CN1215068A - Stuffing mother particle for toughening polyolefine and preparation process and usage thereof - Google Patents
Stuffing mother particle for toughening polyolefine and preparation process and usage thereof Download PDFInfo
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- CN1215068A CN1215068A CN 98102448 CN98102448A CN1215068A CN 1215068 A CN1215068 A CN 1215068A CN 98102448 CN98102448 CN 98102448 CN 98102448 A CN98102448 A CN 98102448A CN 1215068 A CN1215068 A CN 1215068A
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- Prior art keywords
- stuffing
- mother particle
- polyolefine
- toughening
- filler
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 38
- 239000002245 particle Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000008187 granular material Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000011049 filling Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims description 37
- -1 stearoyl titanic acid ester Chemical class 0.000 claims description 31
- 239000004743 Polypropylene Substances 0.000 claims description 24
- 229920001155 polypropylene Polymers 0.000 claims description 24
- 239000012764 mineral filler Substances 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 16
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical group O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 15
- 229920001903 high density polyethylene Polymers 0.000 claims description 13
- 239000004700 high-density polyethylene Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000012756 surface treatment agent Substances 0.000 claims description 10
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 9
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 6
- 235000013539 calcium stearate Nutrition 0.000 claims description 6
- 239000008116 calcium stearate Substances 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 4
- 229920001684 low density polyethylene Polymers 0.000 claims description 4
- 239000004702 low-density polyethylene Substances 0.000 claims description 4
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 3
- MPHWUNZPDZNDAG-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(OC)(OC)OC Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(OC)(OC)OC MPHWUNZPDZNDAG-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 229940070765 laurate Drugs 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims 1
- 235000010215 titanium dioxide Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 238000012545 processing Methods 0.000 abstract description 15
- 229920002725 thermoplastic elastomer Polymers 0.000 abstract description 4
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 230000008774 maternal effect Effects 0.000 abstract 2
- 239000002671 adjuvant Substances 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000010954 inorganic particle Substances 0.000 abstract 1
- 229920003023 plastic Polymers 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- 229920000178 Acrylic resin Polymers 0.000 description 10
- 239000004925 Acrylic resin Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004594 Masterbatch (MB) Substances 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000007822 coupling agent Substances 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
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- 238000001746 injection moulding Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- 229920013649 Paracril Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- 239000006185 dispersion Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004702 methyl esters Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000011160 research Methods 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
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention relates to filling material granules for toughening polyolefine and its preparation method and application, belonging to the field of inorganic particle toughened polyolefine material. Said filling maternal granules are made up by using the inorganic filling material whose particle diameter is 0.5-40 micrometers, surfactant, functionalized thermoplastic elastomer, thermoplastic resin and its mixture and processing adjuvant, and adopting the processes of uniformly mixing all ingredients, extruding by using double screw extruder or mixing by using double roll mixing mill and granulating. Said invented maternal granules contain uniformly-dispersed inorganic filling material, and when they are compounded with polyolefine material, they can be distributed in the polyolefine basal body in the form of "nuclea-shell" structure,so that said invented composite material possesses high rigidity and high toughness.
Description
The present invention relates to a kind of filler parent granule that can strengthen the toughening polyolefine material, specially refer to a kind of cheap, polyolefine filler parent granule of increasing rigidity, high toughening type.
Usually, in the plastic working process, the auxiliary agent, compound such as the stablizer that add, fire retardant, pigment etc. are concentrated in and make filler parent granule on the vector resin, it has lot of advantages, good as the plastics stability, be easy to metered charge and blend operation, purify Working environment etc., so the functionalization research of filler parent granule becomes focus as the filler parent granule that development has enhancing, toughening functions.
Xu Shengxiu is in Chinese invention patent " plastic filler parent granule " (notification number 1021857), reported a kind of plastic filler parent granule of high dispersive type, it is based on pearl filler, chelating titanates etc. are the surface treatment agent of filler, petroleum resin, ethylene-propylene rubber(EPR) etc. form for preparing carriers, the characteristics of this filler parent granule are to have good dispersing property in polymeric matrix, and can be under bigger loading level, improve the rigidity of plastics, as add 20% (wt%) this filler parent granule and be used to make the polypropylene strap, the tensile strength of its goods can by departmental standard＞160kg/cm
2Be increased to 329kg/cm
2, unit elongation by departmental standard＜25% be reduced to 17%, but therefore plastics do not obtain high tenacity.
Sun Shaoxuan is in Chinese invention patent " all purpose plastics packing parent grain and preparation method thereof " (publication number 1061028A), related to the filler parent granule that a kind of general purpose grade plastics are used, it be by through superfine grinding to the filler zeolite of 1-20 μ and white carbon black, molecular weight is that the carrier polyethylene of 1000-6000 and conditioning agent turps and white oil or oneself penta tetrol methyl esters form through mediating granulation, the characteristics of this filler parent granule are applied widely, can be used among most of thermoplasticss, because this master batch is carrier with the low molecular weight polyethylene, so this master batch can not be very remarkable to the enhancing toughening effect of plastics.
People such as Zhang Yun is bright, multitude Paine are in Chinese invention patent " toughening mother particle for polyolefine plastics and manufacture method thereof " (notification number 1124747) and " Supertough master-pellets for polypropylene plastics and manufacture method thereof " (notification number 1131165), reported with multi-functional coupling agent and help coupling agent to come coupling master batch vector resin and mineral filler to prepare the method for plasticizing mother particle and Supertough master-pellets, this filler parent granule has good toughening effect to polyolefin plastics, and optimum toughening effect can make the notched Izod impact strength of polypropylene material by 7.3KJ/m
2Be increased to 70～80KJ/m
2But this method is because being connected mineral filler and coupling agent the two is a chemical bonding between mineral filler and master batch carrier, the two only is the molecular chain physical entanglement and helping coupling agent and carrier, therefore this filler parent granule and polyolefinic matrix material are difficult to obtain high strength, high rigidity, as when above-mentioned master batch filled polypropylene material obtains optimum tenacity, the tensile strength of polypropylene material is reduced to 17～18MPa by 33.2MPa.
In order to overcome the shortcoming that can not obtain the composite polyolefine material of high rigidity, high tenacity in the above-mentioned prior art simultaneously, the invention provides and adopting mineral filler is main body, the easy dispersion that thermoplastic elastomer, thermoplastic resin, polymer emulsion and composition thereof form for preparing carriers, enhancing, high toughening type filler parent granule, this filler parent granule and polyolefine material carry out compound tense, can obtain cheap, have mineral filler for nuclear carrier be the high rigidity of " nuclear-shell " structured particles of shell, the composite polyolefine material of high tenacity.
It is based on mineral filler that the technology of a kind of stuffing mother particle for toughening polyolefine of the present invention constitutes, coupling agent, organic monomer are the surface treatment agent of mineral filler, thermoplastic elastomer, thermoplastic resin, polymer emulsion and composition thereof are carrier, and low-molecular(weight)polymer, low branch seed oil, fatty acid ester, lipid acid and salt thereof are processing aid.Filler parent granule comprises following component and content (weight percentage):
Mineral filler 47.5-84.5
Surface treatment agent 0.5-2.5
Carrier 10-30
Processing aid 5-18
Oxidation inhibitor 0-2
Above-mentioned mineral filler is talcum powder, kaolin, lime carbonate, wollastonite, mica, silicon-dioxide, aluminum oxide, aluminium hydroxide, titanium dioxide, agalmatolite, wilkinite, and its particle dia is at 0.5 μ m-40 μ m, and particle dia is 1.5 μ m-5 μ m preferably.Above-mentioned surface treatment agent is silane coupling agent such as γ-An Jibingjisanyiyangjiguiwan, γ-propyl methacrylate base Trimethoxy silane, γ-Racemic glycidol oxygen propyl trimethoxy silicane, titanate coupling agent such as sec.-propyl three different stearoyl titanic acid ester, positively charged ion, negatively charged ion, nonionic surface active agent, vinyl monomer and esters of gallic acid monomer (containing initiator) are as the mixture of vinylbenzene and maleic anhydride (containing initiator DTBP).Above-mentioned carrier is a natural rubber, cis-1,4-polybutadiene rubber, isoprene-isobutylene rubber; styrene-butadiene rubber(SBR); paracril; chloroprene rubber; polyisoprene rubber; EPDM; EVA; SBS; ethene-alpha-olefin copolymer; polyester; urethane; polyolefine such as hydroxy-terminated polybutadienes; polypropylene; high density polyethylene(HDPE); new LDPE (film grade) and maleic anhydride thereof; bismaleimides; acrylate; the ethylene-propylene-diene copolymer of vinyl monomer grafting or copolymerized grafting modification thermoplastic elastomer and thermoplastic resin such as bismaleimides graft modification; the ethylene-propylene-diene copolymer of trimethoxy propane triacrylate modification; the ethylene-propylene rubber(EPR) of modified by maleic acid anhydride graft, its melt flow rate (MFR) are 0.5g/10min-50g/10min.Above-mentioned processing aid is petroleum resin, Poly Propylene Wax, polyethylene wax, solid paraffin, whiteruss, naphthenic oil, laurate, oleic acid ester, oleic acid, stearate, stearic acid and salt thereof such as calcium stearate.Above-mentioned oxidation inhibitor is homemade phenolic antioxidant, amine antioxidants.
The preparation method of a kind of stuffing mother particle for toughening polyolefine of the present invention follows these steps to order carry out: (1) is percentage ratio by weight, above-mentioned surface treatment agent 0.5-2.5 is added thinner to be handled the surface of mineral filler 47.5-84.5 in super mixer, (2) with the mineral filler 48.0-87.0 that handles well, carrier 10-30, processing aid 5-18, oxidation inhibitor 0-2, in super mixer, mediate evenly, the kneading time is 5-30 minute, mediating temperature is 10 ℃-100 ℃, and extrude kneaded material and granulation forms so that 140 ℃-200 ℃ processing temperature is compound in twin screw extruder (3).
Another preparation method of a kind of stuffing mother particle for toughening polyolefine of the present invention follows these steps to order carry out: (1) is percentage ratio by weight, above-mentioned surface treatment agent 0.5-2.5 is added thinner to be handled the surface of mineral filler 47.5-84.5 in super mixer, (2) with the mineral filler 48.0-87.0 that handles well, carrier 10-30, processing aid 5-18, oxidation inhibitor 0-2, in super mixer, mediate evenly, the kneading time is 5-30 minute, mediating temperature is 10 ℃-100 ℃, (3) with kneaded material in mixing roll, temperature with 120 ℃-150 ℃ is mixing, in flakes, pelletizing forms.
The purposes of a kind of stuffing mother particle for toughening polyolefine of the present invention is the preparation composite polyolefine material.Above-mentioned polyolefine is homo-polypropylene, Co-polypropylene, high density polyethylene(HDPE), new LDPE (film grade), linear low density polyethylene, ethylene copolymer.
The purpose that inorganic filler surface is handled is to introduce reactive group or unsaturated link(age) on its surface, when above-mentioned mineral filler and have can with the carrier or the modified support of the functional group of filling surface reactive group generation chemical reaction, or have can with the carrier of filling surface unsaturated link(age) generation copolymerization or modified support mediate, in the extrusion, cause by heat or initiator, the two surperficial reactive group of mineral filler and carrier partly contacts concurrent biochemical reaction, the two is linked up with certain linking intensity and is present in the filler parent granule of preparation.Filler parent granule and polyolefine compound tense when preparation, filler and master batch carrier can be that the nuclear carrier is that " hard core-soft core " structured particles form of shell is dispersed in the polyolefin substrate with the mineral filler in the filler parent granule, replace simple rubber elastomer toughening polyolefine material.
Stuffing mother particle for toughening polyolefine of the present invention has mineral filler and can be dispersed in the filler parent granule carrier, and is evenly distributed on the characteristics in the polyolefin substrate with mineral filler-master batch carrier " hard core-soft core " structure formation.When the filler parent granule addition is 30-40wt%, can make the modulus of composite polyolefine material improve 0.5-1 doubly, notched Izod impact strength improves 1-4 doubly, and easy to process, and cost is low.
Embodiment 1
To handle through γ-propyl methacrylate base Trimethoxy silane 11.5g, granularity is the talcum powder 774.5g of 5 μ m, the ethylene-propylene-diene copolymer 91.2g of bismaleimides graft modification, its melt flow rate is 2.5g/10min, polypropylene 60.8g, its melt flow rate is 30g/10min, Poly Propylene Wax 53.5g, calcium stearate 10g, N-cyclohexyl-N '-diphenyl-para-phenylene diamine 10g, after in homogenizer, mediating 20min under the room temperature, extrude through twin screw extruder, the extruder barrel temperature is followed successively by 150-160-190-200-190 ℃ from the import to the outlet, and the water-cooled pelletizing forms.
With this talcum powder filler parent granule with the ethylene-propylene copolymer acrylic resin mixes 3-5min in 10: 90 ratio (weight percentage) in super mixer after, compound in twin screw extruder, the extruder barrel temperature is followed successively by 195-205-205-220-195 ℃ from the import to the outlet, its composite materials property test result sees Table 1.Embodiment 2:
With the talcum powder filler parent granule of embodiment 1 preparation and ethylene-propylene copolymer polypropylene ratio (weight percentage), with method and the condition composite moulding identical with embodiment 1 in 20: 80.Embodiment 3:
With the talcum powder filler parent granule of embodiment 1 preparation and ethylene-propylene copolymer polypropylene ratio (weight percentage), with method and the condition composite moulding identical with embodiment 1 in 30: 70.Embodiment 4:
With the talcum powder filler parent granule of embodiment 1 preparation and ethylene-propylene copolymer polypropylene ratio (weight percentage), with method and the condition composite moulding identical with embodiment 1 in 40: 60.
After table 1 talcum powder filler parent granule and copolymerization acrylic resin are compound, the mechanical property of its material
Embodiment 5 (comparative example):
| Mixture | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Notched izod shock strength (J/m) tensile strength (MPa) elongation at break (%) flexural strength (MPa) modulus in flexure (GPa) | ???218.0 ???28.5 ???1044.8 ???27.4 ???0.7 | ????267.0 ????27.8 ????1020.0 ????26.1 ????0.8 | ?308.0 ?26.1 ?979.2 ?25.0 ?0.8 | ?525.0 ?24.7 ?997.8 ?23.2 ?0.9 |
With talcum powder and ethylene-propylene copolymer acrylic resin in 10: 90 ratio (weight percentage) after mixing, with the processing conditions compound and injection moulding identical with embodiment 1.Embodiment 6 (comparative example):
With talcum powder and ethylene-propylene copolymer acrylic resin in 20: 80 ratio (weight percentage) after mixing, with the processing conditions compound and injection moulding identical with embodiment 1.Embodiment 7 (comparative example):
With talcum powder and ethylene-propylene copolymer acrylic resin in 30: 70 ratio (weight percentage) after mixing, with the processing conditions compound and injection moulding identical with embodiment 1.Embodiment 8 (comparative example):
With talcum powder and ethylene-propylene copolymer acrylic resin in 40: 60 ratio (weight percentage) after mixing, with the processing conditions compound and injection moulding identical with embodiment 1.
The mechanical property of table 2 talcum powder and copolymerization polypropylene composite material
Embodiment 9:
| Mixture | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Notched izod shock strength (J/m) tensile strength (MPa) elongation at break (%) flexural strength (MPa) modulus in flexure (GPa) | ?181.0 ?29.8 ?1021.2 ?34.1 ?1.0 | ????178.0 ????30.5 ????1122.4 ????37.9 ????1.1 | ?160.5 ?30.2 ?659.8 ?38.5 ?1.2 | ?129.0 ?29.8 ?389.2 ?40.2 ?1.2 |
To handle through sec.-propyl three different stearoyl titanic acid ester 11.5g, granularity is the talcum powder 704.5g of 5 μ m, titanium dioxide 70g, ethene-alpha-olefin copolymer 91.2g, its melt flow rate is 0.5g/10min, polypropylene 60.8g, its melt flow rate is 50g/10min, naphthenic oil 53.5g, calcium stearate 10g, N-cyclohexyl-N '-diphenyl-para-phenylene diamine 10g, in homogenizer, mediate 30min with 40 ℃-50 ℃ kneading temperature after, extrude through twin screw extruder, the extruder barrel temperature is followed successively by 160-180-190-200-170 ℃ from the import to the outlet, the water-cooled pelletizing forms.
With above-mentioned filler parent granule and ethylene-propylene copolymer acrylic resin ratio in 40: 60 (weight percentage), obtain filling the Co-polypropylene matrix material with the working method identical with embodiment 1, its mechanical property sees Table 3.Embodiment 10:
To handle through the 11.5g γ-An Jibingjisanyiyangjiguiwan, granularity is the talcum powder 774.5g of 5 μ m, the ethylene-propylene-diene copolymer 152g of trimethoxy propane triacrylate modification, its melt flow rate is 5g/10min, Poly Propylene Wax 53.5g, calcium stearate 10g, N-cyclohexyl-N '-diphenyl-para-phenylene diamine 10g, under the working method and processing conditions identical, be prepared into filler parent granule and be combined into filled composite materials in the ratio of 40: 60 (weight percentage) with the copolymerization acrylic resin with embodiment 1.Embodiment 11 (comparative example):
Ethylene-propylene copolymer acrylic resin, the trade mark are PP1330, and chemical industry two factories of Beijing Yanshan Petro-Chemical Industry Corporation produce, pellet, and processing conditions and embodiment 9 are together.Embodiment 12 (comparative example):
When Co-polypropylene and ethylene-propylene-diene elastomer are pressed the master batch filled polyolefin matrix material of embodiment 9 preparations, wherein the Co-polypropylene matrix is with after the two identical ratio (weight percentage) of ethylene-propylene-diene elastomer as the master batch carrier mixes, composite molding, condition of molding and embodiment 9 are together.
Table 3 embodiment 9, embodiment 10 and embodiment 8, embodiment 11, embodiment 12 results' comparison
Embodiment 13:
| Mixture | Embodiment 9 | Embodiment 10 | Embodiment 8 | Embodiment 11 | Embodiment 12 |
| Notched izod impact strength (J/m) hot strength (MPa) elongation at break (%) bending strength (MPa) bending modulus (GPa) | ?343.8 ?22.0 ?511.4 ?34.7 ?1.5 | ?429.5 ?24.7 ?752.8 ?25.3 ?1.0 | ?129.0 ?29.8 ?389.2 ?40.2 ?1.2 | ?239.0 ?27.8 ?592.0 ?30.7 ?0.8 | ?615.0 ?21.9 ?530.2 ?24.9 ?0.7 |
To adsorb initiator DTBP0.1g, styrene monomer 8.0g, maleic anhydride 1.6g, granularity is the lime carbonate 750.8g of 1.5 μ m, and propylene-alpha-olefin copolymers 158.0g, its melt flow rate are 0.5g/10min, hydroxy-terminated polybutadienes 39.6g, laurate 7.9g, polyethylene wax 42.1g is at room temperature after homogenizer is mediated 10min, mixing on double roll mill, in flakes, pelletizing forms, and melting temperature is 120-150 ℃.
With above-mentioned filler parent granule and acrylic resin prescription by 40: 60 (weight percentage), the filling polypropylene composite material that obtains with the working method identical with embodiment 1.Embodiment 14 (comparative example):
With lime carbonate and the polypropylene matrix proportioning by 40: 60 (weight percentage), the mechanical property of the filling polypropylene composite material that obtains with working method identical with embodiment 13 and processing conditions also sees Table 4.Embodiment 15 (comparative example):
Homo-polypropylene, the trade mark are PP2401, and chemical industry two factories of Beijing Yanshan Petro-Chemical Industry Corporation produce, pellet, and the processing conditions processing identical with embodiment 13 also is injection molded into national testing standard sample.Table 4 embodiment 13 and embodiment 14, result's contrast of embodiment 15
Embodiment 16:
| Mixture | Notched izod shock strength (J/m) | Tensile strength (MPa) | Elongation at break (%) | Flexural strength (MPa) | Modulus in flexure (GPa) |
| Embodiment 13 embodiment 14 embodiment 15 | ????166.3 ????47.5 ????22.5 | ????29.2 ????35.0 ????37.3 | ????156.0 ????212.6 ????381.7 | ????48.5 ????52.1 ????50.3 | ????2.0 ????1.7 ????1.4 |
2.5 μ m kaolin 679.5g with 7.5g γ-Racemic glycidol oxygen propyl trimethoxy silicane processing, 2.5 μ m aluminium hydroxide 75.5g, high density polyethylene(HDPE) 47.3g, its melt flow rate is 5g/10min, new LDPE (film grade) 47.3g, its melt flow rate is 50g/min, the ethylene-propylene rubber(EPR) 94.6g of maleic anhydride graft, its melt flow rate is 3g/min, whiteruss 37.8g, calcium stearate 8g, four [β-(and 3,5-di-tert-butyl-4-hydroxy phenyl propionic acid] pentaerythritol ester 4g, the two ten diester 6g of thio-2 acid mediate 20min with room temperature in homogenizer after, extrude through twin screw extruder, the extruder barrel temperature is followed successively by 140-160-180-200-190 ℃ from the import to the outlet, and the water-cooled pelletizing forms.
Above-mentioned filler parent granule and high-density polyethylene resin are pressed the prescription of 20: 80 (weight percentage), after simple the mixing, in injector, directly be injection molded into national testing standard sample, injection temperature is 200 ℃, injection pressure is 13.5MPa, and its composite materials property test result sees Table 5.Embodiment 17:
High-density polyethylene resin, the trade mark are HDPE DMD7006, and plastic molding and processing plant of Qilu Petrochemical company produces, pellet, and processing conditions and embodiment 16 are together.Embodiment 18:
Will with the kaolin of embodiment 16 identical proportionings and aluminium hydroxide mixed fillers and high-density polyethylene resin prescription by 20: 80 (weight percentage), with the filling high-density polyethylene matrix material that working method identical with embodiment 16 and processing conditions obtain, its Mechanics Performance Testing result also can see Table 5.
Table 5 embodiment 16 and embodiment 17, embodiment 18 results' contrast
| Mixture | Notched izod shock strength (J/m) | Tensile strength (MPa) | Elongation at break (%) | Flexural strength (MPa) | Modulus in flexure (GPa) |
| Embodiment 16 comparative examples 17 comparative examples 18 | ????56.0 ????34.1 ????37.6 | ????22.7 ????25.9 ????26.3 | ?????72.0 ????150.0 ????136.0 | ????39.8 ????33.8 ????37.6 | ????1.5 ????0.8 ????1.3 |
Claims (10)
1 one kinds of stuffing mother particle for toughening polyolefine is characterized in that described filler parent granule comprises following component and content (weight percentage)
Mineral filler 47.5-84.5
Surface treatment agent 0.5-2.5
Carrier 10-30
Processing aid 5-18
Oxidation inhibitor 0-2
2 a kind of stuffing mother particle for toughening polyolefine according to claim 1 is characterized in that described mineral filler is talcum powder, kaolin, lime carbonate, titanium dioxide or aluminium hydroxide.
3 a kind of stuffing mother particle for toughening polyolefine according to claim 2, the particle dia that it is characterized in that described mineral filler are 1.5 μ m-5 μ m.
4 a kind of stuffing mother particle for toughening polyolefine according to claim 1 is characterized in that described inorganic filler surface treatment agent is the mixture of γ-propyl methacrylate base Trimethoxy silane, γ-An Jibingjisanyiyangjiguiwan, γ-Racemic glycidol oxygen propyl trimethoxy silicane, sec.-propyl three different stearoyl titanic acid ester or vinylbenzene and maleic anhydride.
5 a kind of stuffing mother particle for toughening polyolefine according to claim 1 is characterized in that described carrier is the ethylene-propylene-diene copolymer of bismaleimides graft modification, the ethylene-propylene-diene copolymer of trimethoxy propane triacrylate graft modification, ethylene-propylene rubber(EPR), ethene-alpha-olefin copolymer, polypropylene, new LDPE (film grade), high density polyethylene(HDPE) or the hydroxy-terminated polybutadienes of maleic anhydride graft.
6 a kind of stuffing mother particle for toughening polyolefine according to claim 5, the melt flow rate that it is characterized in that described carrier is 0.5g/10min-50g/10min.
7 a kind of stuffing mother particle for toughening polyolefine according to claim 1 is characterized in that described processing aid is Poly Propylene Wax, polyethylene wax, laurate, calcium stearate, whiteruss or naphthenic oil.
The preparation method of 8 a kind of stuffing mother particle for toughening polyolefine according to claim 1, it is characterized in that following these steps to order carries out: (1) is percentage ratio by weight, surface with surface treatment agent 0.5-2.5 treatment inorganic filling material 47.5-84.5 in super mixer, (2) with the mineral filler 48.0-87.0 and the carrier 10-30 that handle well, processing aid 5-18, oxidation inhibitor 0-2 mediates in super mixer evenly, the kneading time is 20-30 minute, mediating temperature is 25 ℃-50 ℃, (3) above-mentioned kneaded material is extruded through twin screw extruder is compound under 140 ℃-200 ℃, granulation is made.
The preparation method of 9 a kind of stuffing mother particle for toughening polyolefine according to claim 1, it is characterized in that following these steps to order carries out: (1) is percentage ratio by weight, surface with surface treatment agent 0.5-2.5 treatment inorganic filling material 47.5-84.5 in super mixer, (2) with the mineral filler 48.0-87.0 that handles well and carrier 10-30, processing aid 5-18, oxidation inhibitor 0-2, in super mixer, mediate evenly, (3) with above-mentioned kneaded material in 120 ℃ of-150 ℃ of mixing rolls, through mixing, in flakes, pelletizing forms.
The purposes of 10 a kind of stuffing mother particle for toughening polyolefine according to claim 1 is characterized in that described filler parent granule is used to prepare composite polyolefine material.
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| CN98102448A CN1100087C (en) | 1998-06-18 | 1998-06-18 | Stuffing mother particle for toughening polyolefine and preparation process and usage thereof |
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| CN98102448A CN1100087C (en) | 1998-06-18 | 1998-06-18 | Stuffing mother particle for toughening polyolefine and preparation process and usage thereof |
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