WO2002036664A1 - Plastique malleable et son procede de preparation - Google Patents

Plastique malleable et son procede de preparation Download PDF

Info

Publication number
WO2002036664A1
WO2002036664A1 PCT/CN2001/001531 CN0101531W WO0236664A1 WO 2002036664 A1 WO2002036664 A1 WO 2002036664A1 CN 0101531 W CN0101531 W CN 0101531W WO 0236664 A1 WO0236664 A1 WO 0236664A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
powder
plastic
fully vulcanized
mixed
Prior art date
Application number
PCT/CN2001/001531
Other languages
English (en)
French (fr)
Inventor
Jinliang Qiao
Yiqun Liu
Shijun Zhang
Xiaohong Zhang
Jianming Gao
Wei Zhang
Genshuan Wei
Jingbo Shao
Hua Yin
Renli Zhai
Zhihai Song
Fan Huang
Original Assignee
China Petroleum & Chemical Corporation
China Petroleum & Chemical Corporation Beijing Research Institute Of Chemical Industry
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 China Petroleum & Chemical Corporation, China Petroleum & Chemical Corporation Beijing Research Institute Of Chemical Industry filed Critical China Petroleum & Chemical Corporation
Priority to US10/415,769 priority Critical patent/US9181419B2/en
Priority to EP01992734A priority patent/EP1340782B1/en
Priority to KR1020037006189A priority patent/KR100817677B1/ko
Priority to AU2002220473A priority patent/AU2002220473A1/en
Priority to JP2002539416A priority patent/JP3929896B2/ja
Priority to DE60136646T priority patent/DE60136646D1/de
Publication of WO2002036664A1 publication Critical patent/WO2002036664A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • 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
    • C08L25/06—Polystyrene
    • 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
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • 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

Definitions

  • the present invention relates to a toughened plastic and a preparation method thereof. More specifically, the present invention relates to a toughened plastic prepared by blending two or more rubber components with a brittle or relatively brittle plastic and a preparation method thereof.
  • the division of plastics is as follows: when the chain entanglement density Ve of the plastic is ⁇ 0.15 mmol / ml, the chain characteristic ratio When C ⁇ > 7.5, the external impact energy is mainly dissipated by the formation of silver lines on the substrate, which is a brittle plastic, such as polystyrene, polymethyl methacrylate, acrylonitrile-styrene resin, etc .; when the plastic chains are tangled When the density Ve> 0.15mmol / ml and the characteristic ratio C ⁇ ⁇ 7.5, the external impact energy mainly dissipates energy through the shear yield of the matrix, which belongs to ductile plastics.
  • the inventors define them as relatively brittle plastics, such as polyvinyl chloride, polypropylene, and polyoxymethylene Wait.
  • the inventors have found through a large number of experimental studies that using a small particle size crosslinked powdered rubber with unvulcanized rubber and / or thermoplastic elastomers to toughen brittle plastics or brittle plastics can achieve good toughness. Effect, and the method is suitable for toughening various brittle or brittle plastics.
  • an object of the present invention is to provide a toughened plastic obtained by mixing a rubber component to toughen a brittle or relatively brittle plastic.
  • This toughened plastic has good toughness while maintaining high strength and rigidity.
  • Another object of the present invention is to provide a toughening method for brittle or relatively brittle plastics.
  • the method has a simple process and is generally applicable to the toughening of various brittle or relatively brittle plastics.
  • a type of toughened plastic which comprises the following components blended with each other: a brittle or relatively brittle plastic and a mixed rubber component, wherein the mixed rubber component is composed of an average particle size of 0.02 ⁇ m ⁇ 0.5 ⁇ m, powder rubber with a cross-linked structure and at least one of the following materials: unvulcanized rubber and thermoplastic elastomer.
  • a method for preparing the above-mentioned toughened plastic comprises melt-blending a brittle or relatively brittle plastic with a mixed rubber component.
  • the toughened plastic of the present invention comprises the following components blended with each other: a brittle or relatively brittle plastic and a mixed rubber component.
  • the mixed rubber component is composed of an average particle diameter of 0.02 ⁇ m to 0.5 ⁇ m, preferably 0.05 ⁇ ⁇ ! ⁇ 0.2 ⁇ m, powder rubber with cross-linked structure and at least one of the following materials: unvulcanized rubber and thermoplastic elastomer, where the unvulcanized rubber and thermoplastic elastomer can be mixed in any proportion.
  • the weight ratio of the mixed rubber component to the plastic is 1: 99 to 30: 70, preferably 5: 95 to 25: 75. Among them, powdered rubber accounts for 10% to 95% by weight of the total weight of the mixed rubber component, and preferably 50% to 95% by weight.
  • the brittle or relatively brittle plastics as the toughened plastic matrix of the present invention include: polystyrene Ene, acrylonitrile-styrene resin (AS), polyvinyl acetate, polymethyl methacrylate, polyvinyl chloride, polypropylene or polyoxymethylene.
  • the powder rubber particles having a crosslinked structure in the mixed rubber component of the toughened plastic dispersed phase of the present invention are rubber particles having a homogeneous structure, and the gel content thereof is 60% by weight or more, preferably 80% by weight or more ;
  • the average particle diameter of the rubber particles is 0.02 ⁇ m to 0.5 ⁇ m, preferably 0.05 ⁇ m to 0.2 ⁇ m.
  • This rubber particle is preferably a fully vulcanized powder rubber prepared in accordance with Chinese Patent Application No. 99125530.5 (the disclosure of which is incorporated herein by reference) filed by the inventor on December 3, 1999, and specifically includes but is not limited to the following fully vulcanized powder At least one kind of rubber: fully vulcanized powder natural rubber, fully vulcanized powder styrene-butadiene rubber, fully vulcanized powder carboxylated styrene-butadiene rubber, fully vulcanized powdered nitrile rubber, fully vulcanized powdered carboxyl nitrile rubber, fully vulcanized powder neoprene, Vulcanized powder polybutadiene rubber, fully vulcanized powder silicone rubber or fully vulcanized powder acrylate rubber.
  • This kind of fully vulcanized powder rubber refers to discrete rubber powders with a gel content of 60% by weight or more, which can flow freely without adding a release agent after drying.
  • This fully vulcanized powder rubber can be obtained by radiation-crosslinking a rubber emulsion.
  • For a specific preparation method refer to the aforementioned Chinese patent application 99125530.5.
  • the rubber particles described above may also be crosslinked powder rubber.
  • the inventors have found through experimental research that some rubber emulsions undergo a certain crosslinking reaction between the rubber molecules during the synthesis process, so that the obtained rubber emulsion has a certain degree of crosslinking.
  • a crosslinked rubber emulsion For this type of crosslinked rubber emulsion, when its own degree of crosslinking is relatively high, powder rubber can be obtained by spray drying without further irradiation and crosslinking.
  • the degree of cross-linking of this powder rubber is lower than the fully vulcanized powder rubber obtained by irradiation, which we call cross-linked powder rubber.
  • the gel content of this crosslinked powder rubber is basically consistent with the gel content of the crosslinked synthetic rubber emulsion as a raw material, and the gel content is 80% by weight or more, preferably 85% by weight or more high.
  • the powder rubber has a relatively small particle size, with an average of 50 to 300 nm.
  • This crosslinked powder rubber can flow freely without adding a release agent.
  • a release agent can also be added to this crosslinked powder rubber to further improve its flowability and blocking resistance.
  • Each particle in this kind of powder rubber is homogeneous, that is, a single particle is homogeneous in composition, and under the observation of the existing microscopic technology, no stratification and equal heterogeneity have been found inside the particles.
  • cross-linked powder rubber there are no restrictions on the type of cross-linked powder rubber, and it can be a cross-linked powder rubber made from various cross-linked synthetic rubber emulsions, such as cross-linked powder styrene-butadiene rubber, cross-linked powder styrene-butadiene rubber, Cross-linked powder polybutadiene rubber, cross-linked powder nitrile rubber, cross-linked powder carboxyl nitrile rubber, cross-linked powder neoprene rubber, cross-linked powder acrylate rubber, etc.
  • cross-linked powder rubber made from various cross-linked synthetic rubber emulsions, such as cross-linked powder styrene-butadiene rubber, cross-linked powder styrene-butadiene rubber, Cross-linked powder polybutadiene rubber, cross-linked powder nitrile rubber, cross-linked powder carboxyl nitrile rubber, cross-linked powder neoprene rubber, cross-linked powder acrylate rubber, etc.
  • the cross-linked powder rubber is prepared by using various cross-linked synthetic rubber emulsions as raw materials, and then cross-linked powder rubber can be obtained by drying.
  • the drying process can be carried out by spray drying or precipitation drying, and spray drying is preferred. If spray drying is used, the inlet temperature of the spray dryer can be controlled at 100 ⁇ 200 ° C, and the outlet temperature can be controlled at 20 ⁇ 80 ° C.
  • the type of the crosslinked synthetic latex used may be various types of crosslinked synthetic rubber emulsions, and its gel content is required to be 80% by weight or more, preferably 85% by weight or more .
  • the cross-linked synthetic latex may be selected from the group consisting of: cross-linked styrene-butadiene rubber emulsion, cross-linked carboxyl styrene-butadiene rubber emulsion, cross-linked polybutadiene rubber emulsion, cross-linked nitrile rubber emulsion, and cross-linked carboxylic butyronitrile Rubber emulsion, crosslinked neoprene emulsion, crosslinked acrylate rubber emulsion.
  • a crosslinked powder styrene-butadiene rubber or a crosslinked powder polybutadiene rubber is preferably used first.
  • the unvulcanized rubber in the mixed rubber component of the toughened plastic dispersed phase of the present invention includes at least one of the following rubbers: natural rubber, styrene-butadiene rubber, chitin styrene-butadiene rubber, polybutadiene rubber, polyisoprene Ethylene rubber, ethylene-propylene rubber, neoprene, nitrile rubber, carboxyl nitrile rubber, butyl rubber, acrylic rubber, silicone rubber, fluoro rubber, polyurethane rubber, chloroether rubber, polysulfide rubber, chlorosulfonated polyethylene Or chlorinated polyethylene.
  • the thermoplastic elastomer in the mixed rubber component of the toughened plastic dispersed phase of the present invention includes at least one of the following: styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene Ethylene-styrene block copolymer (SIS), hydrogenated SBS (SEBS), hydrogenated SIS (SEPS), polyether polyurethane thermoplastic elastomer, polyester polyurethane thermoplastic elastomer, polyester thermoplastic elastomer, ethylene copolymer thermoplastic elastomer or polyvinyl chloride thermoplastic elastomer.
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene Ethylene-styrene block copolymer
  • SEBS hydrogenated SBS
  • SEPS hydrogenated SIS
  • the preparation method of the toughened plastic of the present invention is:
  • the toughened plastic is made by brittle or relatively brittle plastic and mixed rubber components by a conventional rubber-plastic blending method.
  • the mixed rubber used is composed of a powder rubber having an average particle diameter of 0.02 ⁇ m to 0.5 ⁇ m, preferably 0.05 ⁇ m to 0.2 ⁇ m, having a crosslinked structure, and at least one of the following materials: unvulcanized rubber and thermoplastic Elastomers, where unvulcanized rubber and thermoplastic elastomers can be mixed in any ratio.
  • the weight ratio of the mixed rubber component to the plastic is 1: 99 to 30: 70, preferably 5: 95 to 25: 75.
  • powdered rubber accounts for 10% to 95% by weight of the total weight of the mixed rubber component, and preferably 50% to 95% by weight.
  • the brittle or relatively brittle plastics used in this method include: polystyrene, acrylonitrile-styrene resin (AS), polyvinyl acetate, polymethyl methacrylate, polyvinyl chloride, polypropylene, or polyformaldehyde.
  • the powdered rubber particles having a crosslinked structure used in the method are rubber particles of a homogeneous structure, and the gel content thereof is 60% by weight or more, preferably 80% by weight or more; the average particle size of the rubber particles is 0.02 ⁇ m to 0.5 ⁇ m, preferably 0.05 ⁇ m to 0.2 ⁇ m.
  • This kind of rubber particles may be a fully vulcanized powder rubber prepared in accordance with Chinese Patent Application No. 99125530.5 (the entire disclosure of which is incorporated herein by reference) filed by the inventor on December 3, 1999, including, but not limited to, the following fully vulcanized powders At least one kind of rubber: fully vulcanized powder natural rubber, fully vulcanized powder styrene-butadiene rubber, fully vulcanized powder carboxylated styrene-butadiene rubber, fully vulcanized powdered nitrile rubber, fully vulcanized powdered carboxylated nitrile rubber, fully vulcanized powdered neoprene, Fully vulcanized powder polybutadiene rubber, fully vulcanized powder silicone rubber Glue or fully vulcanized powder acrylate rubber.
  • This type of fully vulcanized powder rubber refers to discrete rubber powders with a gel content of 60% by weight or higher, which can flow freely without the need for a release agent after drying.
  • This fully vulcanized powder rubber can be obtained by radiation crosslinking of a rubber emulsion.
  • For a specific preparation method refer to the aforementioned Chinese patent application 99125530.5.
  • the rubber particles described above may also be crosslinked powder rubber.
  • the inventors have found through experimental research that some rubber emulsions undergo a certain crosslinking reaction between the rubber molecules during the synthesis process, so that the obtained rubber emulsion has a certain degree of crosslinking.
  • a crosslinked rubber emulsion For this type of crosslinked rubber strand emulsion, when its own degree of crosslinking is relatively high, powder rubber can be obtained by spray drying without further irradiation and crosslinking.
  • the degree of cross-linking of this powder rubber is lower than the fully vulcanized powder rubber obtained by irradiation, which we call cross-linked powder rubber.
  • the gel content of this crosslinked powder rubber is basically consistent with the gel content of the crosslinked synthetic rubber emulsion as a raw material, and the gel content is 80% by weight or more, preferably 85% by weight or more high.
  • the powder rubber has a relatively small particle size, with an average of 50 to 300 nm.
  • This crosslinked powder rubber can flow freely without adding a release agent.
  • a release agent can also be added to this cross-linked powder rubber to further improve its flowability and blocking resistance.
  • Each particle in this kind of powder rubber is homogeneous, that is, the individual particles are homogeneous in composition, and under the observation of the existing microscopic technology, no layering and equal heterogeneity have been found inside the particles.
  • cross-linked powder rubber there are no restrictions on the type of cross-linked powder rubber, and it can be a cross-linked powder rubber made from various cross-linked synthetic rubber emulsions, such as cross-linked powder styrene-butadiene rubber, cross-linked powder carboxyl styrene-butadiene rubber , Cross-linked powder polybutadiene rubber, cross-linked powder nitrile rubber, cross-linked powder carboxyl butadiene rubber, cross-linked powder neoprene rubber, cross-linked powder acrylate rubber, etc.
  • cross-linked powder styrene-butadiene rubber cross-linked powder carboxyl styrene-butadiene rubber
  • Cross-linked powder polybutadiene rubber cross-linked powder nitrile rubber
  • cross-linked powder carboxyl butadiene rubber cross-linked powder neoprene rubber
  • cross-linked powder acrylate rubber etc.
  • the method for preparing the crosslinked powder rubber is as follows: various crosslinked synthetic rubber emulsions are used as raw materials, and the crosslinked powder rubber can be obtained by drying.
  • the drying process may be spray drying or precipitation drying, and spray drying is preferred. If the spray drying method is used, the inlet temperature of the spray dryer can be controlled at 100 ⁇ 200 ° C, and the outlet temperature can be controlled at 20 ⁇ 80 ° C.
  • the type of crosslinked synthetic latex used may be It is various types of crosslinked synthetic rubber emulsions, and its gel content is required to be 80% by weight or more, preferably 85% by weight or more.
  • the cross-linked synthetic latex may be selected from the group consisting of: cross-linked styrene-butadiene rubber emulsion, cross-linked styrene-butadiene rubber emulsion, cross-linked polybutadiene rubber emulsion, cross-linked nitrile rubber emulsion, and cross-linked carboxylic butyronitrile Rubber emulsion, crosslinked neoprene emulsion, crosslinked acrylate rubber emulsion.
  • the rubber particles used may be such crosslinked powder rubbers, and crosslinked powdered styrene-butadiene rubber or crosslinked powdered polybutadiene rubber is preferably used.
  • the unvulcanized rubber used in the method includes at least one of the following rubbers: natural rubber, styrene-butadiene rubber, carboxystyrene-butadiene rubber, polybutadiene rubber, polyisoprene rubber, ethylene-propylene rubber, neoprene, butadiene Nitrile rubber, carboxyl nitrile rubber, butyl rubber, acrylate rubber, silicone rubber, fluorine rubber, polyurethane rubber, chloroether rubber, polysulfide rubber, chlorosulfonated polyethylene or chlorinated polyethylene.
  • the thermoplastic elastomer used in this method includes at least one of the following: styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS) , Hydrogenated SBS (SEBS), hydrogenated SIS (SEPS), polyether polyurethane thermoplastic elastomer, polyester polyurethane thermoplastic elastomer, polyester thermoplastic elastomer, ethylene copolymer thermoplastic elastomer or polyvinyl chloride thermoplastic elastomer.
  • SBS styrene-butadiene-styrene block copolymer
  • SEBS Hydrogenated SBS
  • SEPS hydrogenated SIS
  • polyether polyurethane thermoplastic elastomer polyether polyurethane thermoplastic elastomer
  • polyester polyurethane thermoplastic elastomer polyester thermoplastic elastomer
  • the blending temperature is the blending temperature used in ordinary plastic processing. It can be determined according to the melting temperature of the base plastic. Choose from a range that does not decompose plastic. In addition, according to processing requirements, appropriate amounts of processing aids such as conventional additives for plastics processing, fillers and compatibilizers can be added to the blended materials.
  • the blending equipment used in this method is a universal blending equipment in the rubber and plastics processing industry, and may be a twin-screw extruder, a single-screw extruder, an open mill or an internal mixer.
  • the morphology and particle size distribution of the rubber phase contained in the toughened plastic of the present invention can be carried out by changing the particle diameter of the powdered rubber having a crosslinked structure to be mixed, and selecting an appropriate unvulcanized rubber and / or thermoplastic elastomer to match the mesh Control, has good toughness and processability, and maintains high strength and rigidity.
  • the toughening method of the brittle or relatively brittle plastic of the present invention has a single process tube, and is generally applicable to the toughening of various brittle or relatively brittle plastics.
  • Polypropylene pellets produced by Jinan Oil Refinery, brand T30S
  • fully vulcanized styrene-butadiene powder rubber styrene-butadiene-50 emulsion in Lanhua Latex Development Center, added 3% by weight of styrene-butadiene emulsion dry rubber
  • styrene-butadiene emulsion dry rubber After curing with trimethylolpropane triacrylate, it was irradiated and vulcanized with a radiation dose of 2.5 Mrad, which was obtained after spray drying, with an average particle size of 100 nm and a gel content of 90.4% by weight.
  • EPDM rubber pellets produced by Dupont Dow Elastomers L ⁇ .C., Brand 3745
  • antioxidant Irganox 1010 produced by Ciba Gage, Switzerland
  • the specific composition is: polypropylene and full
  • the weight ratio of vulcanized styrene-butadiene powder rubber and EPDM rubber is 90: 9: 1, and the amount of antioxidant is 0.5 part based on 100 parts of total rubber and plastic weight.
  • ZSK-25 twin-screw extruder from Germany WP company was used for blending and pelletizing.
  • the temperatures of each section of the extruder were: 170 ° C, 185 ° C ;, 190 ° C, 190 ° C, 190 ° C, and 190 ° C (head temperature).
  • the pellets were made into standard splines by injection molding and tested for various mechanical properties. The results are shown in Table 1.
  • Example 3 The weight ratio of polypropylene, fully vulcanized styrene-butadiene powder rubber, and EPDM rubber pellets in Example 1 was changed to 90: 8: 2, and other conditions were the same as in Example 1. The test results are listed in Table 1.
  • Example 3 The weight ratio of polypropylene, fully vulcanized styrene-butadiene powder rubber, and EPDM rubber pellets in Example 1 was changed to 90: 8: 2, and other conditions were the same as in Example 1. The test results are listed in Table 1.
  • Example 3 The weight ratio of polypropylene, fully vulcanized styrene-butadiene powder rubber, and EPDM rubber pellets in Example 1 was changed to 90: 8: 2, and other conditions were the same as in Example 1. The test results are listed in Table 1.
  • Example 3 The test results are listed in Table 1.
  • Example 1 The weight ratio of polypropylene, fully sintered styrene-butadiene powder rubber and EPDM rubber pellets in Example 1 was changed to 90: 5: 5, and the other conditions were the same as in Example 1. The results of the mechanical tests are listed in Table 1. Comparative Example 1
  • Example 1 The polypropylene pellets in Example 1 were directly made into a standard spline by injection molding, and various mechanical property tests were performed. The results are shown in Table 1.
  • Transparent polystyrene pellets produced by Yanshan Petrochemical, grade 666D
  • cross-linked styrene-butadiene powder rubber preparation method is described in detail below
  • SBS thermoplastic elastomer produced by Yanshan Petrochemical, grade 1401
  • antioxidant Irganox 1010 Same as in Example 1
  • the mixed ingredients have the following specific composition: the weight ratio of polystyrene, cross-linked styrene-butadiene powder rubber and SBS thermoplastic elastomer is 85: 13.5: 1.5, and the total weight of rubber and plastic is 100 parts.
  • the dosage is 0.5 part.
  • ZSK-25 twin-screw extruder from Germany WP company was used for blending and pelletizing.
  • the temperatures of each section of the extruder were: 170 ° C, 180 ° C, 180. C, 180 ° C, 180 ° C and 180 ° C (head temperature).
  • the pellets were made into standard splines by injection molding and tested for various mechanical properties. The results are shown in Table 2.
  • the crosslinked styrene-butadiene powder rubber used in this example is prepared as follows: The styrene-butadiene emulsion with a certain degree of cross-linking itself (this kind of cross-linking is caused by a certain cross-linking reaction between rubber molecules during the synthesis of the rubber emulsion, so that the rubber emulsion has a certain degree of cross-linking ), Spray drying with a spray dryer, the inlet temperature of the spray dryer is 140 ° C-160 ° C, the outlet temperature is 40 ° C-60 ° C, the dried styrene-butadiene powder rubber is collected in a cyclone separator, that is, A crosslinked styrene-butadiene powder rubber was obtained with a particle diameter of about 100 nm and a gel content of 88.9% by weight.
  • the styrene-butadiene emulsion uses a cross-linked styrene-butadiene emulsion with a brand of styrene-butadiene-50 and a gel content of about 88% by weight produced by the Blue Rubber Latex Development Center.
  • Example 4 The weight ratio of polystyrene, cross-linked styrene-butadiene powder rubber and SBS thermoplastic elastomer in Example 4 was changed to 85: 12: 3. The rest of the conditions were the same as those in Example 4. The mechanical test results are shown in Table 2.
  • Example 4 The weight ratio of polystyrene, cross-linked styrene-butadiene powder rubber and SBS thermoplastic elastomer in Example 4 was changed to 85: 8: 7. The rest of the conditions were the same as in Example 4. The mechanical test results are shown in Table 2.
  • Example 4 The polystyrene pellets in Example 4 were directly made into a standard spline by injection molding. Various mechanical performance tests were performed, and the results are shown in Table 2.
  • AS resin produced by Taiwan Chi Mei, brand PN-127 L200
  • fully vulcanized styrene-butadiene powder rubber (same as Example 1)
  • SIS thermoplastic elastomer produced by Dow Exxon Chem. CO., Brand 4113
  • antioxidant Irganox 1010 (Same as Example 1)
  • AS resin produced by Taiwan Chi Mei, brand PN-127 L200
  • AS resin produced by Taiwan Chi Mei, brand PN-127 L200
  • SIS thermoplastic elastomer produced by Dow Exxon Chem. CO., Brand 4113
  • antioxidant Irganox 1010 (Same as Example 1)
  • the specific composition is: the weight ratio of AS resin, fully vulcanized styrene-butadiene powder rubber and SIS thermoplastic elastomer is 80: 18: 2, based on the total weight of rubber and plastic as 100 parts of stearic acid (Beijing Changyang Chemical Plant, chemically pure) The dosage is 0.2 parts.
  • ZSK-25 twin-screw extruder from Germany WP company was used for blending and pelletizing.
  • the temperatures of each section of the extruder were: 220 ° C, 240, 240 ° C, 240 ° C, 245 ° C, and 240 ° C (machine Head temperature).
  • the pellets were made into standard splines by injection molding and tested for various mechanical properties. The results are shown in Table 3.
  • Example 8 The weight ratio of the AS resin, the fully vulcanized styrene-butadiene powder rubber, and the SIS thermoplastic elastomer in Example 7 was changed to 80: 16: 4, and the remaining conditions were the same as those in Example 7. The results of the mechanical tests are shown in Table 3.
  • Example 7 The weight ratio of the AS resin, the fully vulcanized styrene-butadiene powder rubber, and the SIS thermoplastic elastomer in Example 7 was 80:10:10. The remaining conditions were the same as those in Example 7. The results of the mechanical tests are shown in Table 3.
  • Example 7 The weight ratio of the AS resin, the fully vulcanized styrene-butadiene powder rubber, and the SIS thermoplastic elastomer in Example 7 was 80: 4: 16. The remaining conditions are the same as in Example 7. The mechanical test results are shown in Table 3.
  • Example 7 The weight ratio of the AS resin, the fully vulcanized styrene-butadiene powder rubber, and the SIS thermoplastic elastomer in Example 7 was 80: 2: 18, and the remaining conditions were the same as those in Example 7. The results of the mechanical tests are shown in Table 3.
  • Example 7 The AS pellets in Example 7 were directly made into a standard spline by injection molding, and various mechanical properties tests were performed. The results are shown in Table 3. Table 3 Tensile tensile fracture Izod notched flexural bending thermal deformation strength elongation impact strength strength modulus temperature unit MPa% J / m MPa GPa "C Example 7 48.9 32.5 .75.6 78.2 2.15 73.6 Example 8 45.6 29.8 65.8 75.6 2.07 72.2 Example 9 42.9 22.5 43.1 69.8 1.92 69.8 Example
  • Comparative example 7 43.2 25.7 45.9 68.3 1.96 71.5 Comparative example 8 33.7 4.5 32.1 53.9 1.62 63.6 Comparative example 9 72.5 3.5 22.8 105.6 2.68 84.5 Test standards ASTM ASTM ASTM ASTM ASTM ASTM

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

增韧塑料及其制备方法 技术领域
本发明涉及增韧塑料及其制备方法， 更具体地说， 本发明涉及 采用两种或两种以上的橡胶组分与脆性或较脆性塑料共混而制得 的增韧塑料及其制备方法。
发明背景
根据美国杜邦公司 的 Souheng Wu 发表于 Polymer International Vol. 29, No. 3, ( 1992 ) 229-247上的文章对塑料的 划分， 当塑料的链缠结密度 Ve < 0.15 mmol/ml、 链特征比 C∞ > 7.5 时， 对于外来冲击能主要以基体形成银纹来耗散， 属于脆性塑料， 如聚苯乙烯、 聚甲基丙烯酸甲酯、 丙烯腈-苯乙烯树脂等； 当塑料的 链缠结密度 Ve > 0.15mmol/ml、 特征比 C∞ < 7.5时， 对于外来冲击 能主要以基体产生剪切屈服来耗散能量， 属于韧性塑料。 介于脆性 和韧性之间的一些塑料以及链缠结密度 Ve接近 0.15 mmol/ml的韧 性塑料， 在本说明书中， 发明人将其定义为较脆性塑料， 如聚氯乙 烯、 聚丙烯、 聚甲醛等。
现有技术中对脆性或较脆性塑料的增韧有在塑料聚合的过程 中加入橡胶的方法， 如将顺丁橡胶溶于苯乙烯单体中， 采用聚合的 方法最后制得含有包藏结构的橡胶粒子增韧的高抗冲聚苯乙烯，但 这种方法的工艺比较繁瑣， 对其它种类的脆性塑料并不一定适合； 另外就是采用橡胶与塑料熔融共混的方法， 即加入未硫化的橡胶或 热塑性弹性体对脆性或较脆性塑料增韧， 例如采用乙丙橡胶来增韧 聚丙烯。 由于橡胶粒子在塑料基质中的形态和分布对增韧效果有很 大影响， 这种方法很难对橡胶在塑料基质中的分散状态进行有效的 控制， 所以增韧效果不很理想， 而且为了达到所需的韧性指标， 常 常需加入较多的橡胶，从而会使塑料的强度、刚性等性能损失较大。 发明概述
本发明人通过大量的试验研究发现， 采用小粒径的具有交联结 构的粉末橡胶与未硫化橡胶和 /或热塑性弹性体混合使用来增韧脆 性塑料或较脆性塑料， 可达到很好的增韧效果， 且该方法适合于各 类脆性或较脆性塑料的增韧。
因此， 本发明的目的是提供一种由混合橡胶组分增韧脆性或较 脆性塑料而得到的增韧塑料。这种增韧塑料在具有良好韧性的同时 保持有较高的强度和刚性。
本发明的另一目的是提供一种脆性或较脆性塑料的增韧方法， 该方法工艺简单， 普遍适用于各种脆性或较脆性塑料的增韧。
在本发明的第一方面， 提供了一类增韧塑料， 其包含相互共混 的以下组分： 脆性或较脆性的塑料和混合橡胶組分， 其中混合橡胶 组分是由平均粒径为 0.02 μ m~0.5 μ m、具有交联结构的粉末橡胶和 下列至少一种物质混合组成： 未硫化的橡胶和热塑性弹性体。
在本发明的另一方面， 提供了一种制备上述增韧塑料的方法， 包括将脆性或较脆性的塑料与混合橡胶组分熔融共混。
发明详述
本发明的增韧塑料包含相互共混的以下组分： 脆性或较脆性的 塑料和混合橡胶組分。 其中混合橡胶组分是由平均粒径为 0.02 μ m~0.5 μ m 优选为 0.05 μ π！〜 0.2 μ m、 具有交联结构的粉末橡胶和 下列至少一种物质混合组成： 未硫化的橡胶和热塑性弹性体， 其中 未硫化的橡胶与热塑性弹性体可以任意配比混合。 混合橡胶組分与 塑料的重量比为 1: 99〜30： 70, 优选为 5: 95-25: 75。 其中粉末 橡胶占混合橡胶组分总重量的 10%〜95%重量， 优选为 50%~95% 重量。
作为本发明的增韧塑料基质的脆性或较脆性塑料包括： 聚苯乙 烯、 丙烯腈 -苯乙烯树脂 （AS ) 、 聚醋酸乙烯酯、 聚甲基丙烯酸甲 酯、 聚氯乙烯、 聚丙烯或聚甲醛。
作为本发明增韧塑料分散相的混合橡胶组分中的具有交联结 构的粉末橡胶粒子为均相结构的橡胶粒子，其凝胶含量为 60%重量 或更高，优选 80%重量或更高；橡胶粒子的平均粒径为 0.02 μ m〜0.5 μ m, 优选为 0.05 μ m~0.2 μ m。
该种橡胶粒子优选采用按照本发明人于 1999年 12月 3日提交 的中国专利申请 99125530.5 (其公开内容全部引入本文供参考）所 制备的全硫化粉末橡胶，具体包括但不限于以下全硫化粉末橡胶的 至少一种： 全硫化粉末天然橡胶、 全硫化粉末丁苯橡胶、 全硫化粉 末羧基丁苯橡胶、全硫化粉末丁腈橡胶、全硫化粉末羧基丁腈橡胶、 全硫化粉末氯丁橡胶、 全硫化粉末聚丁二烯橡胶、 全硫化粉末硅橡 胶或全硫化粉末丙烯酸酯橡胶等。该种全硫化粉末橡胶是指凝胶含 量为 60%重量或更高，干燥后无需加隔离剂即可自由流动的离散的 橡胶微粉。该种全硫化粉末橡胶可以通过将橡胶乳液辐照交联而得 到， 具体制备方法参见上述中国专利申请 99125530.5。
以上所述的橡胶粒子还可以采用交联型粉末橡胶。
本发明人通过实验研究发现， 有一些橡胶乳液在合成的过程中 橡胶分子之间会发生一定的交联反应，从而使所得到的橡胶乳液具 有一定的交联程度。 我们称之为交联型橡胶乳液。 对于这种交联型 橡胶乳液， 当其自身的交联程度较高时， 无需进一步辐照交联即可 经喷雾干燥制得粉末橡胶。 当然对于同种橡胶而言这种粉末橡胶的 交联程度要低于经辐照得到的全硫化粉末橡胶， 我们称之为交联型 粉末橡胶。
这种交联型粉末橡胶的凝胶含量与作为原料的交联型合成橡 胶乳液的凝胶含量是基本保持一致的，其凝胶含量为 80%重量或更 高， 优选为 85%重量或更高。 该粉末橡胶具有较小的粒径， 平均为 50~300nm。 该种交联型粉末橡胶不需加入隔离剂即可自由流动。 当然如果需要， 这种交联型粉末橡胶中也可加入隔离剂， 以进一步 提高其可流动性和抗粘连性。该种粉末橡胶中的每个微粒都是均相 的， 即单个微粒在组成上都是均质的， 在现有显微技术的观察下微 粒内部没有发现分层、 分相等不均相现象。 交联型粉末橡胶的种类 没有任何限制， 它可以是采用各种交联型的合成橡胶乳液制得的交 联型粉末橡胶， 例如交联型粉末丁苯橡胶、 交联型粉末 丁苯橡 胶、 交联型粉末聚丁二烯橡胶、 联型粉末丁腈橡胶、 交联型粉末 羧基丁腈橡胶、交联型粉末氯丁橡胶、交联型粉末丙烯酸酯橡胶等。
该种交联型粉末橡胶的制备方法是: 以各种交联型的合成橡胶 乳液为原料， 经干燥即可得到交联型粉末橡胶。 干燥过程可以用喷 雾干燥法或是沉淀干燥法， 优选喷雾干燥法。 如果用喷雾干燥法， 喷雾干燥器的进口温度可控制在 100~200°C，出口温度控制在 20〜80 °C。 在制备交联型粉末橡胶时， 所用的交联型合成胶乳的种类可以 是各类交联型的合成橡胶乳液， 要求其凝胶含量为 80%重量或更 高， 优选 85%重量或更高。 交联型合成胶乳可以选自： 交联型丁苯 橡胶乳液、 交联型羧基丁苯橡胶乳液、 交联型聚丁二烯橡胶乳液、 交联型丁腈橡胶乳液、 交联型羧基丁腈橡胶乳液、 交联型氯丁橡胶 乳液、 交联型丙烯酸酯橡胶乳液。
本发明增韧塑料中的橡胶粒子采用这种交联型粉末橡胶时， 优 先选用交联型粉末丁苯橡胶或交联型粉末聚丁二烯橡胶等。
作为本发明增韧塑料分散相的混合橡胶组分中的未硫化橡胶 包括以下橡胶中的至少一种： 天熬橡胶、丁苯橡胶、幾基丁苯橡胶、 聚丁二烯橡胶、聚异戊二烯橡胶、 乙丙橡胶、氯丁橡胶、丁腈橡胶、 羧基丁腈橡胶、 丁基橡胶、 丙烯酸酯橡胶、 硅橡胶、 氟橡胶、 聚氨 酯橡胶、 氯醚橡胶、 聚硫橡胶、 氯磺化聚乙烯或氯化聚乙烯。
作为本发明增韧塑料分散相的混合橡胶组分中的热塑性弹性 体包括以下所述的至少一种： 苯乙烯-丁二烯 -苯乙烯嵌段共聚物 ( SBS ) 、 苯乙烯-异戊二烯 -苯乙烯嵌段共聚物（SIS )、 氢化 SBS ( SEBS ) 、 氢化 SIS ( SEPS ) 、 聚醚型聚氨酯热塑性弹性体、 聚 酯型聚氨酯热塑性弹性体、 聚酯类热塑性弹性体、 乙烯共聚物热塑 性弹性体或聚氯乙烯热塑性弹性体。 以上所述的各种未硫化橡胶和 各种热塑性弹性体可以分别单独或以任意方式組合， 作为混合橡胶 组分中的组成部分之一。
本发明的增韧塑料的制备方法是：
将脆性或较脆性的塑料和混合橡胶組分通过常规橡塑共混方 法而制得所述的增韧塑料。 所用的混合橡胶是由平均粒径为 0.02 μ ιη〜0.5 μ ιη、 优选为 0.05 μ m~0.2 μ m、 具有交联结构的粉末橡胶和 下列至少一种物质混合组成： 未硫化的橡胶和热塑性弹性体， 其中 未硫化的橡胶与热塑性弹性体可以任意配比混合。 混合橡胶組分与 塑料的重量比为 1: 99〜30： 70， 优选为 5: 95-25: 75。 其中粉末 橡胶占混合橡胶组分总重量的 10%~95%重量， 优选为 50%〜95% 重量。
本方法中所用的脆性或较脆性塑料包括： 聚苯乙烯、 丙烯腈- 苯乙烯树脂（AS )、聚醋酸乙烯酯、聚甲基丙烯酸甲酯、聚氯乙烯、 聚丙烯或聚甲醛。
本方法中所用的具有交联结构的粉末橡胶粒子为均相结构的 橡胶粒子， 其凝胶含量为 60%重量或更高， 优选为 80%重量或更 高； 橡胶粒子的平均粒径为 0.02 μ m〜0.5 μ m, 优选为 0.05 μ m~0.2 μ m。
该种橡胶粒子可采用按照本发明人于 1999年 12月 3日提交的 中国专利申请 99125530.5 (其公开内容全部引入本文供参考 )所制 备的全硫化粉末橡胶， 具体包括但不限于以下全硫化粉末橡胶的至 少一种： 全硫化粉末天然橡胶、 全硫化粉末丁苯橡胶、 全硫化粉末 羧基丁苯橡胶、 全硫化粉末丁腈橡胶、 全 u化粉末羧基丁腈橡胶、 全硫化粉末氯丁橡胶、 全硫化粉末聚丁二烯橡胶、 全硫化粉末硅橡 胶或全硫化粉末丙烯酸酯橡胶等。该种全硫化粉末橡胶是指凝胶含 量为 60%重量或更高，干燥后无需加隔离剂即可自由流动的离散的 橡胶微粉。该种全硫化粉末橡胶可以通过将橡胶乳液辐照交联而得 到， 具体制备方法参见上述中国专利申请 99125530.5。
以上所述的橡胶粒子还可以采用交联型粉末橡胶。
本发明人通过实驗研究发现， 有一些橡胶乳液在合成的过程中 橡胶分子之间会发生一定的交联反应，从而使所得到的橡胶乳液具 有一定的交联程度。 我们称之为交联型橡胶乳液。 对于这种交联型 橡股乳液， 当其自身的交联程度较高时， 无需进一步辐照交联即可 经喷雾干燥制得粉末橡胶。 当然对于同种橡胶而言这种粉末橡胶的 交联程度要低于经辐照得到的全硫化粉末橡胶， 我们称之为交联型 粉末橡胶。
这种交联型粉末橡胶的凝胶含量与作为原料的交联型合成橡 胶乳液的凝胶含量是基本保持一致的，其凝胶含量为 80%重量或更 高， 优选为 85%重量或更高。 该粉末橡胶具有较小的粒径， 平均为 50〜300nm。 该种交联型粉末橡胶不需加入隔离剂即可自由流动。 当然如果需要， 这种交联型粉末橡胶中也可加入隔离剂， 以进一步 提高其可流动性和抗粘连性。该种粉末橡胶中的每个微粒都是均相 的， 即单个微粒在组成上都是均质的， 在现有显微技术的观察下微 粒内部没有发现分层、 分相等不均相现象。 交联型粉末橡胶的种类 没有任何限制， 它可以是采用各种交联型的合成橡胶乳液制得的交 联型粉末橡胶， 例如交联型粉末丁苯橡胶、 交联型粉末羧基丁苯橡 胶、 交联型粉末聚丁二浠橡胶、 交联型粉末丁腈橡胶、 交联型粉末 羧基丁膪橡胶、交联型粉末氯丁橡胶、交联型粉末丙烯酸酯橡胶等。
该种交联型粉末橡胶的制备方法是： 以各种交联型的合成橡胶 乳液为原料， 经干燥即可得到交联型粉末橡胶。 干燥过程可以用喷 雾干燥法或是沉淀干燥法， 优选喷雾干燥法。 如果用喷雾干燥法， 喷雾干燥器的进口温度可控制在 100〜200°C，出口温度控制在 20〜80 °C。 在制备交联型粉末橡胶时， 所用的交联型合成胶乳的种类可以 是各类交联型的合成橡胶乳液， 要求其凝胶含量为 80%重量或更 高， 优选 85%重量或更高。 交联型合成胶乳可以选自： 交联型丁苯 橡胶乳液、 交联型羧基丁苯橡胶乳液、 交联型聚丁二烯橡胶乳液、 交联型丁腈橡胶乳液、 交联型羧基丁腈橡胶乳液、 交联型氯丁橡胶 乳液、 交联型丙烯酸酯橡胶乳液。
在制备本发明的增韧塑料时， 所用橡胶粒子可采用这种交联型 粉末橡胶，优先选用交联型粉末丁苯橡胶或交联型粉末聚丁二烯橡 胶等。
本方法中所用的未硫化橡胶包括以下橡胶中的至少一种： 天然 橡胶、丁苯橡胶、羧基丁苯橡胶、聚丁二烯橡胶、 聚异戊二烯橡胶、 乙丙橡胶、 氯丁橡胶、 丁腈橡胶、 羧基丁腈橡胶、 丁基橡胶、 丙烯 酸酯橡胶、 硅橡胶、 氟橡胶、 聚氨酯橡胶、 氯醚橡胶、 聚硫橡胶、 氯磺化聚乙烯或氯化聚乙烯。
本方法所用的热塑性弹性体包括以下所述的至少一种： 苯乙烯 一丁二烯 -苯乙烯嵌段共聚物（SBS )、 苯乙烯-异戊二烯 -苯乙烯嵌段 共聚物（ SIS ) 、 氢化 SBS ( SEBS ) 、 氢化 SIS ( SEPS ) 、 聚醚型 聚氨酯热塑性弹性体、 聚酯型聚氨酯热塑性弹性体、 聚酯类热塑性 弹性体、 乙烯共聚物热塑性弹性体或聚氯乙烯热塑性弹性体。 以上 所述的各种未硫化橡胶和各种热塑性弹性体可以分别单独或以任 意方式组合， 作为混合橡胶组分中的组成部分之一。
采用橡塑共混方法制备本发明的增韧塑料过程中， 共混温度即 为普通塑料加工中所用的共混温度， 可根据基体塑料的熔融温度而 定，应该在既保证基体塑料完全熔融又不会使塑料分解的范围内选 择。 此外， 根据加工需要， 可在共混物料中适量加入塑料加工的常 规助剂、 填料和增容剂等加工助剂。
本方法所使用的共混设备为橡塑加工业中的通用共混设备， 可 以是双螺杆挤出机、 单螺杆挤出机、 开炼机或密炼机等。 本发明的增韧塑料所含橡胶相的形态和粒径分布可通过改变 所混入的具有交联结构的粉末橡胶的粒径及选择适当的未硫化橡 胶和 /或热塑性弹性体与^目配合来进行控制，具有良好的韧性和加 工性能， 并保持有较高的强度和刚性。
本发明的脆性或较脆性塑料的增韧方法， 工艺筒单， 普遍适用 于各种脆性或较脆性塑料的增韧。
实施例
下面结合实施例进一步描述本发明， 本发明的范围不受这些实 施例的限制。 本发明的范围在权利要求书中给出。
实施例 1
将聚丙烯粒料（济南炼油厂生产， 牌号 T30S )、 全硫化丁苯粉 末橡胶（在兰化胶乳研制中心的丁苯 -50 乳液中， 按丁苯乳液干胶 重量的 3 %加入交联助剂三羟甲基丙烷三丙烯酸酯后， 进行辐照硫 化，辐照剂量为 2.5Mrad, 经喷雾干燥后得到，平均粒径为 100nm， 凝胶含量为 90.4%重量； 具体制备过程参见前述中国专利申请 99125530.5 ) 、 三元乙丙橡胶粒料（Dupont Dow Elastomers L丄 .C. 生产， 牌号 3745 )及抗氧剂 Irganox 1010 (瑞士汽巴嘉基生产）混 合配料， 具体组成为： 聚丙烯与全硫化丁苯粉末橡胶及三元乙丙胶 的重量比为 90: 9: 1 , 以橡胶及塑料总重为 100份计抗氧剂用量为 0.5份。采用德国 WP公司的 ZSK-25双螺杆挤出机共混造粒，挤出 机各段温度分别为： 170 °C、 185 °C；、 190 °C、 190 °C、 190 °C和 190 °C (机头温度）。 粒料经注塑法制成标准样条， 进行各项力学性能 测试， 其结果如表 1所示。
实施例 2
将实施例 1中的聚丙烯、 全硫化丁苯粉末橡胶及三元乙丙橡胶 粒料三者的重量比改为 90: 8: 2， 其余条件与实施例 1相同， 力学 测试结果列于表 1。 实施例 3
将实施例 1中的聚丙烯、 全疏化丁苯粉末橡胶及三元乙丙橡胶 粒料三者的重量比改为 90: 5: 5, 其余条件与实施例 1相同， 力学 测试结果列于表 1。 比较例 1
除了不加三元乙丙橡胶粒料， 聚丙烯与全硫化丁苯粉末橡胶的 重量比为 90: 10夕卜， 其余条件与实施例 1相同， 力学测试结果列 于表 1。
比较例 2
除了不加全硫化丁苯粉末橡胶， 聚丙烯与三元乙丙橡胶粒料的 重量比为 90: 10夕卜。 其余条件与实施例 1相同， 力学测试结果列 于表 1。
比较例 3
将实施例 1中的聚丙烯粒料直接经注塑法制成标准样条， 进行 各项力学性能测试， 结果列于表 1。
表 1
Figure imgf000011_0001
实施例 4
将透明聚苯乙烯粒料（燕山石化生产， 牌号 666D )、 交联型丁 苯粉末橡胶 (制备方法具体描述如下）、 SBS热塑性弹性体 (燕山 石化生产， 牌号 1401 )及抗氧剂 Irganox 1010 (同实施例 1 ) 混合 配料， 具体组成为： 聚苯乙烯、 交联型丁苯粉末橡胶及 SBS热塑性 弹性体的重量比为 85: 13.5: 1.5， 以橡胶及塑料总重为 100份计抗 氧剂用量为 0.5份。 采用德国 WP公司的 ZSK-25双螺杆挤出机共 混造粒， 挤出机各段温度分别为： 170 °C、 180 °C、 180。C、 180 °C、 180°C和 180°C (机头温度）。 粒料经注塑法制成标准样条， 进行各 项力学性能测试， 其结果如表 2所示。
本实施例所用交联型丁苯粉末橡胶按如下制备： 将本身具有一定交联程度的丁苯乳液（该种交联是由于橡胶乳 液在合成的过程中橡胶分子之间发生一定的交联反应而带来的，从 而使橡胶乳液具有一定的交联程度） ， 通过喷雾干燥器喷雾干燥， 喷雾干燥器的进口温度为 140°C-160°C , 出口温度为 40°C-60°C， 于 旋风分离器中收集干燥后的丁苯粉末橡胶， 即得到交联型丁苯粉末 橡胶， 其粒径约为 100nm， 凝胶含量为 88.9%重量。 在此丁苯乳液 采用兰化胶乳研制中心生产的牌号为丁苯 -50、 凝胶含量约为 88% 重量的交联型丁苯乳液。
实施例 5
将实施例 4中的聚苯乙烯、交联型丁苯粉末橡胶及 SBS热塑性弹 性体三者重量比改为 85: 12: 3 , 其余条件与实施例 4相同， 力学测 试结果列于表 2。
实施例 6
将实施例 4中的聚苯乙烯、交联型丁苯粉末橡胶及 SBS热塑性弹 性体三者重量比改为 85: 8: 7， 其余条件与实施例 4相同， 力学测 试结果列于表 2。
比较例 4
除了不加 SBS热塑性弹性体， 聚苯乙烯、 交联型丁苯粉末橡胶 重量比为 85: 15外， 其余条件与实施例 4相同， 力学测试结果列 于表 2。
比较例 5
除了不加交联型丁苯粉末橡胶，聚苯乙烯与 SBS热塑性弹性体 的重量比为 85: 15外， 其余条件与实施例 4相同， 力学测试结果 列于表 2。
比较例 6
将实施例 4中的聚苯乙烯粒料直接经注塑法制成标准样条， 进 行各项力学性能测试， 结果列于表 2。
表 2
Figure imgf000013_0001
实施例 7
将 AS树脂 (台湾奇美生产， 牌号 PN-127 L200 ) 、 全硫化丁 苯粉末橡胶 (同实施例 1 ) 、 SIS热塑性弹性体（ Dow Exxon Chem. CO。 生产， 牌号 4113 )及抗氧剂 Irganox 1010 (同实施例 1 )混合 配料， 具体组成为： AS树脂、 全硫化丁苯粉末橡胶及 SIS热塑性 弹性体的重量比为 80: 18: 2， 以橡胶及塑料总重为 100份计硬脂 酸 （北京长阳化工厂， 化学纯）用量为 0.2份。 采用德国 WP公 司的 ZSK-25双螺杆挤出机共混造粒，挤出机各段温度分别为： 220 °C、 240 , 240 °C , 240°C、 245°C和 240°C (机头温度） 。 粒料经 注塑法制成标准样条，进行各项力学性能测试，其结果如表 3所示。
实施例 8 将实施例 7中的 AS树脂、 全硫化丁苯粉末橡胶及 SIS热塑性 弹性体三者的重量比改为 80: 16: 4， 其余条件与实施例 7相同， 力学测试结果列于表 3。
实施例 9
将实施例 7中的 AS树脂、 全硫化丁苯粉末橡胶及 SIS热塑性 弹性体三者的重量比为 80: 10: 10， 其余条件与实施例 7相同， 力 学测试结果列于表 3。
实施例 10
将实施例 7中的 AS树脂、 全硫化丁苯粉末橡胶及 SIS热塑性 弹性体三者的重量比为 80: 4: 16, 。 其余条件与实施例 7相同， 力学测试结果列于表 3。
实施例 11
将实施例 7中的 AS树脂、 全硫化丁苯粉末橡胶及 SIS热塑性 弹性体三者的重量比为 80: 2: 18， 其余条件与实施例 7相同， 力 学测试结果列于表 3。
比较例 7
除了不加 SIS热塑性弹性体， AS树脂与全硫化丁苯粉末橡胶 重量比改为 80: 20, 其余条件与实施例 7相同， 力学测试结果列于 表 3。
比较例 8
除了不加全硫化丁苯粉末橡胶， AS树脂与 SIS热塑性弹性体 的重量比改为 80: 20, 其余条件与实施例 7相同， 力学测试结果列 于表 3。
比较例 9
将实施例 7中的 AS粒料直接经注塑法制成标准样条， 进行各 项力学性能测试， 结果列于表 3。 表 3 拉伸 拉伸断裂 Izod缺口 弯曲 弯曲 热变形 强度 伸长率 冲击强度 强度 模量 温度 单位 MPa % J/m MPa GPa "C 实施例 7 48.9 32.5 .75.6 78.2 2.15 73.6 实施例 8 45.6 29.8 65.8 75.6 2.07 72.2 实施例 9 42.9 22.5 43.1 69.8 1.92 69.8 实施例
38.3 15.8 39.5 65.2 1.83 67.2 10
实施例
36.8 12.6 36.9 60.7 1.73 65.1 11
比较例 7 43.2 25.7 45.9 68.3 1.96 71.5 比较例 8 33.7 4.5 32.1 53.9 1.62 63.6 比较例 9 72.5 3.5 22.8 105.6 2.68 84.5 测试标准 ASTM ASTM ASTM ASTM ASTM ASTM
D638 D638 D256 D790 D790 D648

Claims

权 利 要 求
1. 一种含有混合橡胶组分的增韧塑料， 其特征是该增韧塑料包 含相互共混的以下組分： 脆性或较脆性的塑料和混合橡胶组分； 其 中脆性塑料为链缠结密度 Ve < 0.15 mmol/ml,链特征比 C~ > 7.5的 塑料， 较脆性塑料选自聚氯乙烯、 聚丙烯和聚甲醛； 混合橡胶组分 是由平均粒径为 0.02 μ m〜0.5 μ m、具有交联结构的粉末橡胶和下列 至少一种物质混合組成： 未硫化的橡胶和热塑性弹性体。
2. 根据权利要求 1所述的增韧塑料， 其特征是脆性或较脆性塑 料包括： 聚苯乙烯、 丙烯腈-苯乙烯树脂、 聚醋酸乙烯酯、 聚甲基丙 烯酸甲酯、 聚氯乙烯、 聚丙烯或聚甲醛。
3. 根据权利要求 1所述的增韧塑料， 其特征是具有交联结构的 粉末橡胶的平均粒径为 0.05 μ m~0.2 μ m。
4. 根据权利要求 1所述的增韧塑料， 其特征是混合橡胶组分中 的具有交联结构的粉末橡股粒子为均相结构的橡胶粒子 , 其凝股含 量为 60%重量或更高。
5. 根据权利要求 4所述的增韧塑料， 其特征是混合橡胶组分中 的具有交联结构的粉末橡胶粒子的凝胶含量为 80%重量或更高。
6. 根据权利要求 4所述的增韧塑料， 其特征是混合橡胶组分中 橡胶。
7. 根据权利要求 6所述的增韧塑料， 其特征是所述的全硫化粉 末橡胶包括以下物盾的至少一种： 全硫化粉末天然橡胶、 全硫化粉 末丁苯橡胶、 全硫化粉末 丁苯橡胶、 全硫化粉末丁腈橡胶、 全 硫化粉末羧基丁腈橡胶、 全硫化粉末氯丁橡胶、 全硫化粉末聚丁二 烯橡胶、 全硫化粉末硅橡胶或全硫化粉末丙烯酸酯橡胶。
8. 根据权利要求 6所述的增韧塑料， 其特征是所述的交联型粉 末橡胶包括以下物质的至少一种： 交联型粉末丁苯橡胶或交联型粉 末聚丁二烯橡胶。
9. 根据权利要求 1-8 中任一项所述的增韧塑料， 其特征是所述 的混合橡胶组分与塑料的重量比为 1: 99-30: 70, 所述的粉末橡胶 占混合橡胶组分总重量的 10%~^5%重量。
10. 根据权利要求 9所述的增韧塑料，其特征是所述的粉末橡胶 占混合橡胶组分总重量的 50%~95%重量。
11. 根据权利要求 9所述的增韧塑料，其特征是所述的混合橡胶 組分与塑料的重量比为 5: 95-25: 75。
12. 根据权利要求 1-11 中任一项所述的增韧塑料的制备方法， 其特征在于将脆性或较脆性塑料与混合橡胶组分熔融共混而制得 所述增韧塑料。
PCT/CN2001/001531 2000-11-03 2001-11-05 Plastique malleable et son procede de preparation WO2002036664A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US10/415,769 US9181419B2 (en) 2000-11-03 2001-11-05 Toughened plastics and its preparation method
EP01992734A EP1340782B1 (en) 2000-11-03 2001-11-05 Toughened plastics and its preparation method
KR1020037006189A KR100817677B1 (ko) 2000-11-03 2001-11-05 강화 플라스틱 및 이의 제조 방법
AU2002220473A AU2002220473A1 (en) 2000-11-03 2001-11-05 Toughened plastics and its preparation method
JP2002539416A JP3929896B2 (ja) 2000-11-03 2001-11-05 靱性の強化されたプラスチックおよびその製造方法
DE60136646T DE60136646D1 (de) 2000-11-03 2001-11-05 Schlagzäh modifizierte kunststoffe und herstellungsverfahren dafür

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN00130385.6 2000-11-03
CNB001303856A CN1155652C (zh) 2000-11-03 2000-11-03 一种增韧塑料及其制备方法

Publications (1)

Publication Number Publication Date
WO2002036664A1 true WO2002036664A1 (fr) 2002-05-10

Family

ID=4594145

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2001/001531 WO2002036664A1 (fr) 2000-11-03 2001-11-05 Plastique malleable et son procede de preparation

Country Status (8)

Country Link
US (1) US9181419B2 (zh)
EP (1) EP1340782B1 (zh)
JP (1) JP3929896B2 (zh)
KR (1) KR100817677B1 (zh)
CN (1) CN1155652C (zh)
AU (1) AU2002220473A1 (zh)
DE (1) DE60136646D1 (zh)
WO (1) WO2002036664A1 (zh)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH694697A5 (de) * 2004-01-29 2005-06-15 Koelbl Engineering Und Consult Gummimehl-enthaltende Elastomerlegierungen.
CN100348658C (zh) * 2004-10-29 2007-11-14 中国石油化工股份有限公司 一种硬质聚氯乙烯组合物及其制备方法
CN104693658A (zh) * 2006-09-28 2015-06-10 罗门哈斯公司 包含具有非官能芳族端基的聚合物的复合材料
US20090053529A1 (en) * 2007-08-21 2009-02-26 Saint-Gobain Performance Plastics Corporation Roofing sheet material
US8936740B2 (en) 2010-08-13 2015-01-20 Kimberly-Clark Worldwide, Inc. Modified polylactic acid fibers
US10753023B2 (en) 2010-08-13 2020-08-25 Kimberly-Clark Worldwide, Inc. Toughened polylactic acid fibers
CN102731948A (zh) * 2011-03-31 2012-10-17 海洋王照明科技股份有限公司 用于透明灯筒的工程塑料、其制备方法和透明灯筒
CN102532732A (zh) * 2011-12-15 2012-07-04 吴江明峰聚氨酯制品有限公司 一种家电用塑料的制备方法
US8975305B2 (en) 2012-02-10 2015-03-10 Kimberly-Clark Worldwide, Inc. Rigid renewable polyester compositions having a high impact strength and tensile elongation
CN103483716B (zh) * 2012-06-08 2016-02-24 中国石油化工股份有限公司 一种硬质抗冲聚氯乙烯组合物及其制备方法
CN102807715A (zh) * 2012-07-27 2012-12-05 苏州市兴吴工程塑胶有限公司 一种增韧聚苯乙烯塑料的配方
US20140088258A1 (en) * 2012-09-25 2014-03-27 Lehigh Technologies, Inc. Elastomeric compositions comprising reclaimed vulcanized elastomer particles and improved methods of manufacture thereof
CN103244764A (zh) * 2013-05-10 2013-08-14 苏州嘉目工程有限公司 一种使用寿命长的消防水带
CN103524923B (zh) * 2013-09-04 2015-12-23 天津嫣稳伟业塑料制品有限责任公司 一种塑胶铁路枕木配方工艺
BR112017009619B1 (pt) 2014-11-26 2021-10-05 Kimberly-Clark Worldwide, Inc. Material de poliolefina, fibra, trama não tecida, artigo absorvente, e, método para formação de um material de poliolefina
CN106032434B (zh) * 2015-03-18 2019-12-20 中国石油化工股份有限公司 粉末橡胶和硫化粉末橡胶及其制备方法
CN104804323A (zh) * 2015-03-31 2015-07-29 太仓市晨洲塑业有限公司 一种pvc管材
CN105038239A (zh) * 2015-06-30 2015-11-11 苏州洋杰电子有限公司 一种耐候抗静电复合材料的制备方法
CN105937065A (zh) * 2016-06-27 2016-09-14 安庆石油化工总厂联盟化工厂 一种编织袋生产工艺
CN109575426A (zh) * 2017-09-29 2019-04-05 中国石化扬子石油化工有限公司 一种牙刷柄聚丙烯材料及其制备方法
CN109265827A (zh) * 2018-09-18 2019-01-25 江山市星耀新材料有限公司 一种改性弹性塑胶粉及其制备方法
CN111100342A (zh) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 一种橡胶增韧塑料及其制备方法
CN114276165B (zh) * 2021-12-24 2022-10-21 中国人民解放军陆军装甲兵学院 一种降低硬脆材料表面脆性的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1132517A (zh) * 1993-09-02 1996-10-02 陶氏化学公司 改进的橡胶改性聚苯乙烯
EP0811657A2 (en) * 1996-06-06 1997-12-10 Mitsuboshi Belting Ltd. Thermoplastic elastomer composition for powder slush molding and process for the preparation of the composition
CN1225931A (zh) * 1998-12-17 1999-08-18 湖北大学化学与材料科学学院 乙丙橡胶/聚丙烯共混型热塑弹性体及其制备方法

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3130177A (en) * 1961-03-24 1964-04-21 Borg Warner Blends of polycarbonates with polybutadiene, styrene, acrylonitrile graft copolymers
US3838490A (en) * 1966-08-01 1974-10-01 Co General D Electro Ceramique Assembly of insulators
US3865354A (en) * 1972-03-17 1975-02-11 Du Pont Apparatus
US4161472A (en) * 1978-01-23 1979-07-17 The B. F. Goodrich Company Impact modified vinyl chloride polymer composition
DE3229078A1 (de) * 1982-08-04 1984-02-09 Bayer Ag, 5090 Leverkusen Formmassen aus vinylchloridpolymerisat, pfropfpolymeren und polymeren weichmachern mit hoher alterungsbestaendigkeit
DE3339001A1 (de) * 1983-07-06 1985-01-17 Bayer Ag, 5090 Leverkusen Thermoplastische polyester-formmassen mit hoher zaehigkeit
EP0146172B1 (en) * 1983-12-03 1988-06-29 Stamicarbon B.V. Process for the preparation of impact-resistant thermoplastic polymer mixtures and impact-resistant polymer compositions
BR8700523A (pt) * 1986-01-30 1987-12-15 Dow Chemical Co Modificadores de impacto para resinas de cloreto de polivinila
DE3622736A1 (de) * 1986-07-05 1988-01-07 Bayer Ag Thermoplastische formmassen aus vinylchloridpolymerisaten und pfropfpolymerisaten mit verbesserten eigenschaften
JPS6395211A (ja) * 1986-10-09 1988-04-26 Mitsubishi Rayon Co Ltd 熱可塑性樹脂組成物
DE3800603A1 (de) * 1988-01-12 1989-07-20 Bayer Ag Formmassen aus aromatischen polyestern, vinyl-copolymerisaten und gepfropftem siliconkautschuk
JP2683548B2 (ja) * 1988-12-27 1997-12-03 出光石油化学株式会社 ポリプロピレン樹脂組成物
US5093423A (en) * 1990-09-24 1992-03-03 The West Company, Incorporated Method of making SBR thermoplastic elastomers
DE69128953T2 (de) * 1990-11-22 1998-10-08 Sumitomo Dow Ltd Harzzusammensetzung auf Basis von Polycarbonat und schlagfestes Polystyrol
EP0543597B1 (en) * 1991-11-18 1997-12-03 Dow Corning Corporation Poly(phenylene ether) resin modified with silicone rubber powder
JP3199494B2 (ja) * 1992-11-06 2001-08-20 ジェイエスアール株式会社 熱可塑性エラストマー組成物
DE4443966A1 (de) * 1994-12-09 1996-06-13 Basf Ag Thermoplastische Formmassen
GB2297092A (en) 1995-01-10 1996-07-24 Antonio Fernando Pileci Low compression set thermoplastic elastomers
WO1999011705A1 (fr) * 1997-08-28 1999-03-11 Mitsui Chemicals, Inc. Composition d'elastomere d'olefine thermoplastique
JP3433892B2 (ja) * 1997-09-16 2003-08-04 三菱レイヨン株式会社 加工性良好なアクリルフィルム、およびそのアクリルフィルムを積層した成形品
WO2001040356A1 (fr) * 1999-12-03 2001-06-07 China Petro-Chemical Corporation Caoutchouc en poudre entierement vulcanise a diametre de particules regulable, son procede de preparation et des utilisations
DE19962862A1 (de) * 1999-12-24 2001-06-28 Bayer Ag Kautschukmischungen auf Basis von unvernetzten Kautschuken und vernetzten Kautschukpartikeln sowie multifunktionellen Isocyanaten
CN1330095A (zh) * 2000-06-15 2002-01-09 中国石油化工股份有限公司 一种全硫化热塑性弹性体及其制备方法
CN1330097A (zh) * 2000-06-15 2002-01-09 中国石油化工股份有限公司 全硫化粉末硅橡胶及其制备方法
JP5443661B2 (ja) * 2000-08-22 2014-03-19 中国石油化工股▲分▼有限公司 強化されたプラスチック及びその調製
CN1177895C (zh) * 2001-10-12 2004-12-01 中国石油化工股份有限公司 一种增韧热固性树脂及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1132517A (zh) * 1993-09-02 1996-10-02 陶氏化学公司 改进的橡胶改性聚苯乙烯
EP0811657A2 (en) * 1996-06-06 1997-12-10 Mitsuboshi Belting Ltd. Thermoplastic elastomer composition for powder slush molding and process for the preparation of the composition
CN1225931A (zh) * 1998-12-17 1999-08-18 湖北大学化学与材料科学学院 乙丙橡胶/聚丙烯共混型热塑弹性体及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1340782A4 *

Also Published As

Publication number Publication date
KR20030066651A (ko) 2003-08-09
CN1155652C (zh) 2004-06-30
CN1353135A (zh) 2002-06-12
JP2004512426A (ja) 2004-04-22
JP3929896B2 (ja) 2007-06-13
DE60136646D1 (de) 2009-01-02
KR100817677B1 (ko) 2008-03-27
US9181419B2 (en) 2015-11-10
EP1340782A4 (en) 2005-03-02
EP1340782A1 (en) 2003-09-03
EP1340782B1 (en) 2008-11-19
AU2002220473A1 (en) 2002-05-15
US20040077792A1 (en) 2004-04-22

Similar Documents

Publication Publication Date Title
WO2002036664A1 (fr) Plastique malleable et son procede de preparation
CN1100087C (zh) 一种增韧聚烯烃用填充母粒的制备方法
JP5103391B2 (ja) 動的加硫により熱可塑性エラストマーを調製する方法
WO2001040356A1 (fr) Caoutchouc en poudre entierement vulcanise a diametre de particules regulable, son procede de preparation et des utilisations
Zhang et al. Compatibility of waste rubber powder/polystyrene blends by the addition of styrene grafted styrene butadiene rubber copolymer: effect on morphology and properties
AU609239B2 (en) Styrene-based resin composition
WO2002026869A1 (fr) Matiere plastique malleable et son procede de fabrication
AU610950B2 (en) Styrene-based resin composition
Pan et al. Biocomposites containing cellulose fibers treated with nanosized elastomeric latex for enhancing impact strength
WO2001014464A1 (fr) Elastomere thermoplastique produit a partir de poudre de rebuts de caoutchouc/plastique et article ainsi forme
CN104448679B (zh) 一种辐射交联无卤阻燃abs/pc复合材料及其制备方法
Zhang et al. Toughening of PBT/PC blends with epoxy functionalized core-shell modifiers
JPH054228A (ja) 再生樹脂組成物及びその再生方法
JP4250812B2 (ja) 通気性フィルムの製造方法
CN1229437C (zh) 一种聚对苯二甲酸丁二醇酯组合物及其制备方法
JPH04252232A (ja) ポリアセタール樹脂組成物構造体及びその製造法
JPH08259750A (ja) 繊維強化ポリプロピレン組成物の製造法
JPH0651813B2 (ja) 多孔性シ−トの製造方法
CN109320836A (zh) 一种有机无机杂化核壳纳米粒子增韧聚丙烯的方法
JPH10139945A (ja) 熱可塑性樹脂組成物
JP2004067944A (ja) 極性熱可塑性エラストマー組成物
CN1189846A (zh) 具有改进的冲击强度的丙烯聚合物组合物
JP3431085B2 (ja) ポリプロピレン系複合樹脂組成物
JPH0238441A (ja) 熱可塑性樹脂組成物
Ito et al. Effect of processing on the properties of poly (Methyl methacrylate)/silica nanocomposites.

Legal Events

Date Code Title Description
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1020037006189

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 703/DELNP/2003

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 2002539416

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2001992734

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020037006189

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2001992734

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWE Wipo information: entry into national phase

Ref document number: 10415769

Country of ref document: US

DPE2 Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101)