WO1990012837A1 - Process for production of polyolefin-polyester graft copolymer - Google Patents
Process for production of polyolefin-polyester graft copolymer Download PDFInfo
- Publication number
- WO1990012837A1 WO1990012837A1 PCT/US1990/001970 US9001970W WO9012837A1 WO 1990012837 A1 WO1990012837 A1 WO 1990012837A1 US 9001970 W US9001970 W US 9001970W WO 9012837 A1 WO9012837 A1 WO 9012837A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- polyester
- polyolefin
- parts
- carboxyl group
- Prior art date
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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
-
- 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 compatibilizing agent for both of ingredients in a resin composition comprising an engineering plastic such as a polycarbonate and a polyolefin. More in particular, it relates to a method of preventing gel formation upon producing a graft copolymer of a polyester having specific intrinsic viscosity and concentration of terminal carboxyl group and a modified polyolefin containing epoxy or carboxyl groups.
- Aromatic polycarbonates have excellent impact resistance, heat resistance, rigidity and dimensional stability, but they involve a drawback of insufficient solvent resistance and moldability. For obtaining a composition of well-balanced mechanical properties while compensating these drawbacks, various studies have been made on blends with polyolefin. However, since the compatibility between a polyolefin and a polycarbonate is not so good, it has been attempted to add third ingredients for improving the compatibility.
- 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 meq/Kg, and from 85 to 15 parts by weight of a modified polyolefin containing 0.2 to 5 mol % 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 process for stably producing a polyolefin-polyester graft copolymer which is a satisfactory compatibilizing agent for an engineering plastic such as a polycarbonate resin and a polyolefin, without clogging the extruder while preventing gel formation.
- the present inventors have made earnest studies for attaining the foregoing object and, as a results, have found that it can be attained by the reaction while defining the intrinsic viscosity and the concentration of the terminal carboxyl group of a polyester and the functional group content and the molecular weight of a modified polyolefin to respective predetermined ranges and by adding water to the reaction system thereby accomplishing the present invention.
- a process for producing a polyolefin-polyester graft polymer according to the present invention resides in melt-kneading to react: (a) from 10 to 90 parts by weight of a polyester having a intrinsic viscosity [ ⁇ ] of 0.50 to 1.8 and a concentration of terminal carboxyl group of 10 to 100 meq/Kg, and (b) from 90 to 10 parts by weight of a modified polyolefin containing 0.2 to 5 mol % of carboxyl group or epoxy group and having a weight average molecular weight of 8,000 to 140,000, at 250 - 320°C, wherein from 0.05 to 2.0 parts by weigtrt of water is added to 100 parts by weight of the sum of the polyester and the modified polyolefin.
- 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 0.50, 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 0.50 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 melt viscosity of the graft polymer is increased to cause gelation.
- ttie tereptittvalic acid ingredient in the polyethylene terephthalate may be substituted with alkyl group, halogen group, etc.
- the glycol ingredient may contain, in addition to ethylene glycol, up to about 50% by weight of other glycol, for example, 1,4-butylene glycol, propylene glycol, hexamethylene glycol, etc. in the case of polybutylene terephthalate, it is sufficient that 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.
- glycol ingredient may contain, in addition to 1,4 butylene glycol, up to about 50% by weight of other glycol, for example ethylene glycol, propylene glycol and hexamethylene glycol.
- modified polyolefin used in the present invention is a polyolefin copolymerized with an unsaturated monomer having a functional group.
- the unsaturated monomer having the carboxyl group is an unsaturated carboxylic 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 itaconic acid, dicarboxylic acid anhydride such as maleic acid anhydride or itaconic acid anhydride, 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 itaconic acid
- dicarboxylic acid anhydride such as maleic acid anhydride or itaconic acid anhydride
- dicarboxylic acid and anhydride thereof being particularly preferred.
- the unsaturated monomer having epoxy group there can be mentioned glycidyl ester of metacrylic acid.
- olefins such as ethylene, propylene, butene-1 and pentene-1. These olefins may be used alone or as a mixture of two or more of them. Further, the olefins may be incorporated, as required, with less than 10% by weight of other copolymerizable monomers, for example, vinyl acetate, isoprene, chloroprene and butadiene.
- olefins ethylene, propylene, butene-1 and pentene-1.
- the olefins may be incorporated, as required, with less than 10% by weight of other copolymerizable monomers, for example, vinyl acetate, isoprene, chloroprene and butadiene.
- copolymers of glycidyl acrylate or methacrylate and ethylene are particularly preferred.
- the modified polyolefin containing carboxyl group of epoxy group may be any of block copolymer, graft copolymer, random copolymer or intercopolymer. It is necessary that the weight average molecular weight of the modified polyolefin is from 8,000 to 140,000 and the content of the carboxyl group or epoxy group in the modified polyolefin is from 0.2 to 5 mol %. The weight average molecular weight was measured by a gel permeation chromatography (GPC) and converted as the not-modified polyolefin. Further, the carboxyl group content was determined based on the elemental analysis value. The epoxy group content was determined based on the analysis value for elemental oxygen.
- GPC gel permeation chromatography
- the weight average molecular weight is less than 8,000, the effect of improving the compatibility is insufficient. On the other hand, if it exceeds 140,000, the melt viscosity is increased to worsen the moldability. Further, if the carboxyl group or the epoxy group is less than 0.2 mol %, reactivity with the polyester is poor in which graft copolymer is less formed. On the other hand, if it exceeds 5 mol %, melt viscosity of the reaction product is increased due to excess reaction with the polyester, tending to form gel-like material easily. For graft polymerizing the polyester and the modified polyolefin, both of them are dry blended and then melt-kneaded at 260 - 320°C for 0.5 to 15 min.
- the melt-kneading is preferably conducted in an extruder, particularly, in a twin screw extruder. If the reaction temperature is lower than 260°C, grafting is to sufficient. On the other hand, if it exceeds 320°C, excess reaction occurs to cause blocking in the extruder due to the gel formation. Also, the resin tends to be degraded easily.
- the blending amount of the polyester and the modified polyolefin is from 10 to 90 parts by weight, preferably, from 20 to 80 parts by weight for 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 polyester and the modified polyolefin are reacted under melt-kneading, wherein from 0.05 to 2.0 parts by weight of water is added based on 100 parts by weight of the sum of the polyester and the modified polyolefin. If the addition amounts of the water is less than 0.05 parts by weight, gel formation can not be prevented sufficiently. If it exceeds 2.0 parts by weight, the molecular weight of the graft copolymer is too low to sufficiently attain the improving effect for the compatibility.
- water is continuously supplied to the inside of the extruder by means of a pump.
- the addition of water to the downstream side of a kneading zone of the extruder is preferred.
- the thus obtained polyolefin-polyester graft copolymer is satisfactory as a compatibilizing agent for a polycarbonate resin and a polyolefin, and, generally, it is added at a ratio of 1 to 30 parts by weight based on 100 parts by weight of the sum for both of them.
- grafting rate was determined by isolating ingredients insoluble to both of m-cresol (100°C) and xylene (100°C).
- polyethylene terephthalate or a polybutylene terephthalate each having various intrinsic viscosities [ ⁇ ] and concentrations of terminal carboxyl group and modified polyethylene (graft copolymer of glycidyl methacrylate or acrylate and ethylene) having various contents of epoxy and carboxyl groups and number average molecular weights at a ratio of
- water was added at a ratio shown in Table 1 based on 100 parts by weight of the sum of the polyethylene terethalate and a modified polyethylene to the down- stream side of the kneading zone in a twin screw extruder.
- the residence time in the extruder was about 1 min.
- MFR, grafting ratio, occurrence of gel formation and occurrence of clogging in the extruder were as shown in Table 1.
- Example 10 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 [ ⁇ ] m of 0.70 and a concentration of terminal carboxyl group of 35 meq/Kg, and 50% by weight of a polyethylene terephthalate having an intrinsic viscosity [ ⁇ ] of 0.73 and a concentration of terminal carboxyl group of 60 meq/Kg. The results are also shown in Table 1. Examples 10.
- Example 11 Copolymers were produced in the same manner as in Example 1 except for changing the ratio (by weight) of the polyethylene terephthalate and the modified polyethylene to 50/50 (in Example 10) and 80/20 (in Example 11). The results are also shown in Table 1. As has been described above in the present invention, since polyester having an intrinsic viscosity [ ⁇ ] and a concentration of terminal carboxyl group each within a predetermined range, and a modified polyolefin having carboxyl ic group and epoxy group contents and melt flow rate (MFR) each in a predetermined range are reacted, and since water is added, it is possible to prevent the gel formation due to excess reaction and prevent resin clogging of the extruder while maintaining satisfactory fluidity without reducing the grafting ratio.
- MFR melt flow rate
- the polyolefin-polyester graft copolymer according to the present invention thus obtained is extremely effective as a compatibilizing agent for an engineering resin such as a polycarbonate resin and a polyolefin.
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019910701363A KR920701313A (ko) | 1989-04-18 | 1990-04-11 | 폴리올레핀-폴리에스테르 그래프트 공중합체의 제조방법 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1/98564 | 1989-04-18 | ||
JP9856489 | 1989-04-18 | ||
JP1/324268 | 1989-12-14 | ||
JP1324268A JPH0347843A (ja) | 1989-04-18 | 1989-12-14 | 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 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1990012837A1 true WO1990012837A1 (en) | 1990-11-01 |
Family
ID=26439708
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1990/001970 WO1990012837A1 (en) | 1989-04-18 | 1990-04-11 | Process for production of polyolefin-polyester graft copolymer |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0469038A4 (ko) |
JP (1) | JPH0347843A (ko) |
KR (1) | KR920701313A (ko) |
AU (1) | AU5440390A (ko) |
WO (1) | WO1990012837A1 (ko) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
EP0333414A2 (en) * | 1988-03-16 | 1989-09-20 | Polyplastics Co. Ltd. | Improved thermoplastic polyester resin and process for producing the same |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4555546A (en) * | 1983-12-29 | 1985-11-26 | Monsanto Company | Compatibilized blends of acrylic ester |
WO1986004076A1 (en) * | 1985-01-11 | 1986-07-17 | Copolymer Rubber And Chemical Corporation | Polyesters having improved impact strength |
WO1988005452A1 (en) * | 1987-01-16 | 1988-07-28 | General Electric Company | Olefinic impact modifiers for, and blends with, thermoplastic polyester resins |
-
1989
- 1989-12-14 JP JP1324268A patent/JPH0347843A/ja active Pending
-
1990
- 1990-04-11 WO PCT/US1990/001970 patent/WO1990012837A1/en not_active Application Discontinuation
- 1990-04-11 KR KR1019910701363A patent/KR920701313A/ko not_active Application Discontinuation
- 1990-04-11 EP EP19900906619 patent/EP0469038A4/en not_active Withdrawn
- 1990-04-11 AU AU54403/90A patent/AU5440390A/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
EP0333414A2 (en) * | 1988-03-16 | 1989-09-20 | Polyplastics Co. Ltd. | Improved thermoplastic polyester resin and process for producing the same |
Non-Patent Citations (1)
Title |
---|
See also references of EP0469038A4 * |
Also Published As
Publication number | Publication date |
---|---|
KR920701313A (ko) | 1992-08-11 |
AU5440390A (en) | 1990-11-16 |
EP0469038A1 (en) | 1992-02-05 |
EP0469038A4 (en) | 1992-08-19 |
JPH0347843A (ja) | 1991-02-28 |
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