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WO1991002767A1 - Polymeres a greffes de polyolefines-polyesters presentant un rapport de greffe eleve - Google Patents

Polymeres a greffes de polyolefines-polyesters presentant un rapport de greffe eleve Download PDF

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Publication number
WO1991002767A1
WO1991002767A1 PCT/US1990/004822 US9004822W WO9102767A1 WO 1991002767 A1 WO1991002767 A1 WO 1991002767A1 US 9004822 W US9004822 W US 9004822W WO 9102767 A1 WO9102767 A1 WO 9102767A1
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WO
WIPO (PCT)
Prior art keywords
polyester
polyolefin
modified polyolefin
graft
copolymer
Prior art date
Application number
PCT/US1990/004822
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English (en)
Inventor
Yuji Fujita
Shigeyuki Toki
Original Assignee
Tonen Corporation
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
Priority claimed from JP21832889A external-priority patent/JPH0381333A/ja
Priority claimed from JP21832989A external-priority patent/JPH0381334A/ja
Application filed by Tonen Corporation filed Critical Tonen Corporation
Publication of WO1991002767A1 publication Critical patent/WO1991002767A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences

Definitions

  • the present invention relates to a process for producing a polyolefin-polyester graft copolymer which is effective as a compatibilizer for a resin composition composed of polycarbonates (or other engineering plastics) and polyolefins. More particularly, it is related to a process for producing a graft copolymer, having a high graft ratio, from a polyester and a modified polyolefin.
  • Aromatic polycarbonates have the disadvantages of being poor in solvent resistance and moldability despite their good impact resistance, heat resistance, stiffness, and dimensional stability. Many attempts have been made to blend polycarbonates with a polyolefin to produce a polycarbonate composition free of these disadvantages while retaining good, balanced mechanical properties. Unfortunately, the compatibility of polycarbonates with polyolefins is not good. Efforts have therefore been directed at improvement in compatibility by the incorporation of a third component.
  • Examples of the third components incorporated into the composition of polycarbonate resin and polyolefin resin are: butyl rubber (as disclosed in Japanese Patent Laid-Open No. 108151/1982), ethylene-propylene copolymer and/or ethylene-propylene-diene copolymer (as disclosed in Japanese Patent Laid-open No. 108152/1982), and isoprene rubber and/or methylpentene polymer (as disclosed in 111351/1982).
  • compositions composed of an aromatic polycarbonate and a polyester and/or modified polyolefin have also been produced. (See Japanese Patent Laid-Open Nos. 225245/1986, 235456/1986, and 238847/1986.) These compositions, however, are poor in solvent resistance because of their lack of polyolefin content.
  • thermoplastic resin composition composed of 100 parts by weight of aromatic polycarbonate (95-5 wt%) and polyolefin (5-95 wt%), 2-100 parts by weight of modified polyolefin, and 2-100 parts by weight of polybutylene terephthalate.
  • aromatic polycarbonate 95-5 wt%
  • polyolefin 5-95 wt%
  • 2-100 parts by weight of modified polyolefin 2-100 parts by weight of polybutylene terephthalate.
  • the present inventors previously proposed a process for producing a polyolefin-polyester graft copolymer as a good compatibilizer for polycarbonate resin and polyolefin, by reacting 15-85 parts by weight of polyester and 85-15 parts by weight of modified polyolefin at 260-320°C using a twin-screw extruder, said polyester having an intrinsic viscosity [ ⁇ ] of 0.30-1.20 and containing 15-200 meq./kg of terminal carboxyl groups and said modified polyolefin containing 0.2-5 mole % of epoxy groups and having a weight-average molecular weight of 8000-140,000. (See Japanese Patent Application No. 258883/1988.)
  • the present inventors previously proposed a process for producing a polyolefin- polyester graft copolymer that can be used as a good compatibilizer for polycarbonate resin and polyolefin, by reacting 10-90 parts by weight of polyester and 90- 10 parts by weight of modified polyolefin at 260-320°C in a molten mixture state, said polyester having an intrinsic viscosity [ ⁇ ] of 0.50-1.80 and containing 10-100 meq./kg of terminal carboxyl groups and said modified polyolefin containing 0.2-5 mol% of carboxyl groups or epoxy groups and having a weight-average molecular weight of 8000-140,000, said reaction being carried out in the presence of 0.05-2.0 parts by weight of water for 100 parts by weight of the total amount of said polyester and modified polyolefin. (See Japanese Patent Application No. 98564/1989.)
  • the present invention provides processes for producing high graft ratio polyolefin-polyester copolymers from a modified polyolefin and a polyester.
  • the graft ratio is greatly increased when a polyester and modified polyolefin are melt-mixed together and the resulting product is heat-treated for a long time under an inert gas stream.
  • this aspect of the invention process comprises the steps of (a) melt-mixing 2-98 parts by weight of polyester and 98-2 parts by weight of modified polyolefin containing carboxyl groups or epoxy groups, and (b) subjecting the mixture to heat treatment for 1-100 hours at a temperature 40-150°C lower than the melting point of said polyester. While not wishing to be bound by any theory, it is speculated that heat treatment promotes the reaction between the carboxyl or epoxy groups in the modified polyolefin and the terminal hydroxyl group on the polyester.
  • the graft ratio is greatly increased if a graft copolymer is produced by the reaction of a polyester with a modified polyolefin in the presence of an acid catalyst.
  • the invention process for producing a polyolefin-polyester graft copolymer comprises reacting 2-98 parts by weight of polyester with 98-2 parts by weight of a modified polyolefin containing carboxyl groups or epoxy groups in the presence of an acid catalyst, the catalyst being present in an amount of 0.01-5 parts by weight for each 100 parts by weight of said polyester and modified polyolefin.
  • the acid promotes the reaction between the carboxyl or epoxy group of the modified polyolefin and the terminal hydroxyl group of the polyester.
  • the invention product a high graft ratio copolymer of a polyester and a polyolefin, is especially useful as a compatibilizer in resin compositions that include polyolefins and polycarbonates (or other engineering plastics).
  • the polyester used in the present invention is usually a thermoplastic resin composed of a saturated dicarboxylic acid and a saturated dihydric alcohol. It includes, for example, polyethylene terephthalate, polypropylene terephthalate, polytetramethylene terephthalate (polybutylene terephthalate), polyhexamethylene terephthalate, polycyclohexane-1,4- dimethylol terephthalate, and polyneopentyl terephthalate. Preferable among them are polyethylene perephthalate and polybutylene terephthalate.
  • the useful polyesters also include polycaprolactone and polyvalerolactone, which are polymers of lactone. Preferable among these is polycaprolactone.
  • the polyester should preferably have an intrinsic viscosity [ ⁇ ] of 0.5-1.8 and contain 1-100 meq./kg of terminal carboxyl groups. (The intrinsic viscosity
  • [ ⁇ ] (dl/g) is one which is obtained from the solution viscosity in o-chlorophenol at 25°C.)
  • an intrinsic viscosity [ ⁇ ] lower than 0.5 the polyester does not significantly improve the compatibility.
  • an intrinsic viscosity [ ⁇ ] higher than 1.80 the polyester gives rise to a reaction product which has too high a melt viscosity for ease of processing.
  • a terminal carboxyl group content less than about 5 meq./kg the polyester reactivity with the modified polyolefin is poor.
  • a content of terminal carboxyl groups in excess of 100 meq./kg the polyester is too reactive with the modified polyolefin and tends to form a gel.
  • the intrinsic viscosity [ ⁇ ] should preferably be 0.50-1.0 and the content of terminal carboxyl groups should preferable be 5-100 meq./kg. With an intrinsic viscosity higher than 1.0, the polyethylene terephthalate gives rise to a graft copolymer which has a high melt viscosity and forms gel.
  • the polyethylene terephthalate may have the terephthalic acid component which is substituted by an alkyl group or halogen group; and it may also have the glycol component which contains, in addition to ethylene glycol, up to about 50 wt% of other glycols such as 1,4-butylene glycol, propylene glycol, and hexamethylene glycol.
  • the intrinsic viscosity [n] should preferably be 0.5-1.8 and the content of terminal carboxyl groups should preferably be 5-100 meq./kg.
  • the polybutylene terephthalate may have the terephthalic acid component which is substituted by an alkyl group or halogen group; and it may also have the glycol component which contains, in addition to 1,4-butylene glycol, up to about 50 wt% of other glycols such as ethylene glycol, propylene glycol, and hexamethylene glycol.
  • the polycaprolactone should preferably have a number-average molecular weight (M n ) of 500-200,000 and contain 5-2000 meq./kg of terminal carboxyl groups.
  • the modified polyolefin used in the present invention is a polyolefin formed by its copolymerization with unsaturated monomers having a carboxyl group or epoxy group.
  • the unsaturated monomer having a carboxyl group is an unsaturated carboxylic acid itself or its anhydride.
  • These include monocarboxylic acids (such as acrylic acid and methacrylic acid), dicarboxylic acids (such as maleic acid, fumaric acid, and itaconic acid), and dicarboxylic acid anhydrides (such as maleic anhydride and itaconic anhydride).
  • Preferable among these are the dicarboxylic acids and their anhydrides.
  • Examples of unsaturated monomers having an epoxy group include glycidyl methacrylate and glycidyl acrylate.
  • the unsaturated monomer having a carboxyl group or epoxy group is copolymerized with an olefin, such as, ethylene, propylene, butene-1, and pentene-1.
  • an olefin such as, ethylene, propylene, butene-1, and pentene-1.
  • These olefins may be used alone or in combination with one another.
  • These olefins may further be incorporated with less than 10 wt% of monomer (such as vinyl acetate, isoprene, chloroprene, and butadiene), according to need.
  • Preferable among these modified polyolefins are copolymers of ethylene with acrylic acid, maleic anhydride, or glycidyl methacrylate.
  • the modified polyolefin containing carboxyl groups or epoxy groups may be in the form of block copolymer, graft copolymer, random copolymer, or alternating copolymer.
  • graft copolymerization should preferably be carried out by melt-mixing a polyolefin (which functions as the main chain) with the above-mentioned unsaturated monomer.
  • the above-mentioned modified polyolefin should preferably have a weight-average molecular weight of 8,000-300,000 and contain 0.1-20 mol% of carboxyl groups or epoxy groups, where the weight-average molecular weight is measured by gel permeation chromatography (GPC) and expressed in terms of unmodified polyolefin.
  • the content of carboxyl groups is obtained by elemental analysis, and the content of epoxy groups is obtained by oxygen analysis.
  • the modified polyolefin does not produce a significant improvement in compatibility.
  • the modified polyolefin has such a high melt viscosity than it is poor in moldability.
  • the modified polyolefin With a content of carboxyl groups or epoxy groups less than 0.1 mole%, the modified polyolefin is so low in reactivity with the polyester that it does not form the graft copolymer easily. With a content of carboxyl groups or epoxy groups in excess of 20 mol%, the modified polyolefin is excessively reactive with the polyester and gives rise to a reaction product which has a high melt viscosity and forms gel.
  • the graft polymerization of said polyester and said modified polyolefin may be accomplished by the dry-blending of the two and subsequent melt-mixing.
  • the melt mixing should preferably be performed at about 260-320°C for about 0.5-1.5 minutes in an extruder, particularly in a twin-screw extruder.
  • the reaction temperature is lower than about 260°C, grafting does not take place sufficiently.
  • a reaction temperature higher than about 320°C reactions take place excessively, resulting in the clogging of the extruder due to gel formation. Excessive reactions also lead to the deterioration of resins.
  • the polyester and modified polyolefin should be used in an amount of about 2-98 parts by weight, preferably about 20-80 parts by weight, for the former and about 98-2 parts by weight, preferably about 80-20 parts by weight, for the latter. If the amount of the polyester is less than about 2 parts by weight or more than about 98 parts by weight, the graft copolymer forms in a lesser amount.
  • the mixture of said polyester and said modified polyolefin is heat treated for about 1-100 hours in an inert atmosphere at a temperature about 40-150°C, lower than the melting point of the polyester to increase the graft ratio.
  • the heat treatment temperature is higher than the melting point of the polyester minus about 40°C, the heat treatment will cause pellets to melt, when the heat treatment temperature is lower than the melting point of the polyester minus about 150°C, the heat treatment does not produce a significant effect in increasing the graft ratio.
  • the polyester is polyethylene terephthalate, the preferred heat treatment temperature is in the range of about 120- 230°C.
  • the heat treatment time varies depending on the heat treatment temperature. When the heat treatment time is less than one hour, the heat treatment does not produce a significant effect in increasing the graft ratio. Conversely, the graft ratio does not increase any further when the heat treatment lasts for more than 100 hours. Thus, a preferred heat treatment time ranges from about 5 to about 50 hours.
  • the inert atmosphere in which said heat treatment is performed is an atmosphere which brings about substantially no deterioration of the mixture. These atmospheres include inert gas (such as argon), non-reactive gas (such as nitrogen and hydrogen), and vacuum atmospheres. Heat treatment in a nitrogen stream is preferable from a practical point of view. For efficient heat treatment, the mixture should preferably be in the form of granules, like pellets.
  • an acid catalyst is added to the polyester and modified polyolefin.
  • the acid catalyst is any acid which functions as a catalyst. It includes, for example, sulfuric acid, phosphoric acid, hydrofluoric acid, and organic sulfonic acid. Preferable among them is an organic sulfonic acid, particularly p- toluenesulfonic acid.
  • the graft polymerization of said polyester and said modified polyolefin may be accomplished by the melt-mixing method or solution method.
  • the melt-mixing acid-catalyzed method may be practiced by mixing the polyester, modified polyolefin, and acid catalyst in the heated state using a mixer, such as, single-screw extruder, twin- screw extruder, Banbury mixer, mixing roll, Brabender, and kneader.
  • a mixer such as, single-screw extruder, twin- screw extruder, Banbury mixer, mixing roll, Brabender, and kneader.
  • the mixing should last for about 0.5-15 minutes at about 180-320°C, depending on the melting point of the polyester used.
  • Mixing in a twin-screw extruder is preferable.
  • grafting does not take place sufficiently due to insufficient polymer melting.
  • reaction temperature higher than 320°C reactions take place excessively, resulting in the clogging of the extruder due to gel formation. Excessive reactions lead to the deterioration of resins.
  • the solution method may be practiced by stirring a solution of said starting materials in an organic solvent, such as for example xylene, at about 80- 140°C.
  • an organic solvent such as for example xylene
  • the polyester and modified polyolefin should be used in an amount of about 2-98 parts by weight, preferably about 20-80 parts by weight, for the former and about 98-2 parts by weight, preferably about 80-20 parts by weight, for the latter. If the amount of the polyester is less than about 2 parts by weight or more than about 98 parts by weight, the graft copolymer forms in a lesser amount.
  • the acid catalyst should be added in an amount of 0.01-5 parts by weight, preferably 0.1-3 parts by weight, for 100 parts by weight of the total amount of the polyester and modified polyolefin. With an amount less than 0.01 parts by weight, the acid catalyst does not produce a good effect of increasing the graft ratio. With an amount more than 5 parts by weight, the acid catalyst forms gel due to excessive reactions.
  • the polyolefin-polyester graft copolymers obtained from the invention processes have a high graft ratio and are suitable for use as compatibilizers for engineering plastics (such as polycarbonates and polyolefins).
  • the graft copolymer is incorporated in an amount of 1-30 parts by weight for 100 parts by weight of the total amount of the two.
  • PET Polyethylene terephthalate (TR4550), made by Teijin Kasei, having a weight- average molecular weight of 104,000 and an intrinsic viscosity [ ⁇ ] of 0.7, and containing 35 meq./kg of terminal carboxyl groups.
  • PBT Polybutylene terephthalete (TRB-K), made by Teijin Kasei, having a weight- average molecular weight of 38,000 and an intrinsic viscosity [ ⁇ ] of 0.73, and containing 60 meq./kg of terminal carboxyl groups.
  • PCL Polycaprolactone, made by Scientific Polymer Products, Inc., having a weight- average molecular weight of 23,000.
  • Modified PO (1) A copolymer of glycidyl methacrylate and ethylene ("Bondfast E") made by Sumitomo chemical Co., Ltd., containing 4.0 mol% of glycidyl methacrylate and having a weight-average molecular weight of 263,000.
  • Modified PO (2) A copolymer of acrylic acid and ethylene (“Primacol 3440") made by
  • Modified PO (3) A graft copolymer of polypropylene with maleic anhydride, containing 0.25 mol% of maleic anhydride and having a weight-average molecular weight of
  • Acid catalyst P-TSA p-ptoluenesulfonic acid (reagent grade), made by Tokyo Kasei Co., Ltd.
  • H 2 SO 4 Sulfuric acid (reagent grade), made by Tokyo Kasei Co. , Ltd.
  • the weight-average molecular weight is one which is measured by the GPC method, and it is expressed in terms of polyethylene for the modified PO (1) and modified PO (2) and in terms of polypropylene for the modified PO (3).
  • the polyester and modified polyolefin were dry blended at a ratio of 30/70 (by weight) as shown in Table 1, and the dry blend was made into pellets by melt mixing at 280°C and 200 rpm using a 45-mm twin-screw extruder. The resulting pellets underwent heat treatment at 170°C for 24 hours under a nitrogen stream. The copolymer was tested for graft ratio A.
  • the polyester (polyethylene terephthalate or polybutylene terephthalate) and the modified polyolefin (1) were dry-blended in a ratio of 30/70 or 50/50 (by weight) together with p-toluenesulfonic acid as the acid catalyst as shown in Table 1.
  • the dry blend underwent melt mixing for grafting reaction at 280°c and 200 rpm using a 45-mm twin-screw extruder.
  • the resulting polyolefin polyester graft copolymer was tested for graft ratio (graft ratio A).
  • the reaction mixture was poured into methanol to precipitate the polymer formed by the reaction.
  • the precipitates were filtered off and dried at 60oC for 12 hours in a vacuum oven to obtain the polyolefin-polyester graft copolymer.
  • the resulting polyolefin-polyester graft copolymer was tested for graft ratio (graft ratio B).
  • Graft ratio B is calculated by the following formula from xylene insolubles which remain after the separation of unreacted polycaprolactone (soluble in xylene) from the reaction product.
  • X is the amount of xylene insolubles
  • Y is the amount of modified polyolefin (3) used.
  • Example 9 The procedure of Example 9 was repeated except that no acid catalyst was added. the resulting copolymer was tested for graft ratio B. The results are shown in Table 2.
  • the polycaprolactone and the modified polyolefin (3) were melt-mixed for grafting reaction in a ratio of 70/30 (by weight) together with p-toluenesulfonic acid or sulfuric acid as the acid catalyst using a Brabender at 200°C and 60 rpm for 10 minutes, as shown in Table 2.
  • the resulting polyolefin-polyester graft copolymer was tested for graft ratio B. The results are shown in Table 2.
  • Example 12 The procedure of Example 12 was repeated except that no aid catalyst was added. The resulting copolymer was tested for graft ratio B. The results are shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

Nouveaux copolymères de polyesters et de polyoléfines présentant des rapports de greffe élevés, et procédés de production de ces copolymères à greffe. Les procédés consistent à greffer des groupements réactifs tels que des groupes carboxyle ou époxy sur la polyoléfine, et à les faire réagir avec des groupes hydroxyle sur les polyesters, de manière à former des copolymères à rapports de greffe élevés. Selon un aspect, le procédé utilise un traitement thermique afin de produire le rapport de greffe élevé; selon un autre aspect il utilise un catalyseur acide.
PCT/US1990/004822 1989-08-24 1990-08-24 Polymeres a greffes de polyolefines-polyesters presentant un rapport de greffe eleve WO1991002767A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP218328/89 1989-08-24
JP218329/89 1989-08-24
JP21832889A JPH0381333A (ja) 1989-08-24 1989-08-24 ポリオレフィン―ポリエステルグラフト共重合体の製造方法
JP21832989A JPH0381334A (ja) 1989-08-24 1989-08-24 ポリオレフィン―ポリエステルグラフト共重合体の製造方法

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991014248A1 (fr) * 1990-03-08 1991-09-19 Exxon Chemical Patents Inc. Copolymeres greffes a polyolefine cristalline
EP0475142A2 (fr) * 1990-09-05 1992-03-18 Harold Verity Smith Composition de moulage à base du produit de réaction d'un polyéréphatalate d'éthylène et d'un copolymère d'anhydride maléique
WO1992022608A1 (fr) * 1991-06-17 1992-12-23 General Electric Company Compositions derivees de polymeres recycles
US5420199A (en) * 1992-02-25 1995-05-30 Teijin Limited Thermoplastic polyester resin composition containing polybutylene terephthalate, modified polyolefin and polycarbonate resins
EP0745647A1 (fr) * 1995-05-31 1996-12-04 Montell North America Inc. Mélanges de polyoléfines greffées et de polycarbonates
WO1997012919A1 (fr) * 1995-10-06 1997-04-10 The Dow Chemical Company Polymeres blocs d'ethylene ramifies, leur preparation, et compositions les comprenant
US6528586B2 (en) 2000-05-16 2003-03-04 Gordon Mark Cohen Compositions of elastomeric ethylene/(meth)acrylic (acid) ester copolymer and polylactone or polyether
US20160168331A1 (en) * 2011-09-01 2016-06-16 Aspen Research Corporation Methods and systems of graft polymerization on a functionalized substrate

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JPH01213352A (ja) * 1988-02-19 1989-08-28 Toray Ind Inc 熱可塑性樹脂組成物
EP0364304A2 (fr) * 1988-10-14 1990-04-18 Tonen Chemical Corporation Copolymère greffé polyoléfine-polyester modifié, méthode de sa préparation et composition de résine thermoplastique contenant un tel copolymère greffé

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JPS62280227A (ja) * 1986-05-29 1987-12-05 Mitsui Petrochem Ind Ltd 成形物品の製造方法
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EP0364304A2 (fr) * 1988-10-14 1990-04-18 Tonen Chemical Corporation Copolymère greffé polyoléfine-polyester modifié, méthode de sa préparation et composition de résine thermoplastique contenant un tel copolymère greffé

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STN International, File CA, CHEMICAL ABSTRACTS, Volume 112, No. 10, 5 March 1990, (Columbus, Ohio, US), OKAMOTO, MASARU et al.: "Heat- and Impact- Resistant Polyester-Polyolefin Compositions", abstract 78733s; & JP,A,01 190 751, 31 Jul. 1989, Heisei. 11 pp. (Japan). *
STN International, File CA, CHEMICAL ABSTRACTS, Volume 112, No. 12, 19 March 1990, (Columbus, Ohio, US), YONETANI, KIICHI et al.: "Heat- and Water-Resistant Thermoplastic Polyester-Polyolefin Compositions with good Electric Properties", abstract 100058z; & JP,A,01 213 352, 28 Aug. 1989, Heisei. 10 pp. (Japan). *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991014248A1 (fr) * 1990-03-08 1991-09-19 Exxon Chemical Patents Inc. Copolymeres greffes a polyolefine cristalline
EP0475142A2 (fr) * 1990-09-05 1992-03-18 Harold Verity Smith Composition de moulage à base du produit de réaction d'un polyéréphatalate d'éthylène et d'un copolymère d'anhydride maléique
EP0475142A3 (en) * 1990-09-05 1992-10-07 Harold Verity Smith Moulding composition of polyethylene terephthalate reacted with a copolymer of maleic anhydride
AU651992B2 (en) * 1990-09-05 1994-08-11 Harold Verity Smith Polyethylene terephthalate compositions and methods of using thereof
WO1992022608A1 (fr) * 1991-06-17 1992-12-23 General Electric Company Compositions derivees de polymeres recycles
US5264487A (en) * 1991-06-17 1993-11-23 General Electric Company Compositions derived from recycled polymers
US5420199A (en) * 1992-02-25 1995-05-30 Teijin Limited Thermoplastic polyester resin composition containing polybutylene terephthalate, modified polyolefin and polycarbonate resins
EP0745647A1 (fr) * 1995-05-31 1996-12-04 Montell North America Inc. Mélanges de polyoléfines greffées et de polycarbonates
WO1997012919A1 (fr) * 1995-10-06 1997-04-10 The Dow Chemical Company Polymeres blocs d'ethylene ramifies, leur preparation, et compositions les comprenant
US6528586B2 (en) 2000-05-16 2003-03-04 Gordon Mark Cohen Compositions of elastomeric ethylene/(meth)acrylic (acid) ester copolymer and polylactone or polyether
US20160168331A1 (en) * 2011-09-01 2016-06-16 Aspen Research Corporation Methods and systems of graft polymerization on a functionalized substrate
US9676907B2 (en) * 2011-09-01 2017-06-13 Aspen Research Corporation Methods and systems of graft polymerization on a functionalized substrate

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