impact modifier for amorphous aromatic polyester
EP0959372A3 (en) 1998-05-22 2000-07-19 Rohm And Haas Company Light pipe composition
DE69943227D1 (en) 1998-09-09 2011-04-07 Rohm & Haas A method of making a core cup impact modified emulsion
EP1514883B1 (en) * 1998-09-09 2011-02-23 Rohm And Haas Company A process for preparing a core-shell impact modifier emulsion
US7067188B1 (en) * 1999-01-21 2006-06-27 Arkema Polymeric articles having a textured surface and frosted appearance
WO2000052097A1 (en) 1999-03-03 2000-09-08 Eastman Chemical Company Polyamide/emulsion polymer blends
WO2000052083A1 (en) 1999-03-03 2000-09-08 Eastman Chemical Company Silicone polymer diol compositions and condensation polymer/silicone polymer blends
US7309729B1 (en) 2000-03-07 2007-12-18 Rohm And Haas Company Aqueous additive systems for polymeric matrices
US6203973B1 (en) * 1999-03-25 2001-03-20 Eastman Kodak Company Polymer latexes with core-shell morphology
US6515082B1 (en) 1999-05-21 2003-02-04 Rohm And Haas Company Process for preparing polymers
CN1355824A (en) 1999-06-18 2002-06-26 伊斯曼化学公司 Nylon 6-polysilopxane blends
WO2000078842A1 (en) 1999-06-18 2000-12-28 Eastman Chemical Company Amide-type polymer/silicone polymer blends and processes of making the same
DE60043874D1 (en) 1999-09-16 2010-04-08 Rohm & Haas Modified SAN resin compositions and articles made therefrom
EP1085050B1 (en) * 1999-09-16 2010-02-24 Rohm And Haas Company Modified SAN resin blend composition and articles produced therefrom
US6462109B1 (en) 1999-10-12 2002-10-08 Eastman Chemical Company Surfactantless latex compositions and methods of making polymer blends using these compositions
EP1095982A1 (en) * 1999-10-28 2001-05-02 Rohm And Haas Company Impact modifier concentrates for amorphous aromatic polyester
FR2801596B1 (en) * 1999-11-26 2004-12-03 Atofina THERMOPLASTIC POLYESTERS WITH IMPROVED SHOCK PROPERTIES AND SHOCK MODIFIER COMPOSITIONS
US6814905B1 (en) 1999-12-02 2004-11-09 Associated Packaging Enterprises, Inc. Continuous process and apparatus for making thermoformed articles
US6576309B2 (en) 1999-12-02 2003-06-10 Associated Packaging Enterprises Thermoplastic compositions having high dimensional stability
DE10003270A1 (en) * 2000-01-26 2001-08-02 Basf Ag Stabilized fiber-reinforced thermoplastic molding compounds for automotive interior applications
US6989190B2 (en) * 2000-10-17 2006-01-24 General Electric Company Transparent polycarbonate polyester composition and process
US6773735B1 (en) 2000-11-28 2004-08-10 Associated Packaging Enterprises, Inc. Multi-layered thermoplastic container
JP4917710B2 (en) * 2001-01-16 2012-04-18 株式会社カネカ Impact resistance improver and amorphous polyester resin composition containing the same
US20090005476A1 (en) * 2001-04-09 2009-01-01 Eastman Chemical Company Polyol latex compositions and process of making them
US6844390B2 (en) * 2001-04-09 2005-01-18 Eastman Chemical Company Modified alkyd compositions comprising polyol latex compositions and processes of making them
US6699931B2 (en) 2001-04-09 2004-03-02 Eastman Chemical Company Modified alkyd compositions comprising diol latex compositions and processes of making the same
US20050215677A1 (en) * 2002-06-13 2005-09-29 Gaggar Satish K Thermoplastic compositions and process for making thereof
JP4488898B2 (en) * 2002-10-24 2010-06-23 株式会社カネカ Amorphous polyester resin composition
US20050260371A1 (en) * 2002-11-01 2005-11-24 Yu Shi Preform for low natural stretch ratio polymer, container made therewith and methods
US20040091651A1 (en) * 2002-11-01 2004-05-13 Mark Rule Pet copolymer composition with enhanced mechanical properties and stretch ratio, articles made therewith, and methods
US20060041056A1 (en) * 2002-11-07 2006-02-23 Kaneka Corporation Thermoplastic polyester resin composition and molded object obtained therefrom
CN1732217A (en) * 2002-12-23 2006-02-08 陶氏环球技术公司 Electrically conductive polymerized macrocyclic oligomer carbon nanofiber compositions
DE602004023195D1 (en) * 2003-06-18 2009-10-29 Coca Cola Co METHOD FOR HOTFILLING CONTAINERS MADE FROM POLYESTERIC COMPOSITIONS
US7195820B2 (en) * 2003-12-09 2007-03-27 Arkema Inc. Core-shell polymers having hydrophilic shells for improved shell coverage and anti-blocking properties
US20050153084A1 (en) * 2004-01-09 2005-07-14 Yu Shi PET with stress cracking resistance, preform and container made therewith and method
US20050221036A1 (en) * 2004-04-01 2005-10-06 The Coca-Cola Company Polyester composition with enhanced gas barrier, articles made therewith, and methods
US7838112B2 (en) * 2004-11-30 2010-11-23 The Goodyear Tire & Rubber Company Modified gel particles and rubber composition
US7820257B2 (en) * 2005-05-11 2010-10-26 The Coca-Cola Company Preforms for preparing lightweight stretch blow molded PET copolymer containers and methods for making and using same
US7572493B2 (en) * 2005-05-11 2009-08-11 The Coca-Cola Company Low IV pet based copolymer preform with enhanced mechanical properties and cycle time, container made therewith and methods
JP5290495B2 (en) * 2005-08-04 2013-09-18 リケンテクノス株式会社 Laminated sheet
US20080085390A1 (en) * 2006-10-04 2008-04-10 Ryan Thomas Neill Encapsulation of electrically energized articles
KR100994055B1 (en) * 2008-01-16 2010-11-11 주식회사 엘지화학 Impact Strength Modifiers For Thermoplastic Polyester And Thermoplastic Polyester Resin Composition Containing The Same
EP2265665B1 (en) 2008-04-07 2021-10-20 Arkema Inc. Functional mbs impact modifiers for use in engineering resins
US20100015456A1 (en) * 2008-07-16 2010-01-21 Eastman Chemical Company Thermoplastic formulations for enhanced paintability toughness and melt process ability
TR201900151T4 (en) * 2008-08-29 2019-02-21 Arkema Inc Functionalized two-model impact modifiers.
KR20120051675A (en) * 2009-08-07 2012-05-22 미츠비시 가스 가가쿠 가부시키가이샤 Polyester resin composition
WO2012009201A2 (en) 2010-07-13 2012-01-19 Invista Technologies S.A R.L. High dimensional stability polyester compositions
KR101397688B1 (en) * 2010-12-30 2014-05-22 제일모직주식회사 Rubber-modified vinyl graft copolymer and thermoplastic resin composition comprising the same
JP5102388B2 (en) * 2011-07-05 2012-12-19 リケンテクノス株式会社 Laminated sheet
US9332802B2 (en) 2011-12-30 2016-05-10 Ticona Llc Molded polymer articles for use in low temperatures having a low rigidity factor
US9328229B2 (en) 2012-05-09 2016-05-03 Ticona Llc Polymer composition and articles for use in low temperature environments that are wear resistant
US20140066564A1 (en) * 2012-09-06 2014-03-06 Ticona Llc Molded Articles Made From A Translucent Polymer Composition
US8865261B2 (en) 2012-12-06 2014-10-21 Eastman Chemical Company Extrusion coating of elongated substrates
WO2014111292A1 (en) 2013-01-18 2014-07-24 Basf Se Acrylic dispersion-based coating compositions
US9920526B2 (en) 2013-10-18 2018-03-20 Eastman Chemical Company Coated structural members having improved resistance to cracking
US9744707B2 (en) 2013-10-18 2017-08-29 Eastman Chemical Company Extrusion-coated structural members having extruded profile members
WO2021209535A1 (en) 2020-04-15 2021-10-21 Lego A/S Toy building bricks made of recycled abs material
JP2023530350A (en) 2020-06-16 2023-07-14 レゴ エー/エス Toy building elements made of polymeric polyester material
WO2023244956A1 (en) 2022-06-13 2023-12-21 Eastman Chemical Company Copolyester compositions having low coefficient of friction
WO2023244953A1 (en) 2022-06-13 2023-12-21 Eastman Chemical Company Copolyesters compositions having low coefficient of friction
WO2024008762A1 (en) 2022-07-06 2024-01-11 Lego A/S Method of improving functional durability of toy building elements

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3971835A (en) * 1970-07-17 1976-07-27 Rohm And Haas Company Vinyl halide polymer impact modifiers
US3793402A (en) * 1971-11-05 1974-02-19 F Owens Low haze impact resistant compositions containing a multi-stage,sequentially produced polymer
CA1062390A (en) * 1975-08-11 1979-09-11 William Steffancin Amorphous polyester graft polymer alloys
US4034013A (en) * 1975-11-13 1977-07-05 Rohm And Haas Company Impact and melt strength improvement of poly(alkylene terephthalate)
US4180494A (en) * 1977-08-15 1979-12-25 Rohm And Haas Company Thermoplastic polyesters
JPS5448850A (en) * 1977-09-26 1979-04-17 Toray Ind Inc Impact modifier
DE3039115A1 (en) * 1980-10-16 1982-05-13 Bayer Ag, 5090 Leverkusen THERMOPLASTIC POLYESTER MOLDS WITH IMPROVED TOUGHNESS
US4707513A (en) * 1980-11-03 1987-11-17 Monsanto Company Tough thermoplastic nylon compositions
US4563503A (en) * 1982-10-12 1986-01-07 Mobay Chemical Corporation Polycarbonate compositions having improved impact performance
US4659767A (en) * 1985-01-10 1987-04-21 Allied Corporation Impact modified polyester blends
US4607075A (en) * 1986-01-06 1986-08-19 Gaf Corporation Polyester compostions
US4677150A (en) * 1986-01-10 1987-06-30 Celanese Engineering Resins Inc. Modified polyester compositions
US4753986A (en) * 1986-12-22 1988-06-28 General Electric Company Polyester compositions having high impact strength
DE3733838A1 (en) * 1987-10-07 1989-04-20 Basf Ag GLASS FIBER AMPLIFIED THERMOPLASTIC MOLDINGS BASED ON POYESTERS AND POLYMERPROPYLENE
EP0310977A3 (en) * 1987-10-07 1990-07-25 BASF Aktiengesellschaft Glass fibre reinforced thermoplastic moulding compositions based on polyesters and graft polymers
DE3811014A1 (en) * 1988-03-31 1989-10-19 Basf Ag IMPACT RESISTANT THERMOPLASTIC MOLDS AND THEIR USE
US5106097A (en) * 1988-07-12 1992-04-21 Rykodisc Audio quiz game
CA1335908C (en) * 1988-10-07 1995-06-13 Junji Oshima Core-shell polymer, composition containing the polymers and its molded articles.
JP2730153B2 (en) * 1989-03-16 1998-03-25 日本合成ゴム株式会社 Thermoplastic resin composition and method for producing the same
DE69024779T2 (en) * 1989-10-23 1996-07-18 Takeda Chemical Industries Ltd Core-shell polymer and its application
DE4006643A1 (en) * 1990-03-03 1991-09-05 Basf Ag PARTICULATE GRAFT POLYMERIZED WITH IMPROVED LIABILITY BETWEEN THE GRAIN BASE AND THE Graft Shell
JP2999250B2 (en) * 1990-11-30 2000-01-17 呉羽化学工業株式会社 Novel graft copolymer
US5268438A (en) * 1991-09-06 1993-12-07 Rohm And Haas Company Aromatic polyester melt strength improver

Also Published As

Publication number Publication date
DK0577281T3 (en) 2001-12-31
JP3278980B2 (en) 2002-04-30
DE69330696T2 (en) 2002-07-11
ES2161226T3 (en) 2001-12-01
EP0577281A2 (en) 1994-01-05
US5409967A (en) 1995-04-25
JPH0665331A (en) 1994-03-08
DE69330696D1 (en) 2001-10-11
ATE205227T1 (en) 2001-09-15
US5321056A (en) 1994-06-14
EP0577281A3 (en) 1995-11-15
EP0577281B1 (en) 2001-09-05

Similar Documents

Publication Publication Date Title
US5409967A (en) Amorphous, aromatic polyester containing impact modifier
US6130290A (en) Impact modifier for amorphous aromatic polyester
US4801646A (en) Low gloss weather and impact resistant resins
KR101293933B1 (en) Impact modified thermoplastic resin composition
US4397986A (en) Thermoplastic polyester blends
US4052525A (en) Multi-layer structure acrylic polymer composition
US4417026A (en) Thermoplastic polyester moulding compositions having improved toughness
US4473679A (en) Thermoplastic acrylic elastomers
US5068285A (en) Molding compositions with acrylonitrile-styrene-acrylate rubber copolymers
US6316527B1 (en) Modified SAN resin blend compositions and articles produced therefrom
EP0462220A4 (en) Molding compositions comprising carbonate polymer, nitrile-butadiene-vinyl aromatic graft copolymer and methyl(meth)acrylate-butadiene-styrene graft copolymer and blow molding and thermoforming processes using such compositions
US5340875A (en) Blends of polybutylene terephthalate resins and methacrylic acid-containing styrenic copolymers
EP1095982A1 (en) Impact modifier concentrates for amorphous aromatic polyester
EP1085050B1 (en) Modified SAN resin blend composition and articles produced therefrom
US4775717A (en) Process of mixing melts of amorphous polyester and a graft modified polystyrene and composition thereof
KR100278170B1 (en) Core-shell impact modifiers and amorphous aromatic polyester mixtures containing the same
EP0297706A2 (en) Impact resistant acrylic sheet
JPH04505628A (en) Molding compositions comprising a carbonate polymer, a rubber-modified vinyl aromatic nitrile graft copolymer, and a methyl (meth)acrylate-butadiene-styrene graft copolymer, and blow molding and thermoforming methods using such compositions.
JPH02225557A (en) Resin composition
CA2014475A1 (en) Molding compositions comprising carbonate polymer, nitrile-butadiene-vinylaromatic graft copolymer and methyl(meth)acrylate-butadiene-styrene graft copolymer and blow molding and thermoforming processes using such compositions
JPH04185661A (en) Acrylonitrile/vinylaromatic/diene elastomer resin composition

Legal Events

Date Code Title Description
EEER Examination request
FZDE Discontinued