CA2019459A1 - Agent for making abs resin and polyolefin compatible, and abs resin-polyolefin thermoplastic resin composition - Google Patents
Agent for making abs resin and polyolefin compatible, and abs resin-polyolefin thermoplastic resin compositionInfo
- Publication number
- CA2019459A1 CA2019459A1 CA 2019459 CA2019459A CA2019459A1 CA 2019459 A1 CA2019459 A1 CA 2019459A1 CA 2019459 CA2019459 CA 2019459 CA 2019459 A CA2019459 A CA 2019459A CA 2019459 A1 CA2019459 A1 CA 2019459A1
- Authority
- CA
- Canada
- Prior art keywords
- polyolefin
- agent
- component
- vinyl monomer
- abs resin
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions 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
- C08L51/06—Compositions 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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
AGENT FOR MAKING ABS RESIN AND POLYOLEFIN COMPATIBLE, AND ABS RESIN-POLYOLEFIN THERMOPLASTIC RESIN COMPOSITION
ABSTRACT OF THE DISCLOSURE:
This invention provide an agent for making an ABS resin and a polyolefin compatible with each other characterized in that the agent comprises:
(a) 10 to 90 wt.% of a modified polyolefin obtained by graft-polymerizing 0.1 to 1.2 mole % of an .alpha.,.beta.-unsaturated carboxylic acid or derivative thereof with a polyolefin, and (b) 90 to 10 wt.% of a multi-component copolymer comprising at least one hydroxyl-containing vinyl monomer, at least one aromatic vinyl monomer and at least one cyano-containing vinyl monomer;
and an ABS resin-polyolefin thermoplastic resin composition comprising:
a resin component comprising:
(c) 5 to 95 wt.% of a polyolefin, and (d) 95 to 5 wt.% of an ABS resin, and the agent as defined above.
ABSTRACT OF THE DISCLOSURE:
This invention provide an agent for making an ABS resin and a polyolefin compatible with each other characterized in that the agent comprises:
(a) 10 to 90 wt.% of a modified polyolefin obtained by graft-polymerizing 0.1 to 1.2 mole % of an .alpha.,.beta.-unsaturated carboxylic acid or derivative thereof with a polyolefin, and (b) 90 to 10 wt.% of a multi-component copolymer comprising at least one hydroxyl-containing vinyl monomer, at least one aromatic vinyl monomer and at least one cyano-containing vinyl monomer;
and an ABS resin-polyolefin thermoplastic resin composition comprising:
a resin component comprising:
(c) 5 to 95 wt.% of a polyolefin, and (d) 95 to 5 wt.% of an ABS resin, and the agent as defined above.
Description
2 ~
AGENT FOR MAKING ABS RESIN AND POLYOLEFIN COMPATIBLE, AND ABS RESIN-POLYOLEFIN THERMOPLASTIC RESIN COMPOSITION
The present invention relates to an agent for making an ABS resin and a pGlyolefin compatible with each other, and ABS resin-polyolefin thermoplastic resin compositions containing the agent.
Polyolefins, typical of which is polypropylene, have heretofore been widely used for various molded articles since they are inexpensive thermoplastic resins which are excellent in moldability, chemical resistance and other properties. However, polyolefins have the drawback of being low in impact resistance and therefore have found limited use. To remedy the drawbacks of polyolefins, such as low impact resistance, it has been practice to admix some other thermoplastic resin with the polyolefin in a molten state to prepare a polymer blend (hereinafter sometimes referred to as a "polymer alloy").
For example, it appears useful to admix an ABS
resin, which is excellent in hardness, impact resi.stance and moldability, with a polyolefin in a molten state to obtain a polymer alloy. Nevertheless, the ABS resin and the polyolefin are very poor in compatibility with each other because of the difference in chemical structure `" 29~9~
therebetween, failing to afford a homogeneous polymer alloy when merely mixed together in a molten state.
Thus, it is impossible to permit each of the blended polymers to exhibit its own advantages. A polymer alloy is already proposed which comprises an ABS resin, polypropylene and thermoplastic resin admixed with these polymers as a compatibilizing agent and prepared by graft-polymerizing a vinyl monomer with a polypropylene (Unexamined Japanese Patent Publication S~O 64-69651).
~owever, the agent is unable to impart sufficiently high compatibility to the ABS resin and the polypropylene, with the result that the molded product of the polymer alloy containing the agent still remains to be improved in impact resistance.
An object of the present invention is to provide an agent for making the ABS resin and the polyolefin fully compatible with each other.
Another object of the invention is to provide an ABS resin-polyolefin thermoplastic resin composition capable of giving molded bodies which are excellent in impact resistance.
The agent of the present invention for making an ABS resin and a polyolefin compatible with each other is characterized in that the agent comprises:
(a) 10 to gO wt. ~ of a modified polyolefin obtained by 2 ~
graft-polymerizing 0.1 to 1.2 mole ~ of an ~,~-unsaturated carboxylic acid or derivative thereof with a polyolefin, and (b) 90 to 10 wt. % of a multi-component copolymer comprising at least one hydroxyl-containing vinyl monomer, at least one aromatic vinyl monomer and at least one cyano-containing vinyl monomer.
The ABS resin-polyolefin thermoplastic resin composition of the present invention is characterized in that the composition comprises:
a resin component comprising:
(c) 5 to 95 wt. ~ of a polyolefin, and (d) 95 to 5 wt. ~ of an ABS resin, and the above-mentioned agent (compatibilizing agent) in an amount of 5 to 20 parts by weight per 100 parts by weight of the resin component (c and d).
Our research has revealed that the compatibilizing agent of the present invention which comprises the modified polyolefin (a) and the specified multi-component copolymer (b) is capable of remarkably improving the compatibility of the polyolefin (c) and the ABS resin (d) with each other. Consequently, the ABS
resin-polyolefin resin composition of the invention comprising the compatibilizing agent contains the two resins as homogeneously mixed together, permits each 2 ~
resin to retain its own characteristics, exhibits excellent flowability and moldability during molding operations, is highly amenable to working or processing and remarkably remedies the low impact resistance of the polyolefin (c) . Accordingly, the molded product prepared from the composition has high impact resistance which can not be realized by the use of polyolefins.
The reason why the thermoplastic resin composition of the present invention has the excellent properties described above still remains to be fully clarified but will presumably be as follows. The carboxyl group and/or the derivative in the component (a) reacts with the hydroxyl group in the component (b) to form an ester bond, conse~uently forming a kind of graft polymer. The component (a) of this copolymer is compatible with the component (c), while the component (b) of the graft polymer is compatible with the component (d), with the result that these components become mixed together unformly in a finely dispersed state throughout the entire composition, permitting the composition to exhibit the outstanding characteristics.
The component (a) of the compatibilizing agent of the present invention, i.e., the modified polyolefin, is obtained by graft-polymerizing an ~,~-unsaturated carboxylic acid or derivative thereof with a polyolefin.
2 0 ~
The graft ratio of the ~,~-unsaturated carboxylic acid or derivative thereof is preferably 0.1 to 1.2 mole %, more preferably 0.4 to 0.7 mole %. If this ratio is less than 0.1 mole %, improved impact resistance will not result.
The polyolefins to be used include homopolymers of a-olefins and copolymers of at least two of ~-olefins.
Preferred examples of such polyolefins are polymers obtained by singly polymerizing a-olefins such as ethylene, propylene, butene-l, hexene-1, decene-l, 4-methylbutene-1, 4-methylpentene-1 and the like, and copolymers obtained by copolymerizing at least two of such a-olefins.
Examples of a,~-unsaturated carboxylic acids or derivatives thereof to be graft-polymerized with such polyolefins are acrylic acid, methacrylic acid, ethacrylic acid, maleic acid and fumaric acid, or esters, acid anhydrides, imidated products and like derivatives of such acids.
The modified polyolefin (a) can be prepared by a usual method, for example, by adding an a,~- unsaturated carboxylic acid or derivative thereof to a polyolefin and kneading the mixture in a molten state usually at 150 to 300C as by a screw extruder, or by dissolving the polyolefin in an organic solvent and adding the 2 ~
a,~-unsaturated carboxylic acid or derivative thereof to the solution for reaction. To conduct the graft polymerization efficiently, an organic oxide catalyst can be added to the system when desired.
Among modified polyolefins thus prepared, it is desirable to use in the present invention maleic anhydride-modified polypropylene which is obtained by graft-polymerizing maleic anhydride with polypropylene in view of the moldability of the thermoplastic resin composition to be obtained.
The other component (b) of the compatibilizing agent of the present invention, i.e., the multi-component copoymer, comprises at least one hydroxyl-containing vinyl monomer, at least one aromatic vinyl monomer and at least one cyano-containing vinyl monomer as its component monomers.
Examples of useful hydroxyl-containing vinyl monomers are 2-hydroxyethyl (meth)acrylate, 2-hydroxy-butyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)-acrylate, 2-hydroxy-2-methylpropyl (meth)acrylate and like hydroxyalkyl (meth)acrylates; polyethylene glycol mono(meth)acrylate ~with addition of 2 to 10 moles of ethylene oxide), polypropylene glycol mono(meth)acrylate (with addition of 2 to 10 moles of propylene oxide) and 2 ~
like polyalkylene glycol mono(meth)acrylate ; etc.
These vinyl monomers are used singly, or at least two of them are used in combination.
Examples of useful aromatic vinyl monomers are styrene and alkyl-substituted styrenes, such as ~-methyl-styrene, p-methylstyrene and the like. These monomers are used singly, or at least two of them are used in combination. It is most preferable to use styrene.
Examples of useful cyano-containing vinyl monomers are acrylonitrile, methacrylonitrile and the like. These monomers are used singly, or at least two of them are used in combination. Among these, it is desirable to use acrylonitrile.
Preferably, the multi-component copolymer to be used is copolymer of styrene, acrylonitrile and 2-hydroxypropylmethacrylate. The multi-component copolyrner (b) comprises 0.1 to 70 wt. %, preferably 1 to 50 wt. %, of the hydroxyl-containing vinyl monomer, 1 to 80 wt. ~, preferably 30 to 80 wt. %, of the aromatic vinyl monomer, and 1 to 80 wt. %, preferably 10 to 35 wt. ~, of the cyano-containing vinyl monomer. The ratio by weight of the aromatic vinyl monomer to the cyano-containing vinyl monomer is S0:50 to 9S:S, preferably 65:35 to 80:20. When the proportions of the monomers 2~9~
and the monomer ratio are in the above respective ranges, the ABS resin and the polyolefin can be made fully compatible with each other by the agent, giving remarkably improved impact resistance to the resulting thermoplastic resin composition.
The multi-component copolymer can be prepared by a process which is in no way limited, for example, by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization or any other process.
The multi-component copolymer thus obtained is preferably 3000 to 1000000, more preferably 10000 to 500000, in number average molecular weight. If the molecular weight is lower than 3000, the thermoplastic resin composition obtained tends to have lower impact resistance, whereas if it exceeds 1000000, the resin composition tends to exhibit impaired flowability.
The compatibilizing agent of the present invention comprises 10 to 90 wt. %, preferably 20 to 80 wt. %' of the component (a) and 10 to 90 wt. %, preferably 20 to 80 wt. %, of the component (b). If the proportion on the component (a) is less than 10 wt. %, molded products are obtained as colored, whereas if it is over 90 wt. %, the ABS resin and the polyolefin become less compatible with each other, giving lower impact resistance to the 2~94~
resulting resin composition.
Our research has also revealed that the compatibilizing agent of the present invention comprising the component (a) and the component (b) renders the ABS resin (d) and the polyolefin (c) more compatible with each other when further incorporating an amino-containing compound (hereinafter referred to as the ~'component (e)~) therein, imparting still improved impact resistance to the thermoplastic resin composition obtained. The presence of the component (e) produces this effect presumably because the component (e) accelerates the reaction between the carboxyl group in the component (a) and the hydroxyl group in the component (b).
Examples of useful amino-containing compounds are tertiary amine compounds, imidazole compounds and like low-molecular weight compounds, or amino-containing copolymers obtained by copolymerizing at least one compound selected from the group consisting of secondary or tertiary amino-containing (meth)acrylic acid esters, quaternary ammonium-containing (meth)acrylic acid esters, secondary or tertiary amino-containing (meth)acrylamides and quaternary ammonium-containing (meth)acrylamides, with other vinyl monomer copolymerizable with the compound. The amount of the 201~
amino-containing monomer in the copolymer is preferably at least 0.1 wt. %, more preferably 0.5 to 50 wt. %, based on the combined amount of the monomers. Examples of copolymerizable monomers are various vinyl compounds, among which styrene is most preferable. Most preferred amino-containing compound is copolymer of styrene and dimethylaminoethyl (meth)acrylate.
The amino~containing compound (e) is used in an amount of up to 4 parts by weight per 100 parts by weight of the combined amount of component (a) and component (b) because the use of more than 4 parts by weight is of no substantial significance and fails to achieve a more remarkable improvement in impact resistance than when up to 4 parts by weight is used.
The preferred amount of compound (e) to be used is in the range of 1 to 4 wt. % based on the combined amount of component (a) and component (b).
Examples of useful polyolefins (c) for constituting the thermoplastic resin composition of the invention are the same as those exemplified for the preparation of the modified polyolefin (a), i.e., homopolymers of ~-olefins and copolymers of at least two of ~-olefins. Among these, polypropylene obtained by polymerizing propylene is desirable to use in view of the moldability of the thermoplastic resin composition to be obtained by mixing 2019~
the components together in a molten state.
The ABS resin (d) as another component of the thermoplastic resin composition of the present invention can be one of various known ones. Generally useful as such resins are a graft copolymer prepared by subjecting the mixture of an aromatic vinyl monomer and a cyano-containing vinyl monomer to block polymerization, suspension polymerization or emulsion polymerization in the presence of a diene rubber. Another example of the ABS resin is the blend of a copolymer obtained from an aromatic vinyl monomer and a cyano-containing vinyl monomer and a copolymer obtained from a diene monomer and a cyano-containing vinyl monomer.
Examples of useful diene rubbers are natural rubber and synthetic rubbers such as polybutadiene, polyisoprene and copolymer of butadiene, isoprene or like diene monomer and styrene, acrylonitrile or the like. Examples of useful aromatic vinyl monomers are styrene, ~-methylstyrene, p-methylstyrene and the like.
Examples of useful cyano-containing vinyl monomers are acrylonitrile, methacrylonitrile and the like. Examples of useful diene monomers are butadiene, isoprene and the like.
The thermoplastic resin composition of the present invention is prepared by mixing the compatibilizing 2~9~
agent comprising the component (a) and the component (b), or the component (a), the component (b) and the component (e) with the component (c) and the component (d) in a molten state. These ingredients may be melted and mixed together usually at 160 to 260C by a known method using any apparatus such as an extruder, kneader or Banbury mixer. The ingredients can be melted and mixed together in an optional order. For example, the component (a), component (b), component (c) and component (d) are melted and mixed together at a time, along with the component (e) as required, or the component (a~ and component (b), or the component (a), component (b) and component (e) are melted and mixed together first, and the mixture, component (c) and component (d) are then mixed together. Thus, any other method can be resorted to.
The amount of component (c) to be used is 5 to 95 wt. %, preferably 20 to 80 wt. %. If the amount is less than 5 wt. %, reduced weather resistance will result, whereas if the amount is over 95 wt. %, improved impact resistance will not be available. The amount of component (d) to be used is 5 to 95 wt. %, preferably 20 to 80 wt. %" If the amount is less than 5 wt. %, improved impact resistance will not result, whereas presence of more than 95 wt. % of component (d) leads to 20~945~
impaired weather resistance. The compatibilizing agent is used in an amount of 5 to 20 parts by weight per lO0 parts by weight of the combined amount of component (c) and component (d). When the amount is less than 5 parts by weight, no improvement is achieved in impact resistance. Use of more than 20 parts by weight of the agent will not result in a more remarkable improvement in the impact resistance than when S to 20 parts by weight is used.
The dispersed particles of the thermoplastic resin composition thus obtained are preferably up to 6 micrometers, more preferably up to S micrometers, in size.
The thermoplastic resin composition is usable free of the problems to be otherwise involved in moldability, flowability, etc. and is improved also in impact resistance. Accordingly, the present resin composition is usable of course for conventional applications and also for a wide variety of applications, e.g., for electric or electronic and mechanical parts, automotive parts, etc.
The present invention will be described in greater detail with reference to the following preparation examples, examples and comparative examples. However, the invention is not limited to such examples. In the 2 0 1L ~
examples to follow, the parts and percentages are all by weight.
Preparation Example 1 Into a 5-liter flask equipped with a reflux condenser, stirrer, thermometer, dropping funnel and nitrogen supply tube were placed 2900 parts of xylene, 500 parts of polypropylene (brand name:"ACE POLYPRO
M1600", product of ACE POLYMER Co., Ltd.) and 50 parts of maleic anhydride, and the mixture was heated at 120C
for 1 hour while introducing nitrogen into the flask to obtain a solution. A solution of 13.3 parts of benzoyl peroxide in 200 parts of xylene was added dropwise to the solution through a dropping funnel over a period of 30 minutes, and the mixture was thereafter maintained a-t 120C for 2 hours for reaction. After the completion of reaction, the mixture was cooled to 80C, filtered, washed with xylene and dried, giving a modified polypropylene with a graft ratio of 0.5 mole ~. The modified polypropylene will hereinafter be referred to as the "modified PP-A."
Preparation Example 2 Into a 5-liter flask equipped with a reflux condenser, stirrer, thermometer and nitrogen supply tube were placed 2333 parts of ion-exchanged water and 4 parts of polyvinyl alcohol (8:2 weight ratio mixture of ~1945~
"PVA 224" (brand name, 88 mole % in saponification degree, product of Kuraray Co.,Ltd.) and "PVA 124 (brand name, 98.5 mole % in saponification degree, product of Kuraray Co., Ltd.), and the mixture was heated while introducing nitrogen into the flask to prepare a solution. To the solution which was then cooled were added 686 parts of styrene, 294 parts of acrylonitrile, 20 parts of 2-hydroxypropyl methacrylate and 10 parts of azobisisobutyronitrile, and the mixture was subjected to polymerization at 75C for 3 hours with vigorous stirring, affording a copolymer which was 9.0 x 10 in Mn, 3.3 x 105 in Mw and 6.9 mg/KOH in hydroxyl value. The copolymer will hereinafter be referred to as the "copolymer B."
Examples 1 - 6 With reference to Table 1, mixtures were prepared from polypropylene (brand name: "ACE POLYPRO M1600", product of ACE POLYMER Co.,Ltd.). ABS resin (brand name: "Denka GR-2000", product of Denki Kagaku Kogyo K.K.), modified PP-A, and copolymer-B and/or copolymer of styrene and dimethylaminoethyl methacrylate (brand name: "LUNAPALE 912" having an amine value of 100, product of Arakawa Chemical Industries Ltd. hereinafter referred to as the "copolymer-C"). Each of the mixtures were kneaded and pelleti~ed at 210 to 230C using a 2019~5~
kneader, Model KRC S-l, manufactured by Kurimoto Iron Works, Ltd. The pelletized mixture was molded into pieces, 5" x (1/2)" x (1/8)", by an injection molding machine and thereafter checked for properties as stated below. Table 1 shows the results.
Comparative Examples 1 - 5 With reference to Table 2, mixtures were prepared in the same manner as in Example 1 from polypropylene (brand name: "ACE POLYPRO M1600", product of ACE POLYMER
Co.,Ltd.) and ABS resin (brand name: "Denka GR-2000", product of Denki Kagaku Kogyo K.K.) using or without the modified pp-A or the copolymer-B obtained in Preparation Example l or 2. The molded pieces were obtained therefrom in the same manner as in Example 1 and checked for properties in the same manner as in Examples. Table 2 shows the results.
(1) Dispersibility A portion of the molded piece was cut off to prepare a sample, which was then observed under a field emission electron microscope (Model S-800, manufactured by Hitachi, Ltd.) to check the dispersed particles (micrometers).
(2) Izod impact strength The molded piece was tested at 23C according to JIS K 7110, Izod Impact Testing Method for Notched 2~9~
Specimens using an Izod impact tester manufactured by Toyo Seiki Seisakusho Co., Ltd.
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AGENT FOR MAKING ABS RESIN AND POLYOLEFIN COMPATIBLE, AND ABS RESIN-POLYOLEFIN THERMOPLASTIC RESIN COMPOSITION
The present invention relates to an agent for making an ABS resin and a pGlyolefin compatible with each other, and ABS resin-polyolefin thermoplastic resin compositions containing the agent.
Polyolefins, typical of which is polypropylene, have heretofore been widely used for various molded articles since they are inexpensive thermoplastic resins which are excellent in moldability, chemical resistance and other properties. However, polyolefins have the drawback of being low in impact resistance and therefore have found limited use. To remedy the drawbacks of polyolefins, such as low impact resistance, it has been practice to admix some other thermoplastic resin with the polyolefin in a molten state to prepare a polymer blend (hereinafter sometimes referred to as a "polymer alloy").
For example, it appears useful to admix an ABS
resin, which is excellent in hardness, impact resi.stance and moldability, with a polyolefin in a molten state to obtain a polymer alloy. Nevertheless, the ABS resin and the polyolefin are very poor in compatibility with each other because of the difference in chemical structure `" 29~9~
therebetween, failing to afford a homogeneous polymer alloy when merely mixed together in a molten state.
Thus, it is impossible to permit each of the blended polymers to exhibit its own advantages. A polymer alloy is already proposed which comprises an ABS resin, polypropylene and thermoplastic resin admixed with these polymers as a compatibilizing agent and prepared by graft-polymerizing a vinyl monomer with a polypropylene (Unexamined Japanese Patent Publication S~O 64-69651).
~owever, the agent is unable to impart sufficiently high compatibility to the ABS resin and the polypropylene, with the result that the molded product of the polymer alloy containing the agent still remains to be improved in impact resistance.
An object of the present invention is to provide an agent for making the ABS resin and the polyolefin fully compatible with each other.
Another object of the invention is to provide an ABS resin-polyolefin thermoplastic resin composition capable of giving molded bodies which are excellent in impact resistance.
The agent of the present invention for making an ABS resin and a polyolefin compatible with each other is characterized in that the agent comprises:
(a) 10 to gO wt. ~ of a modified polyolefin obtained by 2 ~
graft-polymerizing 0.1 to 1.2 mole ~ of an ~,~-unsaturated carboxylic acid or derivative thereof with a polyolefin, and (b) 90 to 10 wt. % of a multi-component copolymer comprising at least one hydroxyl-containing vinyl monomer, at least one aromatic vinyl monomer and at least one cyano-containing vinyl monomer.
The ABS resin-polyolefin thermoplastic resin composition of the present invention is characterized in that the composition comprises:
a resin component comprising:
(c) 5 to 95 wt. ~ of a polyolefin, and (d) 95 to 5 wt. ~ of an ABS resin, and the above-mentioned agent (compatibilizing agent) in an amount of 5 to 20 parts by weight per 100 parts by weight of the resin component (c and d).
Our research has revealed that the compatibilizing agent of the present invention which comprises the modified polyolefin (a) and the specified multi-component copolymer (b) is capable of remarkably improving the compatibility of the polyolefin (c) and the ABS resin (d) with each other. Consequently, the ABS
resin-polyolefin resin composition of the invention comprising the compatibilizing agent contains the two resins as homogeneously mixed together, permits each 2 ~
resin to retain its own characteristics, exhibits excellent flowability and moldability during molding operations, is highly amenable to working or processing and remarkably remedies the low impact resistance of the polyolefin (c) . Accordingly, the molded product prepared from the composition has high impact resistance which can not be realized by the use of polyolefins.
The reason why the thermoplastic resin composition of the present invention has the excellent properties described above still remains to be fully clarified but will presumably be as follows. The carboxyl group and/or the derivative in the component (a) reacts with the hydroxyl group in the component (b) to form an ester bond, conse~uently forming a kind of graft polymer. The component (a) of this copolymer is compatible with the component (c), while the component (b) of the graft polymer is compatible with the component (d), with the result that these components become mixed together unformly in a finely dispersed state throughout the entire composition, permitting the composition to exhibit the outstanding characteristics.
The component (a) of the compatibilizing agent of the present invention, i.e., the modified polyolefin, is obtained by graft-polymerizing an ~,~-unsaturated carboxylic acid or derivative thereof with a polyolefin.
2 0 ~
The graft ratio of the ~,~-unsaturated carboxylic acid or derivative thereof is preferably 0.1 to 1.2 mole %, more preferably 0.4 to 0.7 mole %. If this ratio is less than 0.1 mole %, improved impact resistance will not result.
The polyolefins to be used include homopolymers of a-olefins and copolymers of at least two of ~-olefins.
Preferred examples of such polyolefins are polymers obtained by singly polymerizing a-olefins such as ethylene, propylene, butene-l, hexene-1, decene-l, 4-methylbutene-1, 4-methylpentene-1 and the like, and copolymers obtained by copolymerizing at least two of such a-olefins.
Examples of a,~-unsaturated carboxylic acids or derivatives thereof to be graft-polymerized with such polyolefins are acrylic acid, methacrylic acid, ethacrylic acid, maleic acid and fumaric acid, or esters, acid anhydrides, imidated products and like derivatives of such acids.
The modified polyolefin (a) can be prepared by a usual method, for example, by adding an a,~- unsaturated carboxylic acid or derivative thereof to a polyolefin and kneading the mixture in a molten state usually at 150 to 300C as by a screw extruder, or by dissolving the polyolefin in an organic solvent and adding the 2 ~
a,~-unsaturated carboxylic acid or derivative thereof to the solution for reaction. To conduct the graft polymerization efficiently, an organic oxide catalyst can be added to the system when desired.
Among modified polyolefins thus prepared, it is desirable to use in the present invention maleic anhydride-modified polypropylene which is obtained by graft-polymerizing maleic anhydride with polypropylene in view of the moldability of the thermoplastic resin composition to be obtained.
The other component (b) of the compatibilizing agent of the present invention, i.e., the multi-component copoymer, comprises at least one hydroxyl-containing vinyl monomer, at least one aromatic vinyl monomer and at least one cyano-containing vinyl monomer as its component monomers.
Examples of useful hydroxyl-containing vinyl monomers are 2-hydroxyethyl (meth)acrylate, 2-hydroxy-butyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)-acrylate, 2-hydroxy-2-methylpropyl (meth)acrylate and like hydroxyalkyl (meth)acrylates; polyethylene glycol mono(meth)acrylate ~with addition of 2 to 10 moles of ethylene oxide), polypropylene glycol mono(meth)acrylate (with addition of 2 to 10 moles of propylene oxide) and 2 ~
like polyalkylene glycol mono(meth)acrylate ; etc.
These vinyl monomers are used singly, or at least two of them are used in combination.
Examples of useful aromatic vinyl monomers are styrene and alkyl-substituted styrenes, such as ~-methyl-styrene, p-methylstyrene and the like. These monomers are used singly, or at least two of them are used in combination. It is most preferable to use styrene.
Examples of useful cyano-containing vinyl monomers are acrylonitrile, methacrylonitrile and the like. These monomers are used singly, or at least two of them are used in combination. Among these, it is desirable to use acrylonitrile.
Preferably, the multi-component copolymer to be used is copolymer of styrene, acrylonitrile and 2-hydroxypropylmethacrylate. The multi-component copolyrner (b) comprises 0.1 to 70 wt. %, preferably 1 to 50 wt. %, of the hydroxyl-containing vinyl monomer, 1 to 80 wt. ~, preferably 30 to 80 wt. %, of the aromatic vinyl monomer, and 1 to 80 wt. %, preferably 10 to 35 wt. ~, of the cyano-containing vinyl monomer. The ratio by weight of the aromatic vinyl monomer to the cyano-containing vinyl monomer is S0:50 to 9S:S, preferably 65:35 to 80:20. When the proportions of the monomers 2~9~
and the monomer ratio are in the above respective ranges, the ABS resin and the polyolefin can be made fully compatible with each other by the agent, giving remarkably improved impact resistance to the resulting thermoplastic resin composition.
The multi-component copolymer can be prepared by a process which is in no way limited, for example, by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization or any other process.
The multi-component copolymer thus obtained is preferably 3000 to 1000000, more preferably 10000 to 500000, in number average molecular weight. If the molecular weight is lower than 3000, the thermoplastic resin composition obtained tends to have lower impact resistance, whereas if it exceeds 1000000, the resin composition tends to exhibit impaired flowability.
The compatibilizing agent of the present invention comprises 10 to 90 wt. %, preferably 20 to 80 wt. %' of the component (a) and 10 to 90 wt. %, preferably 20 to 80 wt. %, of the component (b). If the proportion on the component (a) is less than 10 wt. %, molded products are obtained as colored, whereas if it is over 90 wt. %, the ABS resin and the polyolefin become less compatible with each other, giving lower impact resistance to the 2~94~
resulting resin composition.
Our research has also revealed that the compatibilizing agent of the present invention comprising the component (a) and the component (b) renders the ABS resin (d) and the polyolefin (c) more compatible with each other when further incorporating an amino-containing compound (hereinafter referred to as the ~'component (e)~) therein, imparting still improved impact resistance to the thermoplastic resin composition obtained. The presence of the component (e) produces this effect presumably because the component (e) accelerates the reaction between the carboxyl group in the component (a) and the hydroxyl group in the component (b).
Examples of useful amino-containing compounds are tertiary amine compounds, imidazole compounds and like low-molecular weight compounds, or amino-containing copolymers obtained by copolymerizing at least one compound selected from the group consisting of secondary or tertiary amino-containing (meth)acrylic acid esters, quaternary ammonium-containing (meth)acrylic acid esters, secondary or tertiary amino-containing (meth)acrylamides and quaternary ammonium-containing (meth)acrylamides, with other vinyl monomer copolymerizable with the compound. The amount of the 201~
amino-containing monomer in the copolymer is preferably at least 0.1 wt. %, more preferably 0.5 to 50 wt. %, based on the combined amount of the monomers. Examples of copolymerizable monomers are various vinyl compounds, among which styrene is most preferable. Most preferred amino-containing compound is copolymer of styrene and dimethylaminoethyl (meth)acrylate.
The amino~containing compound (e) is used in an amount of up to 4 parts by weight per 100 parts by weight of the combined amount of component (a) and component (b) because the use of more than 4 parts by weight is of no substantial significance and fails to achieve a more remarkable improvement in impact resistance than when up to 4 parts by weight is used.
The preferred amount of compound (e) to be used is in the range of 1 to 4 wt. % based on the combined amount of component (a) and component (b).
Examples of useful polyolefins (c) for constituting the thermoplastic resin composition of the invention are the same as those exemplified for the preparation of the modified polyolefin (a), i.e., homopolymers of ~-olefins and copolymers of at least two of ~-olefins. Among these, polypropylene obtained by polymerizing propylene is desirable to use in view of the moldability of the thermoplastic resin composition to be obtained by mixing 2019~
the components together in a molten state.
The ABS resin (d) as another component of the thermoplastic resin composition of the present invention can be one of various known ones. Generally useful as such resins are a graft copolymer prepared by subjecting the mixture of an aromatic vinyl monomer and a cyano-containing vinyl monomer to block polymerization, suspension polymerization or emulsion polymerization in the presence of a diene rubber. Another example of the ABS resin is the blend of a copolymer obtained from an aromatic vinyl monomer and a cyano-containing vinyl monomer and a copolymer obtained from a diene monomer and a cyano-containing vinyl monomer.
Examples of useful diene rubbers are natural rubber and synthetic rubbers such as polybutadiene, polyisoprene and copolymer of butadiene, isoprene or like diene monomer and styrene, acrylonitrile or the like. Examples of useful aromatic vinyl monomers are styrene, ~-methylstyrene, p-methylstyrene and the like.
Examples of useful cyano-containing vinyl monomers are acrylonitrile, methacrylonitrile and the like. Examples of useful diene monomers are butadiene, isoprene and the like.
The thermoplastic resin composition of the present invention is prepared by mixing the compatibilizing 2~9~
agent comprising the component (a) and the component (b), or the component (a), the component (b) and the component (e) with the component (c) and the component (d) in a molten state. These ingredients may be melted and mixed together usually at 160 to 260C by a known method using any apparatus such as an extruder, kneader or Banbury mixer. The ingredients can be melted and mixed together in an optional order. For example, the component (a), component (b), component (c) and component (d) are melted and mixed together at a time, along with the component (e) as required, or the component (a~ and component (b), or the component (a), component (b) and component (e) are melted and mixed together first, and the mixture, component (c) and component (d) are then mixed together. Thus, any other method can be resorted to.
The amount of component (c) to be used is 5 to 95 wt. %, preferably 20 to 80 wt. %. If the amount is less than 5 wt. %, reduced weather resistance will result, whereas if the amount is over 95 wt. %, improved impact resistance will not be available. The amount of component (d) to be used is 5 to 95 wt. %, preferably 20 to 80 wt. %" If the amount is less than 5 wt. %, improved impact resistance will not result, whereas presence of more than 95 wt. % of component (d) leads to 20~945~
impaired weather resistance. The compatibilizing agent is used in an amount of 5 to 20 parts by weight per lO0 parts by weight of the combined amount of component (c) and component (d). When the amount is less than 5 parts by weight, no improvement is achieved in impact resistance. Use of more than 20 parts by weight of the agent will not result in a more remarkable improvement in the impact resistance than when S to 20 parts by weight is used.
The dispersed particles of the thermoplastic resin composition thus obtained are preferably up to 6 micrometers, more preferably up to S micrometers, in size.
The thermoplastic resin composition is usable free of the problems to be otherwise involved in moldability, flowability, etc. and is improved also in impact resistance. Accordingly, the present resin composition is usable of course for conventional applications and also for a wide variety of applications, e.g., for electric or electronic and mechanical parts, automotive parts, etc.
The present invention will be described in greater detail with reference to the following preparation examples, examples and comparative examples. However, the invention is not limited to such examples. In the 2 0 1L ~
examples to follow, the parts and percentages are all by weight.
Preparation Example 1 Into a 5-liter flask equipped with a reflux condenser, stirrer, thermometer, dropping funnel and nitrogen supply tube were placed 2900 parts of xylene, 500 parts of polypropylene (brand name:"ACE POLYPRO
M1600", product of ACE POLYMER Co., Ltd.) and 50 parts of maleic anhydride, and the mixture was heated at 120C
for 1 hour while introducing nitrogen into the flask to obtain a solution. A solution of 13.3 parts of benzoyl peroxide in 200 parts of xylene was added dropwise to the solution through a dropping funnel over a period of 30 minutes, and the mixture was thereafter maintained a-t 120C for 2 hours for reaction. After the completion of reaction, the mixture was cooled to 80C, filtered, washed with xylene and dried, giving a modified polypropylene with a graft ratio of 0.5 mole ~. The modified polypropylene will hereinafter be referred to as the "modified PP-A."
Preparation Example 2 Into a 5-liter flask equipped with a reflux condenser, stirrer, thermometer and nitrogen supply tube were placed 2333 parts of ion-exchanged water and 4 parts of polyvinyl alcohol (8:2 weight ratio mixture of ~1945~
"PVA 224" (brand name, 88 mole % in saponification degree, product of Kuraray Co.,Ltd.) and "PVA 124 (brand name, 98.5 mole % in saponification degree, product of Kuraray Co., Ltd.), and the mixture was heated while introducing nitrogen into the flask to prepare a solution. To the solution which was then cooled were added 686 parts of styrene, 294 parts of acrylonitrile, 20 parts of 2-hydroxypropyl methacrylate and 10 parts of azobisisobutyronitrile, and the mixture was subjected to polymerization at 75C for 3 hours with vigorous stirring, affording a copolymer which was 9.0 x 10 in Mn, 3.3 x 105 in Mw and 6.9 mg/KOH in hydroxyl value. The copolymer will hereinafter be referred to as the "copolymer B."
Examples 1 - 6 With reference to Table 1, mixtures were prepared from polypropylene (brand name: "ACE POLYPRO M1600", product of ACE POLYMER Co.,Ltd.). ABS resin (brand name: "Denka GR-2000", product of Denki Kagaku Kogyo K.K.), modified PP-A, and copolymer-B and/or copolymer of styrene and dimethylaminoethyl methacrylate (brand name: "LUNAPALE 912" having an amine value of 100, product of Arakawa Chemical Industries Ltd. hereinafter referred to as the "copolymer-C"). Each of the mixtures were kneaded and pelleti~ed at 210 to 230C using a 2019~5~
kneader, Model KRC S-l, manufactured by Kurimoto Iron Works, Ltd. The pelletized mixture was molded into pieces, 5" x (1/2)" x (1/8)", by an injection molding machine and thereafter checked for properties as stated below. Table 1 shows the results.
Comparative Examples 1 - 5 With reference to Table 2, mixtures were prepared in the same manner as in Example 1 from polypropylene (brand name: "ACE POLYPRO M1600", product of ACE POLYMER
Co.,Ltd.) and ABS resin (brand name: "Denka GR-2000", product of Denki Kagaku Kogyo K.K.) using or without the modified pp-A or the copolymer-B obtained in Preparation Example l or 2. The molded pieces were obtained therefrom in the same manner as in Example 1 and checked for properties in the same manner as in Examples. Table 2 shows the results.
(1) Dispersibility A portion of the molded piece was cut off to prepare a sample, which was then observed under a field emission electron microscope (Model S-800, manufactured by Hitachi, Ltd.) to check the dispersed particles (micrometers).
(2) Izod impact strength The molded piece was tested at 23C according to JIS K 7110, Izod Impact Testing Method for Notched 2~9~
Specimens using an Izod impact tester manufactured by Toyo Seiki Seisakusho Co., Ltd.
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Claims (12)
1. An agent for making an ABS resin and a polyolefin compatible with each other characterized in that the agent comprises:
(a) 10 to 90 wt. % of a modified polyolefin obtained by graft-polymerizing 0.1 to 1.2 mole % of an .alpha.,.beta.-unsaturated carboxylic acid or derivative thereof with a polyolefin, and (b) 90 to 10 wt. % of a multi-component copolymer comprising at least one hydroxyl-containing vinyl monomer, at least one aromatic vinyl monomer and at least one cyano-containing vinyl monomer.
(a) 10 to 90 wt. % of a modified polyolefin obtained by graft-polymerizing 0.1 to 1.2 mole % of an .alpha.,.beta.-unsaturated carboxylic acid or derivative thereof with a polyolefin, and (b) 90 to 10 wt. % of a multi-component copolymer comprising at least one hydroxyl-containing vinyl monomer, at least one aromatic vinyl monomer and at least one cyano-containing vinyl monomer.
2. An agent as defined in claim 1 wherein the modified polyolefin (a) is maleic anhydride-modified polypropylene.
3. An agent as defined in claim 1 wherein the multi-component copolymer (b) is copolymer of styrene, acrylonitrile and 2-hydroxypropyl-methacrylate.
4. An agent as defined in claim 1 wherein the multi-component copolymer (b) is 3000 to 1000000 in number average molecular weight.
5. An agent as defined in claim 4 wherein the multi-component copolymer (b) is 10000 to 500000 in number average molecular weight.
6. An agent as defined in claim 1 which comprises 20 to 80 wt. % of the modified polyolefin (a) and 20 to 80 wt. % of the multi-component copolymer (b).
7. An agent as defined in claim 1 wherein the multi-component copolymer (b) comprises 0.1 to 70 wt. %
of the hydroxyl-containing vinyl monomer, 1 to 80 wt. %
of the aromatic vinyl monomer and 1 to 80 wt. % of the cyano-containing vinyl monomer, and the ratio by weight of the aromatic vinyl monomer to the cyano-containing vinyl monomer is 50:50 to 95: 5.
of the hydroxyl-containing vinyl monomer, 1 to 80 wt. %
of the aromatic vinyl monomer and 1 to 80 wt. % of the cyano-containing vinyl monomer, and the ratio by weight of the aromatic vinyl monomer to the cyano-containing vinyl monomer is 50:50 to 95: 5.
8. An agent as defined in claim 1 wherein the hydroxyl-containing vinyl monomer of the multi-component copolymer (b) is a hydroxyalkyl acrylate or hydroxyalkyl methacrylate.
9. An agent as defined in claim 1 which further comprises an amino-containing compound in an amount of up to 4 parts by weight per 100 parts by weight of the combined amount of the modified polyolefin (a) and the multi-component copolymer (b).
10. An agent as defined in claim 1 wherein the amino-containing compound is copolymer of styrene and dimethylaminoethyl (meth)acrylate.
11. An ABS resin-polyolefin thermoplastic resin composition comprising:
a resin component comprising:
(c) 5 to 95 wt. % of a polyolefin, and (d) 95 to 5 wt. % of an ABS resin, and an agent as defined in any one of claims 1 to 10 in an amount of 5 to 20 parts by weight per 100 parts by weight of the resin component.
a resin component comprising:
(c) 5 to 95 wt. % of a polyolefin, and (d) 95 to 5 wt. % of an ABS resin, and an agent as defined in any one of claims 1 to 10 in an amount of 5 to 20 parts by weight per 100 parts by weight of the resin component.
12. A composition as defined in claim 11 wherein the polyolefin (c) is polypropylene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16923989A JPH0618954B2 (en) | 1989-06-29 | 1989-06-29 | ABS resin-Compatibilizing agent for polyolefin and thermoplastic resin composition containing the compatibilizing agent |
| JP169239/1989 | 1989-06-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2019459A1 true CA2019459A1 (en) | 1990-12-29 |
Family
ID=15882821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2019459 Abandoned CA2019459A1 (en) | 1989-06-29 | 1990-06-20 | Agent for making abs resin and polyolefin compatible, and abs resin-polyolefin thermoplastic resin composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH0618954B2 (en) |
| CA (1) | CA2019459A1 (en) |
| DE (1) | DE4020603A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117683319A (en) * | 2024-02-02 | 2024-03-12 | 佛山市舍与得新材料科技有限公司 | PP-ABS compatible master batch, PP-ABS alloy and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4342605A1 (en) * | 1993-12-14 | 1995-06-22 | Buna Gmbh | Functionalized olefin homo- and copolymers |
-
1989
- 1989-06-29 JP JP16923989A patent/JPH0618954B2/en not_active Expired - Lifetime
-
1990
- 1990-06-20 CA CA 2019459 patent/CA2019459A1/en not_active Abandoned
- 1990-06-28 DE DE19904020603 patent/DE4020603A1/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117683319A (en) * | 2024-02-02 | 2024-03-12 | 佛山市舍与得新材料科技有限公司 | PP-ABS compatible master batch, PP-ABS alloy and preparation method thereof |
| CN117683319B (en) * | 2024-02-02 | 2024-04-26 | 佛山市舍与得新材料科技有限公司 | PP-ABS compatible master batch, PP-ABS alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0618954B2 (en) | 1994-03-16 |
| DE4020603A1 (en) | 1991-01-03 |
| JPH0333141A (en) | 1991-02-13 |
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