CN1225498C - Polypropylene resin composition having thermal resistance, high-rigidity and low warpage properties - Google Patents
Polypropylene resin composition having thermal resistance, high-rigidity and low warpage properties Download PDFInfo
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- CN1225498C CN1225498C CN00820094.7A CN00820094A CN1225498C CN 1225498 C CN1225498 C CN 1225498C CN 00820094 A CN00820094 A CN 00820094A CN 1225498 C CN1225498 C CN 1225498C
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- China
- Prior art keywords
- polypropylene
- weight
- polypropylene resin
- resin composite
- mica
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- Expired - Lifetime
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- -1 Polypropylene Polymers 0.000 title claims abstract description 66
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 56
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 56
- 239000011342 resin composition Substances 0.000 title abstract description 9
- 239000010445 mica Substances 0.000 claims abstract description 32
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 32
- 239000003365 glass fiber Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- 239000000805 composite resin Substances 0.000 claims description 21
- 239000012764 mineral filler Substances 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 4
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 2
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 claims description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 229940047670 sodium acrylate Drugs 0.000 claims description 2
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims 1
- 229920001384 propylene homopolymer Polymers 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 abstract description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011256 inorganic filler Substances 0.000 abstract 1
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 20
- 239000004925 Acrylic resin Substances 0.000 description 12
- 229920000178 Acrylic resin Polymers 0.000 description 12
- 239000000945 filler Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 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
- 238000007664 blowing Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004381 surface treatment Methods 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
- 239000012745 toughening agent Substances 0.000 description 2
- JBHRGAHUHVVXQI-UHFFFAOYSA-N 1-triethoxysilylpropan-1-amine Chemical compound CCO[Si](OCC)(OCC)C(N)CC JBHRGAHUHVVXQI-UHFFFAOYSA-N 0.000 description 1
- OPWQHYSPLFFRMU-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-amine Chemical compound CCC(N)[Si](OC)(OC)OC OPWQHYSPLFFRMU-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 101000837805 Homo sapiens Testis-expressed protein 44 Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001282153 Scopelogadus mizolepis Species 0.000 description 1
- 102100028514 Testis-expressed protein 44 Human genes 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910012375 magnesium hydride Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- FNBIAJGPJUOAPB-UHFFFAOYSA-N trimethoxy-[1-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)C(CC)OCC1CO1 FNBIAJGPJUOAPB-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- 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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Abstract
The present invention provides a low-flexibility polypropylene resin composition which comprises a polypropylene resin composition with the following components: 20 to 69 wt% of polypropylene, 1.0 to 30 wt% of modified polypropylene, 30 to 50 wt% of glass fiber and mica and 0.01 to 2.0 wt% of an organic silane composition, wherein the modified polypropylene is modified by grafted unsaturated carboxylic acid or other derivatives, and the glass fiber and the mica are used as inorganic fillers. The low-flexibility polypropylene resin composition of the present invention has excellent heat resistance and rigidity.
Description
Technical field
The present invention relates to a kind of polypropylene resin composite, it has than better rigidity of the acrylic resin of prior art and thermotolerance, and the low warpage properties that further improves, more specifically, the present invention relates to a kind of polypropylene resin composite, it comprises acrylic resin, organic silane compound, the polyacrylic polymer of acid modification and as the mica and the glass fibre of mineral filler.
Background technology
Because acrylic resin demonstrates excellent physical properties, chemical-resistant and mouldability, it is at the automotive interior member, and there is the wide industrial purposes in household electrical appliance and Industrial materials field.But because the chemical structure of its molecule is nonpolar, acrylic resin is at secondary workability, particularly solid-state coating and relatively poor with the adhesivity of other material.And acrylic resin lacks dimensional stability, because its crystalline structure and thermotolerance and rigidity be inferior to other resin, and for example polystyrene and styrene-acrylonitrile copolymer, they are applied to household electrical appliance competitively.Therefore, proposed a kind of method, it is by adding the acrylic resin that mineral filler or other resin exploitation are used for automobile or electronics/electric equipment products parts in acrylic resin.
About these resins, Japanese Laid-Open Patent Application Sho 64-87645 and Sho 1-174550 disclose a kind of resin combination, it is by styrene-butadiene block copolymer and polypropene blended mechanical rigid with improvement, thermotolerance and coating property with styrene polymer and commercial use.Though these compositions have the mechanical property of improvement, be not suitable for as general purpose material, because used relatively costly industrial additive.
The open Hei 3-126740 of Japanese Patent discloses a kind of resin combination, it be by will having the nylon resin of excellent heat resistance, having the polypropylene of the glass fibre of very big influence and sour modification and acrylic resin blend and make improving rigidity and thermotolerance as mineral filler.Above-mentioned composition uses the nylon resin lower than polypropylene viscosity, so the matrix of the resin combination that makes is the nylon resin that can use composition under 150-170 ℃ high temperature.But, although this resin has superior stiffness, coating property, chemical-resistant and thermotolerance, restricted when being used for general purpose, because the cost of nylon resin is higher.
On the other hand, in order to improve rigidity, thermotolerance and other mechanical property are used the mineral filler of following filler as acrylic resin: aciculiform filler such as glass fibre, carbon fiber and palpus crystalline substance, laminal filler such as mica and talcum, or ball filler such as lime carbonate and aluminum oxide.Especially, need to be used to high rigidity and stable on heating product with glass fibre filled acrylic resin.
Glass fibre has great influence to improving mechanical property, because compare such as spherical or flaky mineral filler with other, this fibrous texture has higher long-width ratio.
Usually, along with the increase of the glass fibre amount of in acrylic resin, filling, rigidity and improved heat resistance, but high-orientation makes moulded parts produce very big difference at flow direction with between hanging down as for the contraction rate of mobile direction.This difference causes the warpage of end article, makes it be difficult to use this resin in revolving part that needs high-dimensional stability such as fan, and makes degraded appearance.And, big warpage and deformation can take place in the big scale goods.
For warpage is minimized, and make product have superior stiffness and good surface appearance, can use sheet mica as filler.Because the mica cost is relatively low and have various material color (grey, white, yellow and coffee color), it can be used to not have the electronics or the electric parts of color effectively, and automobile component.But, at tensile yield strength, modulus in flexure, cantilever-type impact strength and thermotolerance aspect, mica is inferior to the needle-like filler, and it has lower filler tap density.Therefore, when production has the composition of high filler content (for example, surpassing 40 weight %), add material and become difficult, reduced productivity and processing characteristics.
Summary of the invention
The objective of the invention is to have excellent rigidity and stable on heating polypropylene resin composite by providing, it can be applicable to trolley part and electronics/electric elements, and, solve the problem of above-mentioned prior art compositions with the glass fibre with low warpage (deformation) property and mica filled.
Polypropylene resin composite of the present invention comprises the organic silane compound of 100 weight part polypropylene-base compositions (after this being called base resin composition) and 0.01-2.0 weight part, described base resin composition contains the polypropylene of 20-69 weight %, 1.0-30 the modified polypropene of weight % with the modification of unsaturated carboxylic acid or derivatives thereof, glass fibre and the mica of the 30-50 weight % of total amount as mineral filler.
Polypropylene in polypropylene resin composite of the present invention is preferably the isotaxy crystaline polypropylene polymer with/10 minutes (ASTM D1238,230 ℃) melt indexs (MI) of 5-70 gram.When melt index was lower than 5 grams/10 minutes the time, productivity reduces, because the plasticity-of member degenerates, and is higher than 70 when restraining/10 minutes when melt index, and shock strength greatly reduces.
Modified polypropene in polypropylene resin composite of the present invention is with the modification of unsaturated carboxylic acid or derivatives thereof.This polyacrylic example has homopolymer polypropylene, ethylene/propene copolymer or propylene/alpha-olefins non-conjugated diene compound copolymer (for example EPDM).Described alpha-olefin can be an ethene, 1-butylene, 1-heptene, 1-hexene, 4-methylpentene, or its mixture.
The unsaturated carboxylic acid that is used for modified polypropene has for example vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, Ba Dousuan, ditraconic acid, Sorbic Acid or phosphorus grica acid.The derivative of unsaturated carboxylic acid can be an acid anhydrides, ester, acid amides, imide or metal-salt, the example has maleic anhydride, itaconic anhydride, the ditraconic acid anhydrides, methyl acrylate, methyl methacrylate, ethyl propenoate, butyl acrylate, toxilic acid monoether/ester, acrylamide, toxilic acid monoamide, N-butyl maleimide, sodium acrylate and sodium methacrylate, its mixture that can be used as independent compound or two or more compounds uses.
A kind of method that is used for modified polypropene is that polypropylene is dissolved in appropriate organic solvent, mixes with unsaturated carboxylic acid or derivatives thereof and radical-forming agent then.Another kind method is by using forcing machine to come the graft copolymerization said components.
The amount that is used as the unsaturated carboxylic acid or derivatives thereof of properties-correcting agent in modified polypropylene resin is preferably 0.1-10 weight %.When this measured less than 0.1 weight %, modified polypropene was very little as the effect of expanding material.When this amount surpasses 10 weight %, by and in the process of production polypropylene resin composite with mica or glass fibre melting mixing, many properties-correcting agent are unreacted in polypropylene, and these unreacted properties-correcting agent distillations and staying in the air, produce stronger smell.In addition, the polypropylene resin composite that obtains is a yellowish brown, and the value of product is descended.
In whole base resin composition, the quantity of modified polypropene is preferably 1.0-30 weight %.When the quantity of modified polypropene was lower than 1.0 weight %, filler and acrylic resin can not be kept surface adhesion intensity, and can not improve the physicals of resin combination.When the quantity of modified polypropene surpasses 30 weight %,, no longer include effect to improving physicals along with the increase of quantity.
Use the mineral filler of glass fibre and mica as polypropylene resin composite of the present invention.Under the situation of glass fibre, its mean diameter can be the 5-15 micron, or is preferably the 9-13 micron, and length is 1-16mm.When the mean diameter of glass fibre during less than 5 microns, it is easy to break in mixing process, so rigidity is weakened.When the mean diameter of glass fibre during greater than 15 microns, can not obtain mechanical rigid, and since the deformation that worsens, degraded appearance.In the present invention, the length of glass fibre is not limited to fixed length, and can use commercially available any glass fibre, but considers the Working environment of hybrid process, preferably uses the filament of length as the chopping of 1-8mm.
The mica of polypropylene resin composite of the present invention is to contain basic metal such as potassium, magnesium, and the silico-aluminate of aluminium or iron, it is usually as filler and toughener.The available mica is white mica (white mica), cat gold (phlogopite), black mica (biotite), yellow soda ash mica, silk Muscovitum, iron mica, vanagine mica etc.Can use commercially available any mica, and its mean diameter is the 10-500 micron, or 50-250 micron more preferably.When mean diameter during, can not obtain required thermotolerance and rigidity, and when mean diameter during greater than 500 microns, mica particles is a visible, makes outward appearance somewhat poor less than 10 microns.
The mineral filler of the appropriate amount in whole base resin composition, promptly glass fibre and micaceous total amount are preferably 30-50 weight %.When this amount is lower than 30 weight %, can not reach required effect fully.When this amount was higher than 50 weight %, composition had been disadvantageous aspect the dispersiveness of resin and outward appearance.The amount of glass fibre in whole mineral filler preferably is no more than 45 weight %.When this content surpasses 45 weight %, the degraded appearance of moulded parts, and Working environment worsens in the process of mixing extruded material.
Preferred glass fibers and micaceous weight ratio are 1: 0.5-8 (glass fibre: mica).When the micaceous ratio is lower than 0.5, can not reaches the effect of the warpage that prevents the goods produced by resin combination, and when this ratio is higher than 8, can not obtain required rigidity, because the amount of glass fibre is relatively low.
The organic silane compound of polypropylene resin composite of the present invention is not limited to specific kind.The example has γ-An Bingjisanyiyangjiguiwan, α-glycidoxy-propyltrimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, Beta-methyl acryloyl-oxy propyl trimethoxy silicane, α-aminopropyl triethoxysilane, N-β-(aminoethyl)-α-oxygen propyl trimethoxy silicane and N-β-(aminoethyl)-α-aminopropyl methyldiethoxysilane.Particularly, in the present invention, the amino silane compounds that contains 1 or 2 amino is preferred.
The appropriate amount that is used to improve the organic silane compound of physical properties is 0.01-2.0 weight part/100 weight part base resin composition, or more preferably 0.05-1.0 weight part.
Various common additives, toughener for example, filler; the thermotolerance stablizer; the weathering resistance stablizer, electrization protection agent, lubricant; slip(ping)agent; nucleating additive, flame-retardant additive, pigment and dyestuff; can add in the polypropylene resin composite of the present invention, as long as additive capacity does not show side effect to resin combination of the present invention.Specific examples has talcum, carbon fiber, lime carbonate, clay, silicon-dioxide, aluminum oxide, carbon black, magnesium hydride, zeolite and barium sulfate.
When producing resin combination of the present invention, preferably use single shaft or biaxial extruder to mix.Usually can use the processing conditions of known production polypropylene resin composite, and each component can be mixed under above-mentioned polyacrylic fusing point.But,, in extrusion, insert glass fibre and mica basically at the same time or separately in order to keep the shape of filler fully.
With reference to embodiment and comparative example the present invention is described in more detail below.But these embodiment just for illustrative purposes, and be not intended to qualification protection scope of the present invention.
Implement best mode of the present invention
The amount of each component in embodiment 1-3 and the physical properties of each composition are shown in Table 1.
The component of using in embodiment 1-3 and among the comparative example 1-4 is as follows:
1) polypropylene: melt index is the homopolymer polypropylene of 10 grams/10 minutes (230 ℃)
2) mineral filler:
-glass fibre: the surface is the fiber that the aminosilane-treated of 3mm is crossed with 11 microns of mean diameters, length
-mica: mean diameter is 250 microns a brown suzorite mica (without surface treatment, mica (1)), and mean diameter is 60 microns a brown suzorite mica (without surface treatment, mica (2))
3) modified polypropene: containing above 0.2 weight % maleic anhydride and melt index is/10 minutes homopolymer polypropylenes of 110 grams.
4) organic silane compound: the amino silane compounds that contains one or 2 amino.
According to the component and the quantity of table 1, in JSW TEX44 ALPHA 2-axle mixing forcing machine, do mixed polypropylene, the polypropylene of modification, organic silane compound and additive with the Hensel mixing machine.And be incorporated into simultaneously in the big hopper.In extrusion, introduce mica and glass fibre by operating weight type feeder, make resin combination.Use Samsung Kloekner FCM-110 (formation capacity: 110 tons) this resin combination of blowing then, produce specimen, measure heat-drawn wire as the ASTM prescribed by standard, cantilever-type impact strength, tensile strength, elongation, modulus in flexure, shrinking percentage and dimensional stability.
The test condition of each sample is as follows:
1) heat-drawn wire
Based on D648, measure down at load (4.6kg).
2) cantilever-type impact strength
Based on D256, measure with the V notched specimen in room temperature
3) tensile strength and elongation
Based on D638, at room temperature measuring
4) modulus in flexure
Based on D790, at room temperature measuring
5) shrinking percentage (warpage/deformation extent)
The thick 2mm of blowing, wide and long all be the thin slice of 100mm, under room temperature and 50% humidity, keep for some time then, be determined at flow direction and perpendicular to the size on the mobile direction.
Table 1
| E1 | E2 | E3 | CE1 | CE2 | CE3 | CE4 | ||
| Polypropylene | 660 | 660 | 560 | 700 | 600 | 600 | 650 | |
| Glass fibre | 100 | 100 | 200 | - | - | - | 300 | |
| Mica (1) | 200 | 200 | 200 | 300 | 400 | - | - | |
| Mica (2) | - | - | - | - | - | 400 | - | |
| Modified polypropene | 40 | 40 | 40 | - | - | - | 50 | |
| Organic silane compound (1) | 0.3 | 0.15 | 0.3 | - | - | - | - | |
| Organic silane compound (2) | 0.1 | 0.05 | 0.1 | - | - | - | - | |
| Organic silane compound (3) | - | 0.1 | - | 0.3 | 0.3 | 0.3 | - | |
| Test result | Heat-drawn wire (℃) | 160 | 162 | 162 | 145 | 146 | 147 | 161 |
| Tensile strength (kgf/cm 2) | 570 | 570 | 730 | 358 | 367 | 366 | 780 | |
| Elongation (%) | ＜10 | ＜10 | ＜10 | ＜10 | ＜10 | ＜10 | ＜10 | |
| Modulus in flexure (kgf/cm 2) | 60,000 | 61,000 | 79,000 | 56,000 | 64,000 | 62,000 | 58,000 | |
| Shock strength (kgf, cm/cm) | 4.7 | 4.7 | 5.8 | 4.1 | 3.3 | 3.2 | 8.1 | |
| Shrinking percentage (MD/TD), 1/000mm | 4.0/6.0 | 4.0/6.0 | 3.0/5.0 | 8.0/9.0 | 7.0/8.0 | 7.0/8.0 | 2.0/7.0 | |
| Dimensional stability (low warpage properties) | ○ | ○ | ○ | ◎ | ◎ | ◎ | × | |
Note:
E: embodiment, CE: comparative example
Organic silane compound (1): α-aminopropyl trimethoxysilane
Organic silane compound (2): Beta-methyl acryloxy propyl trimethoxy silicane
Organic silane compound (3): γ-An Jibingjisanyiyangjiguiwan
(◎: warpage not, zero: warpage a little, *: big warpage, because very big) in the shrinking percentage difference of vertical and horizontal
As can be seen from Table 1, compare with the composition of comparative example 1-3, the composition of embodiment 1-3 has high heat-drawn wire, big tensile strength, flexural strength and shock strength, little shrinking percentage and good dimensional stability.The composition of comparative example 4 aspect dimensional stability inferior to other embodiment.
Polypropylene resin composite according to the present invention's preparation has the favorable mechanical performance, and for example favorable rigidity and thermotolerance also demonstrate low warpage properties and low deformability.Therefore, polypropylene resin composite of the present invention is suitable for rotating member, fan for example, and it causes final moulded parts warpage and requires high-dimensional stability.
Claims (5)
1. polypropylene resin composite, it comprises the polypropylene-base composition of 100 weight parts, the amino silane compounds that contains 1 or 2 amino with the 0.01-2.0 weight part, the melt index in the time of 230 ℃ that described polypropylene-base composition comprises 20-69 weight % is/10 minutes an isotaxy crystalline propylene homopolymer of 5-70 gram, 1.0-30 the modified polypropene with the modification of unsaturated carboxylic acid or derivatives thereof of weight %, the weight ratio as mineral filler of 30-50 weight % is 1: the glass fibre of 1-8 and mica.
2. according to the polypropylene resin composite of claim 1, wherein said modified polypropene is homopolymer polypropylene, ethylene/propene copolymer or the propylene/alpha-olefins non-conjugated diene compound copolymer with the modification of unsaturated carboxylic acid or derivatives thereof.
3. according to the polypropylene resin composite of claim 2, wherein said unsaturated carboxylic acid is to be selected from down two or more that organize: maleic anhydride, itaconic anhydride, the ditraconic acid anhydrides, methyl acrylate, methyl methacrylate, ethyl propenoate, butyl acrylate, the toxilic acid monoesters, acrylamide, toxilic acid monoamide, N-butyl maleimide, sodium acrylate and sodium methacrylate.
4. according to the polypropylene resin composite of claim 2, the amount of wherein adding the described unsaturated carboxylic acid or derivatives thereof in the modified polypropene to is 0.1-10 weight %.
5. according to the polypropylene resin composite of claim 1, the mean diameter of wherein said glass fibre is the 5-15 micron, and length is 1-16mm, and described micaceous mean diameter is the 10-500 micron.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2000/001520 WO2002051930A1 (en) | 2000-12-22 | 2000-12-22 | Polypropylene resin composition having thermal resistance, high rigidity and low warpage properties |
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| CN1479765A CN1479765A (en) | 2004-03-03 |
| CN1225498C true CN1225498C (en) | 2005-11-02 |
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| CN (1) | CN1225498C (en) |
| WO (1) | WO2002051930A1 (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY143758A (en) | 2004-09-13 | 2011-07-15 | Ciba Holding Inc | Polyolefin articles |
| KR100702739B1 (en) * | 2005-09-30 | 2007-04-03 | 엘에스전선 주식회사 | Flame retardant resin composition with improved whitening resistance in bending deformation |
| CN100389149C (en) * | 2005-11-28 | 2008-05-21 | 乌鲁木齐汇源新科技开发有限公司 | Engineering material synthesized by mica |
| CN101374902B (en) * | 2005-12-14 | 2011-05-04 | 住友化学株式会社 | Polyolefin resin composition, molded product thereof and preparation of polyolefin resin composition |
| EP2371897B1 (en) * | 2008-12-25 | 2014-04-09 | Toray Industries, Inc. | Fiber-reinforced propylene resin composition |
| CN101608067B (en) * | 2009-07-06 | 2011-04-20 | 惠州市沃特新材料有限公司 | Conductive engineering plastics and preparation method thereof |
| CN101942147A (en) * | 2010-03-31 | 2011-01-12 | 深圳市科聚新材料有限公司 | Hardened transparent polypropylene material for fan blades and preparation method thereof |
| CN102329454B (en) * | 2011-10-18 | 2013-10-16 | 深圳市科聚新材料有限公司 | Polypropylene composite material as well as preparation method and application thereof |
| JP6309509B2 (en) * | 2012-05-22 | 2018-04-11 | ボルージュ コンパウンディング シャンハイ カンパニー リミテッド | Low warpage molded article |
| KR101465902B1 (en) * | 2012-12-24 | 2014-11-26 | 주식회사 엘지화학 | Encapsulant film |
| CN105440439A (en) * | 2015-12-11 | 2016-03-30 | 天津金发新材料有限公司 | Low-smell and high-rigidity mica powder filled polypropylene material and preparation method thereof |
| ZA201705821B (en) * | 2016-08-26 | 2021-07-28 | Csir | Isotatic polypropylene based composite |
| JP2018048229A (en) * | 2016-09-20 | 2018-03-29 | 株式会社Ｔｂｍ | Sheet and packaging container |
| CN110914360B (en) * | 2017-07-13 | 2021-10-29 | 博禄塑料（上海）有限公司 | Low odor glass fiber reinforced composition |
| CN109206740A (en) * | 2018-08-03 | 2019-01-15 | 江苏兆维塑料科技有限公司 | Low warpage flame-proof reinforced polypropylene material of a kind of uvioresistant and preparation method thereof |
| CN110483889B (en) * | 2019-08-16 | 2021-10-29 | 上海交通大学 | Rotational molding polypropylene alloy material and preparation method thereof |
| KR102231991B1 (en) * | 2019-10-30 | 2021-03-25 | 주식회사 서연이화 | Polypropylene resin composition for Tail gate inner panel, and molded articles thereof |
| CN111978631B (en) * | 2020-07-27 | 2022-06-21 | 青岛中新华美塑料有限公司 | Polypropylene warm edge spacing strip and preparation method thereof |
| CN114456498B (en) * | 2020-10-22 | 2023-04-14 | 中国石油化工股份有限公司 | High-rigidity wear-resistant polypropylene composition and preparation method thereof |
| WO2022120648A1 (en) * | 2020-12-09 | 2022-06-16 | Borouge Compounding Shanghai Co., Ltd. | Glass fiber-filled polyolefin compositions with low shrinkage and warpage |
| CN114213748A (en) * | 2021-11-16 | 2022-03-22 | 上海金发科技发展有限公司 | Mica filled polypropylene composite material and preparation method and application thereof |
| CN114921104B (en) * | 2022-07-06 | 2023-10-20 | 广东圆融新材料有限公司 | Polypropylene composite material and preparation method thereof |
| CN115340726A (en) * | 2022-09-16 | 2022-11-15 | 苏州保莱成医疗包装有限公司 | Medical plastic uptake box modified plastic and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5817545B2 (en) * | 1979-02-07 | 1983-04-07 | 宇部興産株式会社 | Method for producing mica-reinforced polypropylene composition |
| JPS5842639A (en) * | 1981-09-07 | 1983-03-12 | Toa Nenryo Kogyo Kk | Polyolefin composition |
| JPS58206659A (en) * | 1982-05-26 | 1983-12-01 | Ube Ind Ltd | Reinforced polypropylene composition |
| JPS58217532A (en) * | 1982-06-11 | 1983-12-17 | Unitika Ltd | Production of glass fiber-reinforced polyolefin |
| JPS6257428A (en) * | 1985-09-06 | 1987-03-13 | Ube Ind Ltd | Glass-fiber reinforced composite meterial |
-
2000
- 2000-12-22 CN CN00820094.7A patent/CN1225498C/en not_active Expired - Lifetime
- 2000-12-22 WO PCT/KR2000/001520 patent/WO2002051930A1/en active Search and Examination
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| CN1479765A (en) | 2004-03-03 |
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