CN101173074B - Polypropelene composition with scratch resistant capability and processes for producing same - Google Patents
Polypropelene composition with scratch resistant capability and processes for producing same Download PDFInfo
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- CN101173074B CN101173074B CN2007101717098A CN200710171709A CN101173074B CN 101173074 B CN101173074 B CN 101173074B CN 2007101717098 A CN2007101717098 A CN 2007101717098A CN 200710171709 A CN200710171709 A CN 200710171709A CN 101173074 B CN101173074 B CN 101173074B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Abstract
The invention relates to a polypropylene combination with anti-scoring property. The polypropylene combination is characterized in that the invention consists of the following raw materials by weight part: 40 to 100 parts of polypropylene, 0.5 to 5 parts of maleic anhydride or glyceryl methacrylate copolymer or graft Alpha- olefin copolymer, 0.2 to 2 parts of aliphatics acid amide, 0 to 40 parts of mineral filler, 0 to 20 parts of toughening agent, 0.1 to 1 part of antioxidant agent, and 0.1 to 1 part of retardant agent. The polypropylene combination of the invention is provided with good aging-resistant, flame retardant and anti-scoring properties, and is used for vehicle inner decorating pieces, home appliances shells, etc.
Description
Technical field
The present invention relates to a kind of polypropene composition and preparation method thereof, be applied to automobile, household electrical appliances and mechanical industry field, belong to the polypropylene modification technical field with scratch resistant performance.
Background technology
Polypropylene has advantages such as light weight, anti-solvent, easily processing, excellent mechanical property, easy recovery because of it, obtained widespread use, and particularly the application at automotive industry, household electrical appliances and mechanical field improves constantly.Automotive industry will develop to directions such as energy-saving and environmental protection, safety future.This just requires that used quality of materials is light, processing is simple, easily reclaim etc., and polypropylene has satisfied these requirements.But polypropylene material is because surface hardness is low with respect to other material, and scratch resistant performance is poor, can not be satisfied with the requirement of automotive upholstery especially, as dashboard, auxiliary fasia console, door-plate, column, glove box, pull cover plate etc.These parts inevitably are subjected to the grazing of hard thing in production, transportation and use, scratch as fingernail.So automaker is launched respectively the damage resistant relevant criterion, be used to satisfy the needs of automobile.Polypropylene is used for appliance shell and machinery also requires good scratch resistant performance.
So many patents are by the damage resistant problem of number of ways solution polypropylene material, publication number is that the patent of CN1236375A improves scratch resistant performance by the degree of crystallinity that improves polypropylene material; Publication number is that the patent of CN1294614A improves scratch resistant performance by graft copolymer; Publication number is that the patent of CN1647247A improves scratch resistant performance by raising degree of crystallinity and partial cross-linked method; Publication number is that the patent of CN1479766A adopts the method for silicon grafted polyethylene to improve scratch resistant performance, and publication number is that the patent of CN1580115A adopts silicone elastomer to solve the damage resistant problem; Publication number is that the patent of CN1631959A adopts raising crystalling propylene degree to improve scratch resistant performance; Publication number is that the patent of CN1631960A adopts silicone elastomer and the method for preparing master batch to improve scratch resistant performance.
Though these methods have solved certain damage resistant problem in specific composition and system, can not fundamentally solve the damage resistant problem.
Summary of the invention
The purpose of this invention is to provide a kind of polypropene composition and preparation method thereof with scratch resistant performance.
For realizing above purpose, technical scheme of the present invention provides a kind of polypropene composition with scratch resistant performance, it is characterized in that, form: 0.5 part-5 parts of 40 parts-100 parts of polypropylene, maleic anhydride or glycidyl methacrylate copolymerization or grafting alpha-olefin copolymers, 0.2 part-2 parts of aliphatics primary amides, mineral filler 0-40 part, toughner 0-20 part, 0.1 part-1 part in oxidation inhibitor, 0.1 part-1 part of weather resisting agent by following weight part raw material;
Described aliphatics primary amide be stearylamide, erucicamide, mountain Yu acid amides, stearyl erucicamide, wherein one or more mixing;
Described maleic anhydride or glycidyl methacrylate copolymerization or grafting alpha-olefin copolymer are: ethylene-methyl acrylate-copolymer-maleic anhydride, ethylene-propylene acid butyl ester-glycidyl methacrylate copolymer, ethylene-methyl methacrylate glycidyl ester copolymer, maleic anhydride grafted ethene-octene copolymer, maleic anhydride grafted ethene-acetate ethylene copolymer, one or more are compound for the glycidyl methacrylate graft ethylene-acrylic acid copolymer.
Described mineral filler is a talcum powder; Described toughner is a kind of in amorphous ethylene-alpha-olefin copolymer and the styryl thermoplastic elastomer or their mixture; Described oxidation inhibitor is Hinered phenols and phosphorous acid esters, be four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethane and tricresyl phosphite (2,4 di-tert-butyl-phenyls) one or both of ester are composite, and described weather resisting agent is that one or more of hindered amines, ketone and benzotriazole category are composite.
A kind of preparation method with polypropene composition of scratch resistant performance is characterized in that, the steps include:
The first step. take by weighing each raw material by weight;
Second step. place mixing machine to mix 3-8 minute polypropylene, maleic anhydride or glycidyl methacrylate copolymerization or grafting alpha-olefin copolymer, aliphatics primary amide, toughner, oxidation inhibitor and weather resisting agent, obtain mixture;
The 3rd step. the mixture that mineral filler and step 2 are obtained is sent into respectively in twin screw or the reciprocation type list screw extruder with 180-235 ℃ temperature melt blending, extruding pelletization, and screw slenderness ratio is not less than 32.
The length-to-diameter ratio of the twin screw extrusion equipment that adopts is at least 32, and have precise dose control and a vacuum-pumping equipment, screw speed is at 100-600 rev/min, it is 180 ℃～200 ℃ in a district that its twin screw is extruded working temperature, 200 ℃～230 ℃ in two districts, 200 ℃～230 ℃ in three districts, 200 ℃～230 ℃ in four districts, residence time 1-2 minute;
The 4th goes on foot, extrudes, tie rod, and cooling, pelletizing obtains finished product at last.
Polypropylene is homo-polypropylene and Co-polypropylene, and homo-polypropylene comprises isotatic polypropylene, syndiotactic polypropylene and Atactic Polypropelene, and Co-polypropylene is a segmented copolymer.Adopt alpha-olefin as multipolymer.Alpha-olefin is propylene, 1-butylene, 1-hexene, 1-octene, perhaps any mixture with alpha-olefin of 3-12 carbon atom.Preferential selection ethylene content is the multipolymer of 5-15 weight part.
Toughner is to improve shock proof elastomerics, and oxidation inhibitor is a kind of chemical assistant that can suppress and delay polymer materials oxidation and degraded, and weather resisting agent is to improve the auxiliary agent of polymer materials light stability.
Aliphatics primary amide of the present invention is the damage resistant functional agent.By adding the aliphatics primary amide, improve the surface property of polypropylene composite material.Aliphatics primary amides such as erucicamide can reduce the frictional coefficient of material, thereby improve scratch resistant performance.
Advantage of the present invention is to have excellent ageing-resistant, weather-proof and scratch resistant performance.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment
Embodiments of the invention are estimated the damage resistant degree with the damage resistant tester.On the frosting of preparation, scrape a line segment figure with a mechanically operated scraper.Each scraper is only scraped once in one direction.Utilize a colourimeter to record the not misalignment on scratch surface then.Test condition is:
Temperature: 23 ± 5 ℃
Anchorage force: 10N
Scuffing speed: 1000mm/min
Scraper: diameter is 1mm.
The percentage number average by weight in the present invention.
Embodiment 1
Copolymerization PP, trade mark J641, Sinopec Guangzhou petrochemical industry branch office produces, 54.6 parts of consumptions; The aliphatics primary amide is selected erucicamide, trade mark Lutamide ER, the sky, Sichuan oil chemistry company limited, 0.8 part of consumption; Ethylene-methyl acrylate-copolymer-maleic anhydride, trade mark LOADERMAH, A Kema chemistry company limited, 3 parts of consumptions; Mineral filler is a talcum powder, 3000 orders, the wide talcum powder in osmanthus, Guilin company limited, 30 parts of consumptions; Toughner is POE, trade mark ENGAGE8440, du pont company, 10 parts of consumptions; Oxidation inhibitor four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethane, the trade mark is 1010, vapour crust fine chemistry Industrial Co., Ltd, 0.4 part of consumption, weather resisting agent is a hindered amine as light stabilizer, and the trade mark is 944,0.4 part of vapour crust fine chemistry Industrial Co., Ltd, the phthalein mountain valley with clumps of trees and bamboo is green, 0.8 part, process by twin screw extruder
Processing temperature 195-220 ℃.
Aberration Δ E=0.13 after the scuffing.
Embodiment 2
Copolymerization PP, trade mark J641, Sinopec Guangzhou petrochemical industry branch office produces, 64.6 parts of consumptions; The aliphatics primary amide is selected stearylamide, and the trade mark is Lutamide S, the sky, Sichuan oil chemistry company limited, 0.8 part of consumption; Maleic anhydride grafted ethene-acetate ethylene copolymer, trade mark 0A-1, Guangzhou Lu Shan chemical materials company limited, 3 parts of consumptions; Mineral filler is a talcum powder, 3000 orders, the wide talcum powder in osmanthus, Guilin company limited, 35 parts of consumptions; Toughner is POE, trade mark ENGAGE8150, du pont company, 10 parts of consumptions; Oxidation inhibitor four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethane, the trade mark is 1010, vapour crust fine chemistry Industrial Co., Ltd, 0.4 part of consumption; Weather resisting agent is a hindered amine as light stabilizer, and the trade mark is 744,0.4 part of vapour crust fine chemistry Industrial Co., Ltd; Phthalein mountain valley with clumps of trees and bamboo basket, 0.8 part.By twin screw extruder processing, processing temperature 195-220 ℃.
Aberration Δ E=0.1 after the scuffing.
Embodiment 3
Copolymerization PP, trade mark J641, Sinopec Guangzhou petrochemical industry branch office produces, 69.6 parts of consumptions; The aliphatics primary amide is selected mountain Yu acid amides, and the trade mark is Lutamide BR, the sky, Sichuan oil chemistry company limited, 0.8 part of consumption; Maleic anhydride grafted ethene-octene copolymer, trade mark OE-1, Guangzhou Lu Shan chemical materials company limited, 3 parts of consumptions; Mineral filler is a talcum powder, 3000 orders, the wide talcum powder in osmanthus, Guilin company limited, 30 parts of consumptions; Toughner is POE, trade mark ENGAGE8450, DOW Chemical Industrial Co., Ltd, 10 parts of consumptions; Oxidation inhibitor four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethane, the trade mark is 1010,0.2 part of consumption; Vapour crust fine chemistry Industrial Co., Ltd's tricresyl phosphite (2,4 di-tert-butyl-phenyl) ester, the trade mark is 168, vapour crust fine chemistry Industrial Co., Ltd, 0.2 part of consumption; Weather resisting agent is a benzotriazole light stabilizer, and the trade mark is 320,0.4 part of vapour crust fine chemistry Industrial Co., Ltd; The ultramarine basket, 0.8 part.By twin screw extruder processing, processing temperature 195-220 ℃.
Aberration Δ E=0.3 after the scuffing.
Embodiment 4
Copolymerization PP, trade mark SP179, Sinopec Shandong stock company produces, 89.6 parts of consumptions; The aliphatics primary amide is selected mountain Yu acid amides and stearylamide, and the mountain Yu acid amides trade mark is Lutamide BR, the sky, Sichuan oil chemistry company limited, 0.4 part of consumption; Select stearylamide, the trade mark is Lutamide S, the sky, Sichuan oil chemistry company limited, 0.4 part of consumption; Ethylene-methyl acrylate-copolymer-maleic anhydride, trade mark LOTADERMAH4403, A Kema chemistry company limited, 3 parts of consumptions; Mineral filler is a talcum powder, 3000 orders, the wide talcum powder in osmanthus, Guilin company limited, 10 parts of consumptions; Toughner is POE, trade mark ENGAGE8180, DOW Chemical Industrial Co., Ltd, 10 parts of consumptions; Oxidation inhibitor four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethane, the trade mark is 1010,0.2 part of consumption; Vapour crust fine chemistry Industrial Co., Ltd's tricresyl phosphite (2,4 di-tert-butyl-phenyl) ester, the trade mark is 168, vapour crust fine chemistry Industrial Co., Ltd, 0.2 part of consumption; Weather resisting agent is a benzophenone light stabilizer, and the trade mark is UV-531,0.4 part in Wuhan chemical assistant factory; Solid forever orange, 0.8 part.By twin screw extruder processing, processing temperature 195-220 ℃.Aberration Δ E=0.2 after the scuffing.
Embodiment 5
Copolymerization PP, trade mark SP179, Sinopec Shandong stock company produces, 79.6 parts of consumptions; The aliphatics primary amide is selected the stearyl erucicamide, and the trade mark is Lutamide S98, the sky, Sichuan oil chemistry company limited, ethylene-methyl methacrylate glycidyl ester copolymer, trade mark LOTADER AX8840, A Kema chemistry company limited, 3 parts of consumptions; Mineral filler is a talcum powder, 3000 orders, the wide talcum powder in osmanthus, Guilin company limited, 20 parts of consumptions; Toughner is POE, trade mark ENGAGE8401, DOW Chemical Industrial Co., Ltd, 10 parts of consumptions; Oxidation inhibitor four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethane, the trade mark is 1010,0.2 part of consumption; Vapour crust fine chemistry Industrial Co., Ltd's tricresyl phosphite (2,4 di-tert-butyl-phenyl) ester, the trade mark is 168, vapour crust fine chemistry Industrial Co., Ltd, 0.2 part of consumption; Weather resisting agent is a benzophenone light stabilizer, and the trade mark is UV-531,0.4 part in Wuhan chemical assistant factory; Plastic brown, 0.8 part.By twin screw extruder processing, processing temperature 195-220 ℃.
Aberration Δ E=0.3 after the scuffing.
Embodiment 6
Copolymerization PP, trade mark SP179, Sinopec Shandong stock company produces, 74.6 parts of consumptions; The aliphatics primary amide is selected stearyl erucicamide and erucicamide, the stearylamide erucicamide trade mark is Lutamide S98, consumption is 0.2 part, the erucicamide trade mark is Lutamide ER, and consumption is 0.7 part, is the sky, Sichuan oil chemistry company limited, ethylene-propylene acid butyl ester-glycidyl methacrylate copolymer, trade mark Elvaloy PTW, Dupont, 3 parts of consumptions; Mineral filler is a talcum powder, 3000 orders, the wide talcum powder in osmanthus, Guilin company limited, 25 parts of consumptions; Toughner is POE, trade mark ENGAGE8401, DOW Chemical Industrial Co., Ltd, 10 parts of consumptions; Oxidation inhibitor four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethane, the trade mark is 1010,0.2 part of consumption; Vapour crust fine chemistry Industrial Co., Ltd's tricresyl phosphite (2,4 di-tert-butyl-phenyl) ester, the trade mark is 168, vapour crust fine chemistry Industrial Co., Ltd, 0.2 part of consumption; Weather resisting agent is a benzophenone light stabilizer, and the trade mark is UV-531,0.4 part in Wuhan chemical assistant factory; Permanent yellow, 0.8 part.By twin screw extruder processing, processing temperature 195-220 ℃.
Aberration Δ E=0.2 after the scuffing.
Embodiment 7
Copolymerization PP, trade mark SP179, Sinopec Shandong stock company produces, 78.6 parts of consumptions; The aliphatics primary amide is selected stearyl erucicamide and erucicamide, the stearylamide erucicamide trade mark is LutamideS98, consumption is 0.2, the erucicamide trade mark is Lutamide ER, consumption is 0.7 part, is the sky, Sichuan oil chemistry company limited, the glycidyl methacrylate graft ethylene-acrylic acid copolymer, Guangzhou Jinfa Science ﹠ Technology Co. Ltd's self-control, 4 parts of consumptions; Mineral filler is a talcum powder, 3000 orders, the wide talcum powder in osmanthus, Guilin company limited, 20 parts of consumptions; Toughner is POE, trade mark ENGAGE8150, DOW Chemical Industrial Co., Ltd, 10 parts of consumptions; Oxidation inhibitor four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethane, the trade mark is 1010,0.2 part of consumption; Vapour crust fine chemistry Industrial Co., Ltd's tricresyl phosphite (2,4 di-tert-butyl-phenyl) ester, the trade mark is 168, vapour crust fine chemistry Industrial Co., Ltd, 0.2 part of consumption; Weather resisting agent is a hindered amine as light stabilizer, and the trade mark is 744,0.4 part of vapour crust fine chemistry Industrial Co., Ltd; The phthalein mountain valley with clumps of trees and bamboo is green, 0.8 part; By twin screw extruder processing, processing temperature 195-220 ℃.
Aberration Δ E=0.2 after the scuffing.
Embodiment 8
Copolymerization PP, trade mark 7033N, Exxon Mobil chemistry company limited, 78.6 parts of consumptions; The aliphatics primary amide is selected stearyl erucicamide and erucicamide, the stearylamide erucicamide trade mark is Lutamide S98, consumption is 0.2, the erucicamide trade mark is Lutamide ER, consumption is 0.7 part, is the sky, Sichuan oil chemistry company limited, the glycidyl methacrylate graft ethylene-acrylic acid copolymer, Guangzhou Jinfa Science ﹠ Technology Co. Ltd's self-control, 4 parts of consumptions; Mineral filler is a talcum powder, 3000 orders, the wide talcum powder in osmanthus, Guilin company limited, 20 parts of consumptions; Toughner is POE, trade mark ENGAGE8150, DOW Chemical Industrial Co., Ltd, 10 parts of consumptions; Oxidation inhibitor four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethane, the trade mark is 1010,0.2 part of consumption; Vapour crust fine chemistry Industrial Co., Ltd's tricresyl phosphite (2,4 di-tert-butyl-phenyl) ester, the trade mark is 168, vapour crust fine chemistry Industrial Co., Ltd, 0.2 part of consumption; Weather resisting agent is a hindered amine as light stabilizer, and the trade mark is 744,0.4 part of vapour crust fine chemistry Industrial Co., Ltd; The phthalein mountain valley with clumps of trees and bamboo is green, 0.8 part; By twin screw extruder processing, processing temperature 195-220 ℃.
Aberration Δ E=0.15 after the scuffing.
Claims (6)
1. the polypropene composition with scratch resistant performance is characterized in that, is made up of following weight part raw material:
0.5 part-5 parts of 40 parts-100 parts of polypropylene, maleic anhydride or glycidyl methacrylate copolymerization or grafting alpha-olefin copolymers, 0.2 part-2 parts of aliphatics primary amides, mineral filler 0-40 part, toughner 0-20 part, 0.1 part-1 part in oxidation inhibitor, 0.1 part-1 part of weather resisting agent;
Described aliphatics primary amide be stearylamide, erucicamide, mountain Yu acid amides, stearyl erucicamide wherein-kind or multiple mixing;
Described maleic anhydride or glycidyl methacrylate copolymerization or grafting alpha-olefin copolymer are: ethylene-methyl acrylate-copolymer-maleic anhydride, ethylene-propylene acid butyl ester-glycidyl methacrylate copolymer, ethylene-methyl methacrylate glycidyl ester copolymer, maleic anhydride grafted ethene-octene copolymer, maleic anhydride grafted ethene-acetate ethylene copolymer, the glycidyl methacrylate graft ethylene-acrylic acid copolymer-kind or multiple compound;
Described mineral filler is a talcum powder, and its particle diameter is 500 orders-4000 orders.
2. a kind of polypropene composition with scratch resistant performance according to claim 1 is characterized in that described polypropylene is homopolymerization and Co-polypropylene;
3. a kind of polypropene composition with scratch resistant performance according to claim 1 is characterized in that, described toughner is a kind of in amorphous ethylene-alpha-olefin copolymer and the styryl thermoplastic elastomer or their mixture.
4. a kind of polypropene composition according to claim 1 with scratch resistant performance, it is characterized in that, described oxidation inhibitor is Hinered phenols and phosphorous acid esters, be four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] one or both of tetramethylolmethane and tricresyl phosphite (2,4 di-tert-butyl-phenyl) ester are composite.
5. a kind of polypropene composition with scratch resistant performance according to claim 1 is characterized in that, described weather resisting agent is that one or more of hindered amines, ketone and benzotriazole category are composite.
6. a kind of preparation method with polypropene composition of scratch resistant performance according to claim 1 is characterized in that, the steps include:
The first step. take by weighing each raw material by weight;
Second step. place mixing machine to mix 3-8 minute polypropylene, maleic anhydride or glycidyl methacrylate copolymerization or grafting alpha-olefin copolymer, aliphatics primary amide, toughner, oxidation inhibitor and weather resisting agent, obtain mixture;
The 3rd step. the mixture that mineral filler and step 2 are obtained is sent into respectively in twin screw or the reciprocation type list screw extruder with 180-235 ℃ temperature melt blending, extruding pelletization, and screw slenderness ratio is not less than 32.
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| CN2007101717098A CN101173074B (en) | 2007-12-04 | 2007-12-04 | Polypropelene composition with scratch resistant capability and processes for producing same |
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| CN2007101717098A CN101173074B (en) | 2007-12-04 | 2007-12-04 | Polypropelene composition with scratch resistant capability and processes for producing same |
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| CN101173074B true CN101173074B (en) | 2010-07-14 |
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| CN101948586A (en) * | 2010-10-08 | 2011-01-19 | 苏州旭光聚合物有限公司 | Modified polypropylene composite material and preparation method thereof |
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| JP5747561B2 (en) * | 2011-03-02 | 2015-07-15 | 住友化学株式会社 | Propylene resin composition |
| CN102399392A (en) * | 2011-10-20 | 2012-04-04 | 金发科技股份有限公司 | Scratch-resistant polypropylene composition and preparation method thereof |
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| CN108239340B (en) * | 2018-01-08 | 2021-03-23 | 上海金发科技发展有限公司 | Scratch-resistant polypropylene/amine-terminated branched polymer composition and preparation method thereof |
| CN113150436B (en) * | 2021-03-31 | 2022-12-02 | 金发科技股份有限公司 | Polypropylene composition and preparation method thereof |
| CN114736458B (en) * | 2022-04-13 | 2023-10-31 | 金发科技(印度)有限公司 | Scratch-resistant polypropylene composite material and preparation method and application thereof |
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