CN104558818B - Polypropene composition of dimensionally stable and preparation method thereof - Google Patents
Polypropene composition of dimensionally stable and preparation method thereof Download PDFInfo
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- CN104558818B CN104558818B CN201310482803.0A CN201310482803A CN104558818B CN 104558818 B CN104558818 B CN 104558818B CN 201310482803 A CN201310482803 A CN 201310482803A CN 104558818 B CN104558818 B CN 104558818B
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- resins
- magnesium sulfate
- crystal whisker
- sulfate crystal
- alkali magnesium
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 82
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 75
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 90
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 52
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 45
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 44
- 239000003513 alkali Substances 0.000 claims abstract description 41
- 239000013078 crystal Substances 0.000 claims abstract description 37
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000077 silane Inorganic materials 0.000 claims abstract description 6
- -1 compatilizer Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- 238000007334 copolymerization reaction Methods 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 8
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 8
- 239000004611 light stabiliser Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 5
- 235000005979 Citrus limon Nutrition 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 238000004040 coloring Methods 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000001994 activation Methods 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 244000248349 Citrus limon Species 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 27
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 4
- 238000005453 pelletization Methods 0.000 abstract description 3
- 238000009775 high-speed stirring Methods 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 description 11
- 239000012745 toughening agent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- 239000000945 filler Substances 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 239000012764 mineral filler Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 244000131522 Citrus pyriformis Species 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 101100205892 Caenorhabditis elegans taf-2 gene Proteins 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical group C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LDGZSKOAALVKLH-UHFFFAOYSA-N ethene octadecanoic acid Chemical compound C=C.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O LDGZSKOAALVKLH-UHFFFAOYSA-N 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 210000003195 fascia Anatomy 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Landscapes
- 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
The invention belongs to polymeric material field, it is related to a kind of polypropene composition of dimensionally stable and preparation method thereof, is made up of following raw materials, the parts by weight of each component is：PP resins：100；MLLDPE resins：28~50；Compatilizer：2~9；Alkali magnesium sulfate crystal whisker：25~43；Lubricant：1~2.5；Antioxidant：1~1.5；Other auxiliary agents：1~3.Preparation process be by alkali magnesium sulfate crystal whisker drying, then will dry alkali magnesium sulfate crystal whisker and silane coupler mixed at high speed stirring；Mixture is mixed to obtain to leftover materials are put into blend；Mixture is placed in extruder, extruding pelletization, dry prepared product.Product of the present invention not only has excellent in dimension stability and heat resistance, while said composition also has excellent rigidity-toughness balanced performance and processing fluidity higher, can be used as the raw materials for production of the large-sized inside gadget PP materials of automobile.
Description
Technical field
The present invention relates to a kind of polypropene composition of dimensionally stable and preparation method thereof, belong to polymeric material field.
Background technology
Demand for development and environmental requirement with automotive engineering, to safety of the working of plastics including automotive upholstery, energy-conservation, relax
Suitable, practical, clean and tidy, attractive in appearance etc. require also increasingly to improve.The conventional plastic resin of automotive upholstery is polypropylene (PP), but general
It is big to there is shrinkage factor in PP materials, poor impact resistance, the shortcomings of loss of properties on aging, it is impossible to meet the application requirement of inside gadget, and
Automobile large scale inside gadget then requires that material will have more preferable heat resistance, warpage-resistant including instrument board, door side guard plate etc.
And rigidity-toughness balanced performance, it is therefore necessary to being modified to apply.
Current automotive upholstery（Including large scale inside gadget）It is exactly in PP materials with the general method of modifying of PP materials
The modifying agent such as a certain amount of toughener, filler are added, filled toughening effect is played, the combination property of material is improved.Toughener
It is general to use rubber, SIS/SEBS (SEBS), ethylene-propylene-octene terpolymer
(POE), ethylene-vinyl acetate copolymer（EVA）, can additionally add LLDPE（LLDPE）, high-density polyethylene
Alkene（HDPE）Further improve the toughness of material.Although such toughener can significantly improve the impact toughness and lower temperature resistance of PP,
But the cost of raw material is high, or intensity and poor rigidity, or fusing point and heat distortion temperature it is low.Filler is generally heat-resisting, high rigidity high
Inorganic fillers, the general inorganic filler system of current automotive upholstery mainly has two classes：Common scaly talc powder and
Spherical calcium carbonate, its aspect ratio is relatively low, and another kind of is the filler with high aspect ratio, such as：Bamboo fibre, carbon fiber and glass fibre
Deng material.Talcum powder, talcum grain, calcium carbonate material under certain content dimensional stability it is not high, bamboo fibre is used as filler
Its technology is also immature, and carbon fiber cost is high, and glass fibre can be used as reinforcing agent, significantly improve the rigidity of material, also be had
There is an excellent heat resistance and dimensional stability, but the flatness on surface, aesthetic property are poor, the easy buckling deformation of large scale inside gadget,
Some automotive upholstery application fields are limited by automobile industry.
The inside gadgets such as fascia, door side guard plate are big due to surface size, it is easier to which warpage and thermal deformation occur, therefore
It is required that the raw material for being used are except that will have certain rigidity and impact property, the heat resistance that also had, resistance to warpage become
Shape performance.Simultaneously because volume is big, complex-shaped, flow length is long, also require that material has good mobility.Tables 1 and 2
It is the performance requirement of the large-sized inside gadget PP materials of partial domestic automobile and Volkswagen.
Domestic automobile large scale inside gadget PP raw material requirement in the part of table 1
The PP raw material requirement of the Volkswagen's large scale inside gadget of table 2（TL52388 standards）
Chinese patent CN101948586A discloses a kind of modified polypropene composite wood suitable for manufacturing automotive upholstery
Material, including：Polypropylene, elastomer, mineral filler and auxiliary agent, according to weight portion, the weight portion of above-mentioned composition is respectively：Polypropylene
70~90；Elastomer 5~10；Mineral filler 5~20；Auxiliary agent 0.1~1；Wherein, the weight of polypropylene, elastomer and mineral filler
Amount part sum is 100 parts.The composite uses fine mineral filler, without by being surface-treated, although employ few
The maleic anhydride inoculated polypropylene of amount is compatilizer, but filler grain also easily assembles conglomeration in high concentration, thus compatibility and
Dispersiveness cannot be guaranteed, and product quality stability is poor, and the composite of such filler has poor dimensional stability, vertically and horizontally
The shortcomings of shrinkage factor differs greatly, in addition the MFR of the composite can not meet part inside gadget PP materials and mobility is wanted
Ask.
Chinese patent CN1560124 discloses a kind of acrylic resin composite, the polypropylene containing 30-90 weight %
Resin, the microballon of 5-70 weight %, the inorganic micron of 0-50 weight % or nano-particle, 0-50 weight % microfibres.The composite
Rigidity/toughness is balanced, product surface is excellent and case hardness is higher, be difficult scuffing, but a certain amount of due to containing in composition
Elastic body toughening agent, causes the heat distortion temperature of product low.
Chinese patent CN1065554C then discloses a kind of thermoplastic resin composition of automobile instrument disk material, mainly into
Part comprising specific crystalline polypropylene resin, magnesium sulfate and talcum powder mineral filler, the random copolymer rubber of Ethylene/Butylene -1 and
The toughener of ethylene-propylene random copolymer rubber, said composition has toughness and rigidity required by instrument disk material and good
Good surface quality and in short production cycle, but composition also due to contain a certain amount of rubber toughening agent, cause product
Heat distortion temperature it is low.
Chinese patent CN102952342A discloses a kind of Low-shrinkage polypropylene composition, mainly with two kinds of crushing-resistant copolymerizations
Resin based on polypropylene, is increased by adding the inorganic particles such as talcum powder, metallocene linear-low density polyethylene, EPDM or POE
Tough dose and weather-proof auxiliary agent, extruded granulation are obtained with relatively low shrinkage factor, low cost, excellent rigidity-toughness balanced performance and higher
Luster performance modified poly propylene composition.Although the shrinkage factor of product is relatively low, but still the space being improved, and due to using
The inorganic particles such as talcum powder make filler, and the rigidity of product is relatively low, it is impossible to meet the firm of the large-sized inside gadget of automobile
Property require.
The content of the invention
The purpose of the present invention is directed to above-mentioned the deficiencies in the prior art, there is provided a kind of polypropene composition of dimensionally stable and
Its preparation method, said composition not only has excellent in dimension stability and heat resistance, at the same said composition also have it is excellent firm
Tough balance quality and processing fluidity higher, as automobile large-sized inside gadget raw materials for production of PP materials.
The polypropene composition of dimensionally stable of the present invention, is made up of following raw materials, the parts by weight of each component
For：
PP resins：100；MLLDPE resins：28~50；Compatilizer：2~9；Alkali magnesium sulfate crystal whisker：25~43；Lubrication
Agent：1~2.5；Antioxidant：1~1.5；Other auxiliary agents：1~3.
Wherein, the present invention has the characteristic of high aspect ratio using alkali magnesium sulfate crystal whisker, greatly improves the intensity, just of material
Property and dimensional stability, while keep product still have good surface smoothness and aesthetic property.
PP resins are one or more of copolymerization or homopolymerization PP resin, its melt mass flow rate (MFR)（2.16Kg weights
Code）It is 1.5~30.0g/10min；Copolymerization PP resins are the copolymer of ethene and propylene, wherein, the mass content of ethene for 6~
14%。
The mLLDPE resins for using are a kind of metallocene linear-low density polyethylene of melt mass flow rate high, its
MFR（2.16Kg counterweights）It is 20.0~50.0g/10min.This material coordinates a small amount of compatilizer to replace conventional bullet as toughener
Gonosome, cheap, its fusing point and heat distortion temperature are high, good fluidity, and with certain intensity and toughness, crystallinity is low,
The shrinkage factor of PP resins can also be improved, conventional toughener is solved to asking that the next heat resistance of material strips and processing fluidity are reduced
Topic.Its consumption is preferably 30~42 parts.
Compatilizer is maleic anhydride modified SIS/SEBS (SEBS-g-MAH), benzene
Ethylene contents are 13~33%, and maleic anhydride connects skill rate for 0.5~2.5%, compatilizer can not only be greatly improved PP resins,
Compatibility between mLLDPE, alkali magnesium sulfate crystal whisker three, also further improves the tough of material as a kind of auxiliary toughener
Property, its consumption is preferably 2~8 parts.
Wherein, SIS/SEBS（SEBS-g-MAH）It is preferred that FG1901G or FG1924G,
Wherein, the ethylene contents 13% of FG1924G, connect skill rate 0.8%；The styrene-content 30% of FG1901G, connects skill rate 1.6%.
The manufacturer of FG1901G, FG1924G is Kraton Polymer companies of the U.S..
Alkali magnesium sulfate crystal whisker surface treated agent activation process, is a kind of filler, consisting of MgSO4·5Mg
(OH)2·3H2O, with the excellent firm reinforcement of increasing and fire retardation, its product surface is also more smooth.Alkali magnesium sulfate crystal whisker it is straight
Footpath is 0.5~1 μm, and draw ratio is 100~200, and consumption is 30~40 parts.
Wherein, surface conditioning agent is silane coupler, and addition is the 0.5~2% of alkali magnesium sulfate crystal whisker weight.
Lubricant is stearic acid, calcium stearate, zinc stearate, barium stearate or ethylene bis stearic acid amide（EBS）One
Plant or various.
Antioxidant is compounded for Hinered phenols antioxidant 1010 with phosphite ester kind antioxidant 168, and mass ratio is 1：1~2：1.
Silane coupler is KH550, and manufacturer is Nanjing dawn chemical plant.
Other auxiliary agents are the one kind or many in light stabilizer, brightener, colouring agent or cumyl peroxide (DCP) auxiliary agent
Kind.
Light stabilizer is one kind or UV- of benzophenone light stabilizer UV-531 and hindered amine as light stabilizer UV-770
531 and UV-770 presses 0.5：1~1：0.5 mass compares mixture.
Brightener is the one kind in BAB type copolymers TAS-2, TAS-2A or TAF of a low-molecular-weight.TAS-2、TAS-2A
It is photochemistry auxiliary agent Co., Ltd of Wuxian state with the manufacturer of TAF.
Colouring agent is the one kind in carbon black, iron oxide red, lemon yellow or titanium table basket.
The present invention uses parallel dual-screw extruding machine extruding pelletization, and preparation process is as follows：
（1）First by alkali magnesium sulfate crystal whisker through 60-80 DEG C of drying, then the alkali magnesium sulfate crystal whisker and silane idol that will be dried
Join agent in mixing 15-20 minutes, wherein, mixing speed is 800-2000 revs/min；
（2）To step（1）Blend in put into PP resins, mLLDPE resins, compatilizer, lubricant, antioxidant and its
Its auxiliary agent, mixes 5-8 minutes, and mixing speed is 200-600 revs/min；
（3）By step（2）Mixture granulated in melting extrusion at 180-210 DEG C, 60-80 DEG C dries 20-40 minutes system
Obtain product.
Wherein, step（1）Middle mixing time preferably 15 minutes, preferably 1000 revs/min of mixing speed.
Step（2）Middle mixing time preferably 5 minutes, preferably 500 revs/min of mixing speed.
Polypropene composition of the invention is applicable to the large-sized inside gadget of lot of domestic and foreign automobile such as instrument board, door side
The raw materials for production of the working of plastics such as backplate.
Compared with prior art, the invention has the advantages that：
（1）Preparation method process is simple of the present invention, it is with low cost；（2）Raw material used are completely environmentally friendly, the interior trim of production
Part free from extraneous odour, surface smooth；（3）Not only parallel shrinkage factor and vertical shrinkage rate are small for polypropene composition, with good size
Stability and resistance to warpage performance, and with heat distortion temperature（0.45MPa）It is high（≥120℃）, heat resistance is good；（4）Poly- third
Ene compositions also have rational processing fluidity, rigidity and toughness simultaneously, adapt to the requirement of large scale interior trim working of plastics.
Brief description of the drawings
Fig. 1 is the preparation flow figure of polypropene composition of the present invention.
Specific embodiment
With reference to embodiment, the present invention is described further.
Embodiment 1
Raw material and its parts by weight used by the present embodiment are：
Copolymerization PP resins：100；
mLLDPE：50；
FG1924G：：6；
Alkali magnesium sulfate crystal whisker：40；
Stearic acid：0.5；
Zinc stearate：1.5；
Antioxidant 1010/168：0.5/0.5；
UV-531：0.8；
Carbon black：0.2.
Wherein, the MFR=26.5g/10min of copolymerization PP resins, ethylene contents 12%；The MFR=20g/10min of mLLDPE；Alkali
0.7 μm of the footpath of formula magnesium sulfate crystal whisker, draw ratio 150.
Preparation process is as follows：
（1）First by alkali magnesium sulfate crystal whisker through 80 DEG C of drying, then the alkali magnesium sulfate crystal whisker and quality that will be dried are alkali
The KH550 of the 0.5% of formula magnesium sulfate weight is mixed 20 minutes in high speed agitator high speed, wherein, mixing speed is 800
Rev/min；
（2）To step（1）Blend in put into PP resins, mLLDPE resins, compatilizer, lubricant, antioxidant and its
Its auxiliary agent, mixes 5 minutes, and mixing speed is 600 revs/min；
（3）By step（2）Mixture be placed in parallel dual-screw extruding machine, granulated in melting extrusion at 180-210 DEG C,
60 DEG C of dryings, 40 minutes prepared products.
Embodiment 2
Raw material and its parts by weight used by the present embodiment are：
Copolymerization PP resins：67；
Homopolymerization PP resin：33；
mLLDPE：34；
FG1924G：2.0；
Alkali magnesium sulfate crystal whisker：25；
EBS：2.5；
Antioxidant 1010/168：0.8/0.4；
UV-770：0.6；
Lemon yellow：0.15；
TAF brighteners：1.2.
Wherein, the MFR=9.1g/10min of copolymerization PP resins, ethylene contents 10%；The MFR=3.0g/ of homopolymerization PP resin
10min；The MFR=30g/10min of mLLDPE；0.5 μm of the footpath of alkali magnesium sulfate crystal whisker, draw ratio 200.
Preparation process is as follows：
（1）First by alkali magnesium sulfate crystal whisker through 60 DEG C of drying, then the alkali magnesium sulfate crystal whisker and quality that will be dried are alkali
The 1%KH550 of formula magnesium sulfate weight high speed agitator high speed mix 20 minutes, wherein, mixing speed be 1000 turns/
Minute；
（2）To step（1）Blend in put into PP resins, mLLDPE resins, compatilizer, lubricant, antioxidant and its
Its auxiliary agent, mixes 6 minutes, and mixing speed is 500 revs/min；
（3）By step（2）Mixture be placed in parallel dual-screw extruding machine, granulated in melting extrusion at 180-210 DEG C,
75 DEG C of dryings, 30 minutes prepared products.
Embodiment 3：
Raw material and its parts by weight used by the present embodiment are：
Copolymerization PP resins 1：71；
Copolymerization PP resins 2：29；
mLLDPE：28；
FG1901G：9；
Alkali magnesium sulfate crystal whisker：43；
Calcium stearate：0.6；
Barium stearate：0.2
Stearic acid：0.2
Antioxidant 1010/168：0.8/0.4；
UV-531：0.5；
UV-770：0.5；
Titanium table is blue：0.2；
TAS-2A：1.0；
DCP：0.8.
Wherein, the MFR=26.5g/10min of copolymerization PP resins, ethylene contents 12%；The MFR=1.5g/ of copolymerization PP resins
10min, ethylene contents 8%；The MFR=50g/10min of mLLDPE；1.0 μm of the footpath of alkali magnesium sulfate crystal whisker, draw ratio 100.
Preparation process is as follows：
（1）First by alkali magnesium sulfate crystal whisker through 70 DEG C of drying, then the alkali magnesium sulfate crystal whisker and quality that will be dried are alkali
The 2%KH550 of formula magnesium sulfate weight high speed agitator high speed mix 18 minutes, wherein, mixing speed be 1500 turns/
Minute；
（2）To step（1）Blend in put into PP resins, mLLDPE resins, compatilizer, lubricant, antioxidant and its
Its auxiliary agent, mixes 8 minutes, and mixing speed is 200 revs/min；
（3）By step（2）Mixture be placed in parallel dual-screw extruding machine, granulated in melting extrusion at 180-210 DEG C,
80 DEG C of dryings, 30 minutes prepared products.
Embodiment 4
Raw material and its parts by weight used by the present embodiment are：
Copolymerization PP resins：64；
Copolymerization PP resins：36；
mLLDPE：42；
FG1924G：9；
Alkali magnesium sulfate crystal whisker：27；
Zinc stearate：1.0；
Antioxidant 1010/168：1.0/0.5；
UV-531：0.3；
UV-770：0.6；
Lemon yellow：0.18.
Wherein, the MFR=9.0g/10min of copolymerization PP resins, ethylene contents 12%；The MFR=11g/ of copolymerization PP resins
10min, ethylene contents 6.5%；The MFR=30g/10min of mLLDPE；0.8 μm of the footpath of alkali magnesium sulfate crystal whisker, draw ratio 120.
Preparation process is as follows：
（1）First by alkali magnesium sulfate crystal whisker through 80 DEG C of drying, then the alkali magnesium sulfate crystal whisker and quality that will be dried are alkali
The 1.5%KH550 of formula magnesium sulfate weight is mixed 15 minutes in high speed agitator high speed, wherein, mixing speed is 2000
Rev/min；
（2）To step（1）Blend in put into PP resins, mLLDPE resins, compatilizer, lubricant, antioxidant and its
Its auxiliary agent, mixes 5 minutes, and mixing speed is 500 revs/min；
（3）By step（2）Mixture be placed in parallel dual-screw extruding machine, granulated in melting extrusion at 180-210 DEG C,
70 DEG C of dryings, 35 minutes prepared products.
Embodiment 5
Raw material and its parts by weight used by the present embodiment are：
Copolymerization PP resins：63；
Copolymerization PP resins：37；
mLLDPE：31；
FG1901G：5.5；
MOS：42；
EBS：0.5；
Barium stearate：1.0；
Antioxidant 1010/168：0.6/0.4；
UV-531：0.8；
UV-770：0.4；
Carbon black：0.2；
TAF-2 brighteners：0.9；
DCP：0.5.
Wherein, the MFR=1.5g/10min of copolymerization PP resins, ethylene contents 8%；The MFR=3.0g/ of copolymerization PP resins
10min, ethylene contents 6.5%；The MFR=50g/10min of mLLDPE；0.7 μm of the footpath of alkali magnesium sulfate crystal whisker, draw ratio 150.
Preparation process is as follows：
（1）First by alkali magnesium sulfate crystal whisker through 65 DEG C of drying, then the alkali magnesium sulfate crystal whisker and quality that will be dried are alkali
The 1.5%KH550 of formula magnesium sulfate weight is mixed 15 minutes in high speed agitator high speed, wherein, mixing speed is 1000
Rev/min；
（2）To step（1）Blend in put into PP resins, mLLDPE resins, compatilizer, lubricant, antioxidant and its
Its auxiliary agent, mixes 7 minutes, and mixing speed is 350 revs/min；
（3）By step（2）Mixture be placed in parallel dual-screw extruding machine, granulated in melting extrusion at 180-210 DEG C,
80 DEG C of dryings, 20 minutes prepared products.
Comparative example 1
The component and content of this comparative example（Parts by weight）As follows, performance disclosed in the material being made its patent is shown in Table 4.
Polypropylene：125；
Polypropylene 3：22；
ENGAGE8200：8；
Glass microballoon：15
Talcum powder 3000：13；
Barium sulfate：2；
Magnesium sulfate crystal whisker：10；
Coupling agent KH560：0.5；
Antioxidant 1010/168：0.1/0.1；
CAST：0.1；
Toner：1.
Preparation method is same as Example 1.
Comparative example 2
Chinese patent 96100262.X discloses a kind of thermoplastic resin composition of automobile instrument disk material, with patent
Embodiment 1 be comparative example：
Main raw material(s) matches somebody with somebody when preparation method：By 68%（Percentage by weight）Crystalline propylene-ethylene block copolymer
（BC-1）、3%（Percentage by weight）The copolymer rubber of Ethylene/Butylene -1（EBR）、3%（Percentage by weight）Ethylene-propylene copolymer type
Rubber（EPR）、13%（Percentage by weight）It is 0.5-1 μm of threadiness that average fiber length is 10-30 μm and avarage fiber diameter
Oxygen-containing magnesium sulfate（WH）With 13%（Percentage by weight）Average grain diameter is 2 μm of talcum（TAIC）Mix with various stabilizers, its
Afterwards, gained mixture is mediated in predefined conditions, then injection turns into testpieces, and performance disclosed in patent is shown in Table 4.
Comparative example 3
A kind of Low-shrinkage polypropylene composition and preparation method disclosed in Chinese patent 201110252092.9, to implement
Example 8 is comparative example, its composition and ratio（Weight portion meter）And preparation method sees below：
Impact polypropylene resin (QP81N)：55；
Impact polypropylene resin (SP179)：13；
Calcium carbonate：20；
mLLDPE(mPE-200904)：10；
Toughener Engage8402：2；
Ultra-violet absorber (TINUV571)：0.1.
Each composition is placed in homogenizer, 4 ± 1min is stirred under the rotating speed of 1450 ± 30r/min, mixing is equal
It is even；Then the premix that will be obtained is added to melting mixing in parallel dual-screw extruding machine, and extruder highest section temperature is 220 ±
10 DEG C, extruder 180 ± 10r/min of engine speed, feeding 40 ± 5r/min of rotating speed, extruding pelletization is obtained with low-shrinkage
Modified poly propylene composition, performance disclosed in composition patent is shown in Table 4.
Embodiment 1-5 polypropene composition the performance test results, such as table 3.
The polypropene composition embodiment the performance test results of table 3
Performance disclosed in the comparative example patent of table 4
Contrasted by embodiment test result and comparative example test result, the compound in comparative example in performance all
There is a respective defect, or heat distortion temperature is low, or rigidity is not enough, or shrinkage factor is although relatively low, but intensity and bending die
Amount it is relatively low, and polypropene composition of the present invention not only parallel shrinkage factor, vertical shrinkage rate are low, difference is small in both direction, and
And heat distortion temperature is high, high comprehensive performance meets requirement of most large scale inside gadgets with PP materials to technology traditional performance
（1 is shown in Table with table 2）.
Claims (5)
1. a kind of polypropene composition of dimensionally stable, it is characterised in that be made up of following raw materials, the parts by weight of each component
For：
PP resins 100；
MLLDPE resins 28~50；
Compatilizer 2~9；
Alkali magnesium sulfate crystal whisker 25~43；
Lubricant 1~2.5；
Antioxidant 1~1.5；
Other auxiliary agents 1~3；
Alkali magnesium sulfate crystal whisker surface treated agent activation process, a diameter of 0.5~1 μm of alkali magnesium sulfate crystal whisker, draw ratio
It is 100~200；
Compatilizer is maleic anhydride modified SIS/SEBS, styrene-content is 13~
33%；
Surface conditioning agent is silane coupler, and addition is the 0.5~2% of alkali magnesium sulfate crystal whisker weight；
Other auxiliary agents are one or more in light stabilizer, brightener, colouring agent or cumyl peroxide auxiliary agent；
Antioxidant is compounded for Hinered phenols antioxidant 1010 with phosphite ester kind antioxidant 168, and mass ratio is 1：1~2：1.
2. the polypropene composition of dimensionally stable according to claim 1, it is characterised in that PP resins are copolymerization or homopolymerization
One or more of PP resins, its melt mass flow rate is 1.5~30.0g/10min；Copolymerization PP resins are ethene and third
The copolymer of alkene, wherein, the mass content of ethene is 6~14%.
3. the polypropene composition of dimensionally stable according to claim 1, it is characterised in that lubricant is stearic acid, hard
One or more in resin acid calcium, zinc stearate, barium stearate or ethylene bis stearic acid amide.
4. the polypropene composition of dimensionally stable according to claim 1, it is characterised in that light stabilizer is benzophenone
One kind or UV-531 and UV-770 of class light stabilizer UV-531 and hindered amine as light stabilizer UV-770 presses 0.5：1~1：0.5 matter
Amount compares mixture；Brightener is the one kind in BAB type copolymers TAS-2, TAS-2A or TAF of low-molecular-weight；Colouring agent be carbon black,
One kind in iron oxide red, lemon yellow or titanium table basket.
5. the preparation method of the polypropene composition of the dimensionally stable described in a kind of claim 1, it is characterised in that including following
Step：
（1）First by alkali magnesium sulfate crystal whisker through 60-80 DEG C of drying, then the alkali magnesium sulfate crystal whisker and silane coupler that will be dried
In mixing 15-20 minutes, wherein, mixing speed is 800-2000 revs/min；
（2）To step（1）Blend in put into PP resins, mLLDPE resins, compatilizer, lubricant, antioxidant and other help
Agent, mixes 5-8 minutes, and mixing speed is 200-600 revs/min；
（3）By step（2）Mixture granulated in melting extrusion at 180-210 DEG C, 60-80 DEG C dry 20-40 minutes be obtained produce
Product.
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| CN105504529A (en) * | 2015-12-30 | 2016-04-20 | 上海普利特复合材料股份有限公司 | Special polypropylene composite material for bumpers and preparation method thereof |
| CN108329580A (en) * | 2017-01-20 | 2018-07-27 | 合肥杰事杰新材料股份有限公司 | A kind of antibacterial polypropylene material and preparation method thereof |
| CN115298256B (en) * | 2020-03-30 | 2024-01-23 | 宇部材料工业株式会社 | Polypropylene resin composition, method for producing polypropylene resin composition, and molded article |
| CN113845696B (en) * | 2021-04-27 | 2022-12-09 | 朴蓝聚烯烃科技发展（上海）有限公司 | Rigidity-enhancing toughening anti-warping polymer composite additive and polymer composition |
| CN114479290B (en) * | 2022-02-25 | 2023-09-08 | 国高材高分子材料产业创新中心有限公司 | PP-based food contact total migration standard sample and preparation method thereof |
| CN115785566B (en) * | 2022-12-22 | 2024-04-02 | 杭州聚丰新材料有限公司 | Low-shrinkage PP material for 3D printing and preparation method and application thereof |
| CN118344673A (en) * | 2024-05-13 | 2024-07-16 | 广汽本田汽车有限公司 | A polypropylene composite material and its preparation method and application |
| CN119192705A (en) * | 2024-09-02 | 2024-12-27 | 埃克森美孚(惠州)化工有限公司 | Polyolefin composition and use thereof |
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| CN102391575A (en) * | 2011-09-23 | 2012-03-28 | 中国石油化工股份有限公司 | Polypropylene (PP) alloy material with low molding shrinkage and preparation method thereof |
| CN102952336A (en) * | 2012-11-15 | 2013-03-06 | 合肥会通新材料有限公司 | Active basic magnesium sulfate whisker modified polypropylene composite material and preparation method thereof |
| CN103087412A (en) * | 2013-01-18 | 2013-05-08 | 江门市奇德工程塑料科技有限公司 | High-flowability glass fiber reinforced polypropylene composite material and preparation method thereof |
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| CN102391575A (en) * | 2011-09-23 | 2012-03-28 | 中国石油化工股份有限公司 | Polypropylene (PP) alloy material with low molding shrinkage and preparation method thereof |
| CN102952336A (en) * | 2012-11-15 | 2013-03-06 | 合肥会通新材料有限公司 | Active basic magnesium sulfate whisker modified polypropylene composite material and preparation method thereof |
| CN103087412A (en) * | 2013-01-18 | 2013-05-08 | 江门市奇德工程塑料科技有限公司 | High-flowability glass fiber reinforced polypropylene composite material and preparation method thereof |
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