EP0467958A1 - Copolymere greffe de polypropylene-polyester et son procede de production - Google Patents

Copolymere greffe de polypropylene-polyester et son procede de production

Info

Publication number
EP0467958A1
EP0467958A1 EP90906580A EP90906580A EP0467958A1 EP 0467958 A1 EP0467958 A1 EP 0467958A1 EP 90906580 A EP90906580 A EP 90906580A EP 90906580 A EP90906580 A EP 90906580A EP 0467958 A1 EP0467958 A1 EP 0467958A1
Authority
EP
European Patent Office
Prior art keywords
polypropylene
polyester
weight
graft copolymer
carboxyl group
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.)
Withdrawn
Application number
EP90906580A
Other languages
German (de)
English (en)
Other versions
EP0467958A4 (en
Inventor
Tadashi 8-242 Shimodacho 5-Chome Sezume
Akira 5-18 Nishihara 1-Chome Kobayashi
Kikuo 4-4-433 Nishitsurugaoka 1-Chome Inamori
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.)
Tonen General Sekiyu KK
Original Assignee
Tonen Corp
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 Tonen Corp filed Critical Tonen Corp
Publication of EP0467958A1 publication Critical patent/EP0467958A1/fr
Publication of EP0467958A4 publication Critical patent/EP0467958A4/en
Withdrawn legal-status Critical Current

Links

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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a polypropylene-polyester graft copolymer which is effective as a compatibilizing agent for both of ingredients in a resin composition comprising a polycarbonate and a polyolefin, in particular, a polypropylene, and a production process for the graft copolymer. More in particular, it relates to a graft copolymer of a polyester having specific intrinsic viscosity and concentration of terminal carboxyl group and a modified polypropylene having a specific melt flow rate (MFR), as well as a production process thereof.
  • MFR melt flow rate
  • Aromatic polycarbonates have excellent impact resistance, heat resistance, rigidity and dimensional stability, but they involve a drawback of insufficient solvent resistance and moldability.
  • Japanese Patent Laid Open Sho 57-108151 discloses a butyl rubber
  • Japanese Patent Laid Open Sho 57-108152 discloses an ethyl ene-propylene copolymer and/or ethyl ene-propylene-diene copolymer
  • Japanese Patent Laid Open Sho 57-111351 discloses an isoprene rubber and/or methyl pentene polymer.
  • the present inventors have previously proposed a process for producing a polyolefin-polyester graft copolymer that can be used as a satisfactory compatibilizing agent for a polycarbonate resin and a polyolefin by reacting from 15 to 85 parts by weight of a polyester having an intrinsic viscosity [ ⁇ ] of 0.30 and 1.2 and a concentration of terminal carboxyl group of 15 to 200 meg/ g, and from 85 to 15 parts by weight of a modified polyolefin containing 0.2 to 5 moll of epoxy groups and having a weight average molecular weight of 8,000 to 140,000 in a twin screw extruder at 260 - 320°C (Japanese Patent Application Sho 63-258883).
  • an object of the present invention to provide a polypropylene-polyester graft copolymer capable of functioning as a compatibilizing agent for a polycarbonate resin and a polyolefin, particularly, a polypropylene.
  • Another object of the present invention is to provide a process for producing such a propylene-polyester graft copolymer.
  • a graft copolymer of a polyester and a functional group-containing modified polypropylene is effective as a compatibilizing agent for a polycarbonate resin and a polyolefin, particularly, a polypropylene and that a desired polypropylene-polyester graft copolymer can be obtained through grafting reaction by defining the intrinsic viscosity and the concentration of the terminal carboxyl group of the polyester and the functional group content and the melt flow rate (MFR) of the modified polypropylene to respective specific ranges.
  • a polypropylene-polyester graft copolymer according to the present invention comprises from 10 to 90 parts by weight of a polyester having an intrinsic viscosity [ ⁇ ] of 0.5 to 1.8 and a concentration of terminal carboxyl group of 10 to 1000 meq/Kg, and 90 to 10 parts by weight of a modified polypropylene containing 0.2 to 5.0 % by weight of functional groups and a melt flow rate (MFR) measured at 230°C under the load of 2160 g) of 0.5 to 80 g/10 min.
  • a process for producing a polypropylene- polyester graft copolymer according to the present invention comprises reacting:
  • the polyester used in the present invention is, generally, a thermoplastic resin comprising a saturated dicarboxylic acid and a saturated difunctional alcohol and there can be mentioned, for example, polyethylene terephthalate, polypropylene terephthalate, polytetramethylene terephthalate (polybutylene terephthalate), polyhexamethylene terephthalate, polycyclohexane-1,4-dimethylol terephthalate and polyneopentyl terephthalate.
  • polyethylene terephthalate and polybutylene terephthalate are particularly preferred.
  • the polyester has an intrinsic viscosity [ ] Of 0.5 to 1.8 and a concentration of terminal carboxyl group of 10 to 100 meq/Kg.
  • the intrinsic viscosity [ ⁇ ] (dl/g) is determined from a solution viscosity measured in an o-chlorophenol solvent at 25°C. If the intrinsic viscosity [ ⁇ ] of the polyester is less than 0.5, the effect for improving the compatibility is insufficient. On the other hand, if it exceeds 1.8, the melt viscosity of the reaction product is increased to bring about a difficulty in fabrication. Meanwhile, if the concentration of the terminal carboxyl group is less than 10 meq/Kg, reactivity with the modified polypropylene is poor.
  • the intrinsic viscosity [ ⁇ ] is from 0.5 to 1.0 and the concentration of the terminal carboxyl group is from 10 to 100 meq/kg. If the intrinsic viscosity [ ⁇ ] exceeds 1.0, the m melt viscosity of the graft polymer is increased to cause gelation.
  • the terephthalic acid ingredient in the polyethylene terephthalate may be substituted with alkyl group, halogen group, etc.
  • the glycol ingredient may contain, in addition to ethyl ene glycol, up to about 50% by weight of other glycol, for example, 1,4-butylene glycol, propylene glycol, hexamethylene glycol, etc.
  • the intrinsic viscosity [ ⁇ ] is from 0.5 to 1.8 and the concentration of the terminal carboxyl group is from 10 to 100 meq/Kg.
  • the terephthalic acid ingredient may be substituted with alkyl group, halogen group, etc. Further.
  • the modified polypropylene used in the present invention is a polypropylene containing an unsaturated monomer having a functional group.
  • the functional group contained in the modified polypropylene is at least one such group that is reactive with the terminal carboxyl group or hydroxyl group of the polyester and it can include for example carboxyl group, epoxy group, hydroxyl group and amino group.
  • the unsaturated monomer having carboxyl group is an unsaturated carboxyl ic acid or anhydride thereof and it can include, for example, monocarboxylic acid such as acrylic acid or methacrylic acid, dicarboxylic acid such as maleic acid, humaric acid or itanconic acid, dicarboxylic acid anhydride such as maleic acid anhydride or itaconic acid anhydride, the dicarboxylic acid and anhydride thereof being particularly preferred.
  • monocarboxylic acid such as acrylic acid or methacrylic acid
  • dicarboxylic acid such as maleic acid, humaric acid or itanconic acid
  • dicarboxylic acid anhydride such as maleic acid anhydride or itaconic acid anhydride
  • the dicarboxylic acid and anhydride thereof being particularly preferred.
  • the unsaturated monomer having epoxy group there can be mentioned glycidyl ester of metacrylic acid or glycidyl ester of acrylic acid.
  • the backbone for the functional group-containing modified polypropylene may be any of block copolymer, graft copolymer, random copolymer or intercopolymer of, e.g., propylene and it is, particularly preferably, a propylene random copolymer containing a non-conjugated diene comonomer represented by the general formula: where R 1 - R 4 each represents H or an alkyl group with 1 to 6 carbon atoms and n represents an integer of 1 to 20.
  • non-conjugated diene there can be mentioned, for example, 1,4-hexadiene, 7-methyl-1,6-octadiene, 5-methyl- 1,4-hexadiene, 1,9-decadiene, 4-methyl-1,4-heptadiene, 4-ethyl- 1,4-hexadiene and 1,13-tetradecadiene.
  • 1,4-hexadiene, 7-methyl-1,6-octadiene, 5-methyl-1,4-hexadiene and 1,9 decadiene are particularly preferred.
  • Two or more of the non-conjugated diene comonomers may be used in admixture.
  • the ratio of the non-conjugated diene is from 0.05 to 10 mol%. If the content of the non-conjugated diene is less than 0.05 mol%, high grafting rate can not be obtained in the subsequent grafting reaction. On the other hand, if it exceeds 10 mol%, crystal Unity of the copolymer is remarkably reduced. More preferred content of the non-conjugated diene is from 0.1 to 3 mol%.
  • propylene copolymerized with the unsaturated monomer having the functional group as described above may be incorporated as required, with less than 10% by weight of olefin such as ethylene, butene-1 or pentene-1, monomers such as vinyl acetate, isoprene, chloroprene or butadiene.
  • olefin such as ethylene, butene-1 or pentene-1
  • monomers such as vinyl acetate, isoprene, chloroprene or butadiene.
  • the unsaturated monomer having the functional group may be reacted with the polypropylene-non conjugated diene random copolymer by the following methods.
  • melt-kneading method melt-kneading a random copolymer, a monomer and a radical generator using an extruder or the like thereby causing reaction, etc.
  • the melt-kneading method is suitable since the continuous reaction is easy.
  • the reaction time is preferably from 10 sec to 20 min.
  • peroxides such as benzoyl peroxide, lauroyl peroxide, ditertiary butylperoxide, acetyl peroxide, tertiary butyl peroxybenzoic acid, dicumyl peroxide, peroxybenzoic acid, peroxyacetic acid, tertiary butyl peroxypivalate, or diazo compounds such as azobisisobutylonitrile are preferred.
  • the blending ratio is desirably within a range from 0.1 to 10 parts by weight based on 100 parts by weight of the radical polymerizable monomer. It is also possible to cause grafting reaction by kneading under heating without using the radical generator.
  • melt flow rate (MFR) of the modified polypropylene be from 0.5 to 80 g/10 min and the amount of the functional group in the modified polypropylene be from 0.1 to 2.0% by weight.
  • the melt flow rate (MFR) was measured at 230oC under the load of 2160 g and represented by the unit of g/10 min.
  • the functional group content was determined from the analytical value for elemental oxygen. If the melt flow rate (MFR) exceeds 80 g/10 min (that is, if the molecular weight is too low), reaction with polyester minimally occurs, bringing about a difficulty in the snythesis of the graft copolymer.
  • the melt viscosity is increased such that moldability properties are adversely affected.
  • the average molecular weight (Mw) of the modified polypropylene having MFR from 0.5 to 80 g/10 min is about from 70,000 to 300,000.
  • the functional group is less than 0.1% by weight, the reactivity with the polyester is so poor that graft copolymer is minimally formed.
  • it exceeds 2.0% by weight the melt viscosity of the reaction product is increased due to the excess reaction, tending to result in gel-like material.
  • both of them are dry blended and then melt-kneaded at 240 - 300oC, for polypropylene, and at 260 - 320oC for other polyolefins.
  • the melt-kneading is preferably conducted in an extruder, particularly, in a twin screw extruder. If the reaction temperature is lower than described, the grafting is not sufficient. On the other hand, if it exceeds that described, excess reaction occurs and the melting temperature of the reaction product is increased, tending to cause blocking in the extruder. Further, the modified polypropylene adversely tends to be degraded more easily.
  • the time for the grafting reaction is typically from about 0.5 to 15 min although it may vary depending on the reaction conditions.
  • the blending amount of the polyester and the modified polypropylene is from 10 to 90 parts by weight, preferably, from 20 to 80 parts by weight from the former and from 90 to 10 parts by weight and, preferably, from 80 to 20 parts by weight for the latter. If the polyester is less than 10 parts by weight or greater than 90 parts by weight, the amount of the graft copolymer formed is reduced.
  • the thus obtained polypropylene-polyester graft copolymer is useful as a compatibilizing agent for a polycarbonate resin and a polyolefin, particularly a polypropylene and, generally, it is added at a ratio of 1 to 30 parts by weight based on 100 parts by weight of the sum of both of them.
  • the grafting reaction proceeds easily, a graft copolymer of sufficient grafting ratio can be obtained and formation of gel due to excess reaction can be prevented.
  • MFR melt flow rate
  • Examples 1 - 6 Comparative Examples 1 - 3 As shown in Table 1, after blending polyethylene terephthalate or a polybutylene terephthalate each having various intrinsic viscosities [ ] and concentrations of terminal carboxyl group and modified polypropylene (graft copolymer of propylene non-conjugated diene random copolymer and maleic acid anhydride or glycidyl methacrylate) having various functional group contents and melt flow rates (MFR) at a ratio of 20/80 (by weight), they were supplied to a twin screw extruder of 45 mm ⁇ and a melt-kneaded at 280°C at 200 rpm to proceed grafting reaction.
  • MFR melt flow rates
  • Example 7 A copolymer was produced and measured in the same manner as in Example 1 except for using, as a polyester, a mixture of 50% by weight of a polyethylene terephthalate having an intrinsic viscosity [ ] of 0.72 and a concentration of terminal carboxyl group of 30 meq/Kg, and 50% by weight of a polybutylene terephthalate having an intrinsic viscosity [ ⁇ ] of 0.85 and a concentration of terminal carboxyl group of 52 meq/Kg. The results are also shown in Table 1. Also in this example, neither the gel formation nor the clogging of the extruder was observed. Examples 8, 9 Copolymers were produced in the same manner as in Example 1 except for changing the ratio (by weight) of the polybutylene
  • polyester having an intrinsic viscosity [ ⁇ ] and a concentration of terminal carboxyl group each within a predetermined range, and a modified polypropylene having a functional group content and a melt flow rate (MFR) each in a predetermined range are reacted, a copolymer can be obtained at a high grafting ratio.
  • the polypropylene-polyester graft copolymer according to the present invention thus obtained is extremely effective as a compatibilizing agent for a polycarbonate resin and a polyolefin, particularly, a polypropylene.

Landscapes

  • 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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne un agent de compatibilisation efficace pour les compositions de résine d'un polycarbonate et d'une polyléfine, dans lesquelles l'agent de compatibilisation est un copolymère greffé de polypropylène modifié contenant des groupes fonctionnels que l'on a fait réagir avec un polyester ayant une viscosité intrinsèque comprise entre 0,5 et 1,8 et un groupe terminal de carboxyle présent en une quantité allant de 10 à 100 meq/kg.
EP19900906580 1989-04-12 1990-04-11 Polypropylene-polyester graft copolymer and production method thereof Withdrawn EP0467958A4 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP92180/89 1989-04-12
JP9218089 1989-04-12
JP324269/89 1989-12-14
JP1324269A JPH0347844A (ja) 1989-04-12 1989-12-14 ポリプロピレン―ポリエステルグラフト共重合体及びその製造方法

Publications (2)

Publication Number Publication Date
EP0467958A1 true EP0467958A1 (fr) 1992-01-29
EP0467958A4 EP0467958A4 (en) 1992-08-19

Family

ID=26433649

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900906580 Withdrawn EP0467958A4 (en) 1989-04-12 1990-04-11 Polypropylene-polyester graft copolymer and production method thereof

Country Status (6)

Country Link
EP (1) EP0467958A4 (fr)
JP (1) JPH0347844A (fr)
KR (1) KR920701312A (fr)
AU (1) AU5422290A (fr)
CA (1) CA2050283A1 (fr)
WO (1) WO1990012054A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5298557A (en) * 1990-02-02 1994-03-29 Tonen Corporation Thermoplastic resin composition
US5283285A (en) * 1993-04-05 1994-02-01 Alliedsignal Inc. High impact polyester/polycarbonate blends
NO179840C (no) * 1994-04-28 1996-12-27 Borealis As Polymerlegering hvor det som kompatibilisator er anvendt en podet kopolymer av en funksjonalisert polypropylenpolymer og en novolakpolymer
NO179839C (no) * 1994-04-28 1996-12-27 Borealis As Podet kopolymer av en funksjonalisert polypropylenpolymer og en novolakpolymer og fremgangsmåte for fremstilling av denne
US20220169802A1 (en) * 2019-03-29 2022-06-02 Sabic Global Technologies B.V. Film from graft copolymer having a polypropylene backbone, and nanoporous polypropylene membrane
EP4013809B1 (fr) * 2019-08-18 2023-07-19 SABIC Global Technologies, B.V. Utilisation d'une composition pour la fabrication d'un article en mousse

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0158764A1 (fr) * 1983-12-29 1985-10-23 Monsanto Company Mélanges à base de caoutchouc acrylique rendus compatibles
WO1988005452A1 (fr) * 1987-01-16 1988-07-28 General Electric Company Modificateurs d'impact olefiniques pour des resines de polyester plastique et melanges avec celles-ci

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172859A (en) * 1975-05-23 1979-10-30 E. I. Du Pont De Nemours And Company Tough thermoplastic polyester compositions
JPS59215351A (ja) * 1983-05-24 1984-12-05 Mitsui Petrochem Ind Ltd 熱可塑性樹脂組成物
US4654401A (en) * 1984-12-24 1987-03-31 General Electric Company Hydroxyl group graft modified polyolefins
BR8900992A (pt) * 1988-03-16 1989-10-24 Polyplastics Co Processo para producao de resina de poliester termoplastico aperfeicoada e resina de poliester termoplastico produzida
JP2599630B2 (ja) * 1988-10-14 1997-04-09 東燃化学株式会社 ポリオレフィン―ポリエステルグラフト共重合体及びその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0158764A1 (fr) * 1983-12-29 1985-10-23 Monsanto Company Mélanges à base de caoutchouc acrylique rendus compatibles
WO1988005452A1 (fr) * 1987-01-16 1988-07-28 General Electric Company Modificateurs d'impact olefiniques pour des resines de polyester plastique et melanges avec celles-ci

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9012054A1 *

Also Published As

Publication number Publication date
JPH0347844A (ja) 1991-02-28
AU5422290A (en) 1990-11-05
EP0467958A4 (en) 1992-08-19
KR920701312A (ko) 1992-08-11
CA2050283A1 (fr) 1990-10-13
WO1990012054A1 (fr) 1990-10-18

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