CN1450111A - Syndiotactic polystyrene/polyamide/clay nano blended material - Google Patents
Syndiotactic polystyrene/polyamide/clay nano blended material Download PDFInfo
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- CN1450111A CN1450111A CN 02111308 CN02111308A CN1450111A CN 1450111 A CN1450111 A CN 1450111A CN 02111308 CN02111308 CN 02111308 CN 02111308 A CN02111308 A CN 02111308A CN 1450111 A CN1450111 A CN 1450111A
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- polyamide
- clay
- hybrid materials
- clay nano
- syndiotactic
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- 239000000463 material Substances 0.000 title claims abstract description 88
- 239000004927 clay Substances 0.000 title claims abstract description 78
- 229920010524 Syndiotactic polystyrene Polymers 0.000 title claims abstract description 56
- 239000004952 Polyamide Substances 0.000 title claims abstract description 46
- 229920002647 polyamide Polymers 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000009830 intercalation Methods 0.000 claims abstract description 11
- 230000002687 intercalation Effects 0.000 claims abstract description 11
- -1 polyphenylethylene Polymers 0.000 claims description 77
- 229920002292 Nylon 6 Polymers 0.000 claims description 28
- 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 group 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 21
- 150000001408 amides Chemical class 0.000 claims description 21
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 238000006277 sulfonation reaction Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- 229920006122 polyamide resin Polymers 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000003063 flame retardant Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000002689 soil Substances 0.000 claims description 4
- ASFAFOSQXBRFMV-LJQANCHMSA-N 3-n-(2-benzyl-1,3-dihydroxypropan-2-yl)-1-n-[(1r)-1-(4-fluorophenyl)ethyl]-5-[methyl(methylsulfonyl)amino]benzene-1,3-dicarboxamide Chemical compound N([C@H](C)C=1C=CC(F)=CC=1)C(=O)C(C=1)=CC(N(C)S(C)(=O)=O)=CC=1C(=O)NC(CO)(CO)CC1=CC=CC=C1 ASFAFOSQXBRFMV-LJQANCHMSA-N 0.000 claims description 3
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 claims description 3
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 3
- 229920006152 PA1010 Polymers 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004760 aramid Substances 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical group [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 3
- 235000010234 sodium benzoate Nutrition 0.000 claims description 3
- 239000004299 sodium benzoate Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 150000003440 styrenes Chemical class 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 235000012222 talc Nutrition 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 17
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 description 56
- 238000002360 preparation method Methods 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000005453 pelletization Methods 0.000 description 12
- 238000001746 injection moulding Methods 0.000 description 11
- 238000004898 kneading Methods 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 11
- 239000008188 pellet Substances 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 125000000962 organic group Chemical group 0.000 description 8
- 230000035939 shock Effects 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 229920006351 engineering plastic Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920006380 polyphenylene oxide Polymers 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 230000003993 interaction Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012764 mineral filler Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical class CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- PLAFTLBFNIMFNQ-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)CN)C(C)(C)C)C(O)C(CO)(CO)CO Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)CN)C(C)(C)C)C(O)C(CO)(CO)CO PLAFTLBFNIMFNQ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a syndiotactic polystyrene/polyamide/clay nano mixed material, and is aimed at mainly resolving the problems of large brittleness, low impact strength and poor comprehensive performance in the previous composite materials. Said invention utilizes the adoption of its technical scheme of that firstly, an intercalation combination-comixing combination method is adopted to prepare out polyamide/clay nano composite, then the syndiotactic polystyrene and polyamide/clay nano composite (using sulfonated syndiotactic polystyrene as compatibilizer) are melt-mixed and combined so as to better resolve the above-mentioned problems. Said nano mixed material has high impact strength, high strength and high heat-resisting property.
Description
Technical field
The present invention relates to syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials.
Background technology
Syndiotactic polystyrene is a kind of novel engineering plastics, and it is different with general purpose polystyrene, has the following advantages: (1) fusing point height is 270 ℃.(2) degree of crystallinity height, Tc can be controlled at the scope of a broad, is fit to conventional plastics forming method.(3) heat-resisting, chemical resistance is good.Thereby having fabulous development prospect, potential market is boundless.The defective of syndiotactic polystyrene is that fragility is big, thereby has limited its range of application.Must carry out modification to it, with the application of commensurate structure material.The characteristic performance of the syndiotactic polystyrene after the improvement is that density is low, good toughness, good electrical property, can with other engineering plastics competition.The occasion that engineering plastics such as nearly all PET, PBT, PA, PPS are used can be used syndiotactic polystyrene.Aspect electrical equipment, electronics, can be used for high-frequency device, satellite antenna, phone, unicircuit, printed-wiring board (PWB), microwave stove etc.Aspect trolley part, can do safety lever, fuel tank, high temperature resistant motor part etc.Aspect wrapping material, can make heat-resisting, oil resistant, anti-vapor vessel, food packaging film etc.In addition, can also make high gloss insulating film, magnetic recording body, camera housing, fibre product and industrial membrane etc.
The study on the modification of syndiotactic polystyrene mainly concentrates on and strengthens and blending and modifying two aspects.The former normally with glass fibre strengthen (EP508303, EP591823, US5200454, JP10017740).But because syndiotactic polystyrene is a kind of non-polar polymer, so the interface of polarity glass fibre and syndiotactic polystyrene bonding is poor, its interface often becomes the weakest link of mechanical property.Therefore pure adopt glass fibre filled method to the syndiotactic polystyrene over-all properties particularly the raising of impact property be not clearly, and processing difficulties.The latter mainly be with syndiotactic polystyrene respectively with elastomerics (as SEBS, SIS, SBS etc.) (US5391603, JP08319386, JP09052959), polyphenylene oxide (PPO) (EP587098, EP546497, JP08157668), general engineering plastic (as polymeric amide, polyester etc.) (Chinese invention patent, application number: 01105846.3,01105845.5,01105844.7) and blend is with the impact property of further raising syndiotactic polystyrene.Wherein syndiotactic polystyrene and polyphenylene oxide (PPO) blend, because consistency is better between the two, thereby the good combination property of blend.But the blend application is restricted owing to polyphenylene oxide yields poorly, price is high.The employing sulfonated syndiotactic polyphenylethylene is an expanding material, syndiotactic polystyrene and general engineering plastic such as polymeric amide are carried out melt blending, the matrix material that obtains has the shock strength height, and the equal characteristics preferably of flexural strength and tensile strength, is one of effective ways of syndiotactic polystyrene modification.But the intensity of material and thermotolerance still also have the necessity that further improves.Adopt elastomerics (SEBS, SIS, SBS etc.) and syndiotactic polystyrene blend can significantly improve the shock resistance of syndiotactic polystyrene really.But its drawback is also more outstanding, the one, adopt syndiotactic polystyrene and elastomeric graft copolymer as expanding material, wherein the preparation of syndiotactic polystyrene and elastomeric graft copolymer normally earlier with the syndiotactic polystyrene grafted maleic anhydride, obtains graft copolymer by other chemical reaction again.In order to make the syndiotactic polystyrene grafted maleic anhydride, must when syndiotactic polymerization of phenylethylene, add a spot of alpha-methyl styrene and carry out copolymerization.This will make polymerization technique become complicated, also can the taxis and the performance of polymerisate be had a negative impact simultaneously.Industrial application is undesirable.The 2nd, the over-all properties of blend such as thermotolerance, intensity and modulus descend more.For this reason, document (JP06116454, JP06345923 JP07048488) waits and to have reported that adding mineral filler (as glass etc.) in syndiotactic polystyrene/elastomer blended system strengthens, and introduces intensity and the resistance toheat that makes material unaccounted-for (MUF) with compensation because of elastomerics.But because bonding is poor between mineral filler and the polymer-based carbon body interface, filler does not reach the nano-dispersed level in polymeric matrix simultaneously, thereby the enhancing amplitude is limited.If can realize that the dispersion of mineral filler in containing the multicomponent polymeric matrix of syndiotactic polystyrene reaches nanoscale, just rigidity, dimensional stability and the thermostability of inorganics and toughness, processibility and the dielectric properties perfect adaptation of multicomponent polymeric might be got up the syndiotactic polystyrene based nano composite material of obtained performance excellence.Adopt intercalation compound-method that blend combines is expected to reach this target.
At present, intercalation complex method (comprising intercalation polymeric method and polyalcohol intercalation method) has become the important method in organic-inorganic nano composite material (the being also referred to as organic-inorganic nano hybrid material) preparation, its preparation process is that the polymer macromolecule chain is inserted between the interlayer of the silicate clay with laminate structure, forms the sequential 2 D nano composite material; In addition, polymer macromolecule chain intercalation can promote peeling off of clay silicate lamella in some cases, forms the organic-inorganic matrix material of nanometer scale in polymeric matrix.Compare with the polymkeric substance-inorganic filler composite material of routine, the organic-inorganic nano composite material is owing to interfacial area between polymkeric substance and the inorganics is very big, and exist between the two interface than strong interaction power, therefore can give full play to the excellent mechanical property and the high heat resistance of inorganic materials.Just have very strong reinforced effects at the clay consumption seldom the time, the nano composite material that contains 5% left and right sides clay usually is suitable with conventional rigidity, intensity, the thermotolerance that contains have an appointment 30% glass or mineral reinforced composite.Thereby nano composite material has light weight, high strength, high-modulus, high heat resistance and good dimensional stability and good gas barrier; Some nano composite material also has very high self-extinguishing, very low heat release rate and higher smoke-suppressing, is the ideal fire retardant material.The organic-inorganic matrix material that adopts the intercalation complex method to prepare mainly contains nano composite material of epoxy resin/clay [US4889885] at present, nylon 6/ clay nanocomposites [CN1163288A, CN1138593A], random polystyrene/clay nanocomposites [[Chinese invention patent, 98103038], polyethylene terephthalate/Nano composite material of montmorillonite [Chinese invention patent, 97104055,97104294] etc.
Summary of the invention
Technical problem to be solved by this invention is to exist syndiotactic polystyrene blended compound material fragility big in the conventional art in order to overcome, low and polymeric matrix of shock strength and mineral filler interface interaction are weak and the unfavorable problem of composite material combination property that causes provides a kind of new syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials.These hybrid materials have the shock strength height, the high and high characteristics of thermotolerance of intensity.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials comprises following component in parts by weight:
A) syndiotactic polystyrene is 1～99 part;
B) sulfonated syndiotactic polyphenylethylene is 1～50 part;
C) polyamide resin is 1～50 part;
D) the polyamide-clay nano-complex is 1～50 part;
E) be selected from 1～50 part of the auxiliary agent of oxidation inhibitor, fire retardant, nucleator or impact modifying agent and composition thereof;
Wherein hybrid materials medium clay soil disperse phase particle diameter is 5～90 nanometers.
In the technique scheme, be 50～85 parts in the preferable range of parts by weight syndiotactic polystyrene amount, wherein the molecular weight of syndiotactic polystyrene is 20～700,000, and a normality is greater than 96%.The sulfonation degree of used sulfonated syndiotactic polyphenylethylene counts 1～20% with molar percentage, is 1～20 part in the preferable range of parts by weight sulfonated syndiotactic polyphenylethylene amount.Used polyamide resin is selected from polyamide 6, polyamide 66, polyamide 6 10, polyamide 1010, polymeric amide 4, polymeric amide 9, polymeric amide 46, polymeric amide 11, polymeric amide 12 or aromatic polyamides, and preferred version is a polyamide 6.In parts by weight, polyamide resin consumption preferable range is 5～40 parts.The polyamide-clay nano-complex is selected from intercal type or the exfoliated polyamide-clay nano-complex that adopts the intercalation complex method to prepare, and preferred version is polyamide 6/clay nano mixture.In parts by weight, polyamide 6/clay nano mixture consumption preferable range is 3～40 parts.Used clay is selected from the silicate compound or the natural silicate clay of the synthetic with laminate structure, comprise that polynite, talcum, zeolite, vermiculite, sepiolite, synthetic mica, lithium montmorillonite, white clay, the phosphoric acid salt with laminate structure, graphite, metal oxide are or/and disulphide, preferred version is polynite, and the cation exchange capacity of polynite is 40～140 mmoles/100 grams.The polynite preferred version is an organo montmorillonite, is the product of polynite gained after organic agent is handled, and the organo montmorillonite consumption is 1～20% of hybrid materials by weight percentage.Organic agent is selected from the compound with following structural formula: CH
3(CH
2)
nNR
3X and/or HOOC (CH
2)
N-1NH
2, wherein R is H or CH
3X is Cl, Br or I; N=4～60, preferred version are ten monoamino-acids or ten diamino acid.Auxiliary agent comprises oxidation inhibitor, fire retardant, nucleator or impact modifying agent and composition thereof, and wherein oxidation inhibitor is selected from antioxidant 1010, PEP36, Mark Ao-30 or BHT; Nucleator is selected from Sodium Benzoate or p t butylbenzoic acid aluminium; Impact modifying agent is selected from segmented copolymer, ABS or the urethane of segmented copolymer, vinylbenzene and different propylene of segmented copolymer, hydrogenated styrene and the divinyl of styrene-butadiene rubber(SBR), vinylbenzene and divinyl.Hybrid materials medium clay soil disperse phase particle diameter preferable range is 5～50 nanometers.
Sulfonated syndiotactic polyphenylethylene is meant the polymkeric substance that has polarity sulfonic acid group or sulfonate groups on the phenyl ring in the syndiotactic polystyrene molecule.Sulfonic acid group or sulfonate groups generally are distributed in the contraposition of phenyl ring, but position and adjacent reaction between being not precluded within.The sulfonation degree of sulfonated syndiotactic polyphenylethylene generally is controlled at 1～20 mole of %, because the introducing of sulfonic acid group makes sulfonated syndiotactic polyphenylethylene have certain wetting ability, needs drying treatment before therefore using.The sulfonated syndiotactic polyphenylethylene that the present invention uses can be neutralization or unneutralized, in and the contained metal ion of sulfonated syndiotactic polyphenylethylene can be potassium, sodium, lithium, barium, magnesium, manganese, zinc, copper, calcium, cobalt, iron, nickel plasma.General sulfonated syndiotactic polyphenylethylene or the ionomeric consumption of sulfonated syndiotactic polyphenylethylene are 1～50% of syndiotactic polystyrene consumption, and optimum amount is 1～20% of a syndiotactic polystyrene consumption.
Used polymeric amide (C) can be suitability for industrialized production or the not kind of suitability for industrialized production among the present invention.Comprise polyamide 6 (nylon 6), polyamide 6 (nylon 66), polyamide 6 10 (NYLON610), polyamide 1010 (nylon 1010), polymeric amide 4 (nylon 4), polymeric amide 9 (nylon 9), polymeric amide 46 (nylon 46), polymeric amide 11 (Ni Long11), polymeric amide 12 (nylon 12) and aromatic polyamides etc.The polymeric amide consumption is 1～50% of a mixture total amount among the present invention, and optimum amount is 5～40%.If the consumption of polymeric amide surpasses 50%, then the water-intake rate of the water-intake rate of mixture and pure polymeric amide is approaching.
Used polyamide-clay nano-complex is selected from intercal type or the exfoliated polyamide-clay nano-complex that adopts the intercalation complex method to prepare among the present invention.Wherein polymeric amide comprises kind described in (C).Used clay can be synthetic or the natural silicate that the stratiform knot has laminate structure that has, and comprises polynite, talcum, zeolite, vermiculite, sepiolite, synthetic mica, lithium montmorillonite, white clay, the phosphoric acid salt with laminate structure, graphite, metal oxide, disulphide etc.Handle through organic agent before clay uses, used organic agent can be suitability for industrialized production or the not product of suitability for industrialized production among the present invention, and has the compound of following structural formula: CH
3(CH
2)
nNR
3X and/or HOOC (CH
2)
N-1NH
2, wherein R is H or CH
3X is Cl, Br or I; N=4～60.Polyamide-clay nano-complex used among the present invention is counted 1～50 part with parts by weight, and optimum amount is 3～40 parts.
Syndiotactic polyphenylethylene/polyamide involved in the present invention/clay nano hybrid materials can add other auxiliary agents according to the needs of actual situation.Auxiliary agent comprises oxidation inhibitor, fire retardant, nucleator and impact modifying agent etc.Wherein oxidation inhibitor is important, and the adding of oxidation inhibitor mainly is in order to prevent polymkeric substance oxygenolysis when the high-temperature fusion blend.Oxidation inhibitor commonly used comprises antioxidant 1010 (four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol resin), PEP36 (2,6-di-t-butyl-4-aminomethyl phenyl tetramethylolmethane diphosphite fat), Mark AO-30 (1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane) and BHT (2, the 6-tertiary butyl-4-cresols) etc.The consumption of oxidation inhibitor is generally 0.1～1% (weight) of polymer loading.The adding of nucleator mainly is in order to improve the crystallinity of syndiotactic polystyrene, and nucleator commonly used has Sodium Benzoate and p-tert-butyl benzoic acid aluminium etc.The consumption of nucleator is generally 0.3～5% of polymer weight.The adding of impact modifying agent is in order further to improve the impact property of blended complex, impact modifying agent commonly used is rubber or elastomerics etc., for example the segmented copolymer of segmented copolymer (SEBS), vinylbenzene and the different propylene of the segmented copolymer of styrene-butadiene rubber(SBR), vinylbenzene and divinyl (SBS), hydrogenated styrene and divinyl (SI, SIS) and ABS and Polyurethane etc.The consumption of impact modifying agent depends on the needs, usually in 5～20% (weight).
The preparation method of sulfonated syndiotactic polyphenylethylene is as follows:
In 500 milliliters of round-bottomed flasks, put into 3.0 gram sPS (syndiotactic polystyrene) and 340 milliliters 1,2,4-trichloroethane (TCE), reflux (about 150 ℃) is all dissolved to sPS.Solution is chilled to 50～70 ℃ then, feeds nitrogen, and keep reaction soln at 60 ℃, slowly drip the sulfonated reagent of metering according to required sulfonation degree, stir fast simultaneously, 60 ℃ of reactions of constant temperature added 10 ml methanol termination reactions after 1～3 hour.After sulfonation reaction is finished,, should while hot sedimentation in reaction solution impouring 1200 ml methanol be gone out polymkeric substance immediately, after the filtration product be spent the night 70 ℃ of vacuum-dryings in order to prevent gel.
In order further to remove the sulfonated reagent of carrying secretly in the product, it is dissolved among the TCE methyl alcohol sedimentation, suction filtration earlier.Polymkeric substance is put into the Soxhlet extractor again and used methyl alcohol extracting 24 hours, product is spent the night 70 ℃ of vacuum-dryings promptly gets purified SsPS (sulfonated syndiotactic polyphenylethylene) at last.
The measuring method of SsPS sulfonation degree is that SsPS sample 0.3～0.5 gram is dissolved in volume ratio is in 95: 5 the trichloromethane methanol mixed solvent, the SsPS sample that dissolving is good is indicator with phenolphthalein, with the methanol solution titration of NaoH to terminal, the amount according to the NaoH that is consumed calculates sulfonation degree.
The preparation method of organo montmorillonite is as follows:
In 80 ℃ of water of 400 milliliters, add ten diamino acid of 2.6 grams (12.0 mmole) and the vitriol oil of 1.2 milliliters (21.6 mmoles), and then slowly be injected in the 600 ml water solution that contain 10 gram sodium-based montmorillonites, this mixing solutions is arrived room temperature at 12 hours postcooling of 80 ℃ of fierce stirrings, suction filtration, be washed to the sulfate radical-free ion, vacuum-drying to constant weight promptly gets organo montmorillonite, and grinds to form 300～400 order powder, is designated as MTA.
The preparation method of syndiotactic polyphenylethylene/polyamide of the present invention/clay nano hybrid materials is as follows:
In blender, do PA6 and MTA mixed in proportion earlier, and then in mixing roll or two Luo bar forcing machine, mediate, general condition is controlled at: temperature is 230 ℃, rotating speed is 75 rev/mins, mixing time depends on the circumstances, be generally 5～15 minutes (preparation polyamide-clay nano-complex), add syndiotactic polystyrene, sulfonated syndiotactic polyphenylethylene and the auxiliary agent (in blender, doing mixed earlier) of metering again, be warming up to 285 ℃ mixing 5～15 minutes.The material that mixes is in forcing machine behind the extruding pelletization, through injector injection molding.Have high strength, high heat resistance and shock strength preferably by the syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials of above-mentioned each component preparation.Be expected as electronic apparatus material, industrial structure material, automobile component, civil electric appliance parts and other machine part etc.
The present invention adopt intercalation compound-method that blend combines prepares the nano hybrid material, this novel method is to use traditional polymer processing prepared nano composite material, has the advantages that technology is simple, be easy to industrial applications.The present invention introduces sulfonated syndiotactic polyphenylethylene in syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials preparation process, owing to have special interaction between the sulfonic acid group of sulfonated syndiotactic polyphenylethylene and the amide group of polymeric amide, as hydrogen bond action and coordination etc., and syndiotactic polystyrene and sulfonated syndiotactic polyphenylethylene consistency are very good, thereby promoted the compatibilization effect of whole matrix material greatly, improved the over-all properties of matrix material.Owing to also have special interaction between the sulfonic acid group of sulfonated syndiotactic polyphenylethylene and the surface of clay polar group,, also promoted the bonding interface performance of polymeric matrix and surface of clay simultaneously as hydrogen bond action.In addition, adopting the syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials of the inventive method preparation is exfoliated nano-composite, and clay silicate lamella is stripped from into nanoscale and is dispersed in the polymeric matrix.Significantly improved the over-all properties of nano composite material, the flexural strength, tensile strength that makes syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials is respectively by the 48.6MPa of pure syndiotactic polystyrene material; 33.6MPa bring up to 70.7MPa; 63.9MPa.The shock strength of nano composite material is also from 5.3 kilojoule/rice simultaneously
2Bring up to 16.3 kilojoule/rice
2
The present invention is further elaborated below by embodiment.
Embodiment [embodiment 1]
The preparation of syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials
With 20 parts of (weight, as follows) polyamide 6 (PA6) (molecular weight is 18000), 4 parts of organo montmorillonites (MTA) and 0.1 part of antioxidant 1010 do mixed earlier in blender, and then mixing kneading in mixing roll, mixing condition is: temperature is 230～235 ℃, rotating speed is 75 rev/mins, mixing time is 8 minutes, and the material that mixes extruding pelletization in forcing machine promptly gets polyamide 6/montmorillonite nano complex.
80 parts of (weight, as follows) syndiotactic polystyrene (weight-average molecular weight is 350,000, a normality 97%, fusing point is 272 ℃) in, add 24 parts of polyamide 6/montmorillonite nano complexes that prepare above, 5 parts of sulfonated syndiotactic polyphenylethylenes (SsPS, sulfonation degree is 8.65 moles of %) and 0.1 part of antioxidant 1010 are done above-mentioned material mixed earlier in blender, and then mixing kneading in mixing roll, mixing condition is: temperature is 285 ℃, and rotating speed is 75 rev/mins, and mixing time is 6 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.[embodiment 2]
The preparation of syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials
In blender, do 20 parts of polyamide 6s (PA6) (molecular weight is 18000), 4 parts of organo montmorillonites (MTA) and 0.1 part of antioxidant 1010 mixed earlier, and then mixing kneading in mixing roll, mixing condition is: temperature is 230～235 ℃, and rotating speed is 75 rev/mins, and mixing time is 8 minutes.Add then and in blender, done mixed blended stock in advance, (weight-average molecular weight is 350,000 to the 80 parts of syndiotactic polystyrenes that consist of of blended stock, between normality 97%, fusing point is 272 ℃), 5 parts of sulfonated syndiotactic polyphenylethylenes (SsPS, sulfonation degree is 8.65 moles of %) and 0.1 part of antioxidant 1010.Being warming up to temperature in 3 minutes is 285 ℃, and the control rotating speed is 75 rev/mins, continues mixing 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.[embodiment 3]
The preparation of syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials
In blender, do 20 parts of polyamide 6s (PA6) (molecular weight is 18000), 6 parts of organo montmorillonites (MTA) and 0.1 part of antioxidant 1010 mixed earlier, and then mixing kneading in mixing roll, mixing condition is: temperature is 230～235 ℃, and rotating speed is 75 rev/mins, and mixing time is 8 minutes.Add then and in blender, done mixed blended stock in advance, (weight-average molecular weight is 350,000 to the 80 parts of syndiotactic polystyrenes that consist of of blended stock, between normality 97%, fusing point is 272 ℃), 5 parts of sulfonated syndiotactic polyphenylethylenes (SsPS, sulfonation degree is 8.65 moles of %) and 0.1 part of antioxidant 1010.Being warming up to temperature in 3 minutes is 285 ℃, and the control rotating speed is 75 rev/mins, continues mixing 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.[embodiment 4]
The preparation of syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials
In blender, do 20 parts of polyamide 6s (PA6) (molecular weight is 18000), 6 parts of organo montmorillonites (MTA) and 0.1 part of antioxidant 1010 mixed earlier, and then mixing kneading in mixing roll, mixing condition is: temperature is 230～235 ℃, and rotating speed is 75 rev/mins, and mixing time is 8 minutes.Add then and in blender, done mixed blended stock in advance, (weight-average molecular weight is 250,000 to the 80 parts of syndiotactic polystyrenes that consist of of blended stock, between normality 97%, fusing point is 272 ℃), 5 parts of sulfonated syndiotactic polyphenylethylenes (SsPS, sulfonation degree is 8.65 moles of %) and 0.1 part of antioxidant 1010.Being warming up to temperature in 3 minutes is 285 ℃, and the control rotating speed is 75 rev/mins, continues mixing 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.[embodiment 5]
The preparation of syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials
In blender, do 20 parts of polyamide 6s (PA6) (molecular weight is 18000), 6 parts of organo montmorillonites (MTA) and 0.1 part of antioxidant 1010 mixed earlier, and then mixing kneading in mixing roll, mixing condition is: temperature is 230～235 ℃, and rotating speed is 75 rev/mins, and mixing time is 8 minutes.Add then and in blender, done mixed blended stock in advance, (weight-average molecular weight is 600,000 to the 80 parts of syndiotactic polystyrenes that consist of of blended stock, between normality 97%, fusing point is 272 ℃), 5 parts of sulfonated syndiotactic polyphenylethylenes (SsPS, sulfonation degree is 8.65 moles of %) and 0.1 part of antioxidant 1010.Being warming up to temperature in 3 minutes is 285 ℃, and the control rotating speed is 75 rev/mins, continues mixing 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.[embodiment 6]
The preparation of syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials
In blender, do 20 parts of polyamide 6s (PA6) (molecular weight is 18000), 8 parts of organo montmorillonites (MTA) and 0.1 part of antioxidant 1010 mixed earlier, and then mixing kneading in mixing roll, mixing condition is: temperature is 230～235 ℃, and rotating speed is 75 rev/mins, and mixing time is 8 minutes.Add then and in blender, done mixed blended stock in advance, (weight-average molecular weight is 350,000 to the 80 parts of syndiotactic polystyrenes that consist of of blended stock, between normality 97%, fusing point is 272 ℃), 5 parts of sulfonated syndiotactic polyphenylethylenes (SsPS, sulfonation degree is 8.65 moles of %) and 0.1 part of antioxidant 1010.Being warming up to temperature in 3 minutes is 285 ℃, and the control rotating speed is 75 rev/mins, continues mixing 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.[embodiment 7]
The preparation of syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials
In blender, do 20 parts of polyamide 6s (PA6) (molecular weight is 18000), 4 parts of organo montmorillonites (MTA) and 0.1 part of antioxidant 1010 mixed earlier, and then mixing kneading in mixing roll, mixing condition is: temperature is 230～235 ℃, and rotating speed is 75 rev/mins, and mixing time is 8 minutes.Add then and in blender, done mixed blended stock in advance, (weight-average molecular weight is 350,000 to the 80 parts of syndiotactic polystyrenes that consist of of blended stock, between normality 97%, fusing point is 272 ℃), 5 parts of sulfonated syndiotactic polyphenylethylene zinc salts (sulfonation degree is 8.65 moles of %) and 0.1 part of antioxidant 1010.Being warming up to temperature in 3 minutes is 285 ℃, and the control rotating speed is 75 rev/mins, continues mixing 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.[embodiment 8]
The preparation of syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials
In blender, do 20 parts of polyamide 6s (PA6) (molecular weight is 18000), 6 parts of organo montmorillonites (MTA) and 0.1 part of antioxidant 1010 mixed earlier, and then mixing kneading in mixing roll, mixing condition is: temperature is 230～235 ℃, and rotating speed is 75 rev/mins, and mixing time is 8 minutes.Add then and in blender, done mixed blended stock in advance, (weight-average molecular weight is 350,000 to the 80 parts of syndiotactic polystyrenes that consist of of blended stock, between normality 97%, fusing point is 272 ℃), 5 parts of sulfonated syndiotactic polyphenylethylene zinc salts (sulfonation degree is 8.65 moles of %) and 0.1 part of antioxidant 1010.Being warming up to temperature in 3 minutes is 285 ℃, and the control rotating speed is 75 rev/mins, continues mixing 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.[embodiment 9]
The preparation of syndiotactic polystyrene, sulfonated syndiotactic polyphenylethylene and polyamide resin blends mixture
80 parts of (weight, as follows) syndiotactic polystyrene (weight-average molecular weight is 350,000, a normality 97%, fusing point is 272 ℃) in, add 20 parts of PA6 (molecular weight is 18000), 5 parts of sulfonated syndiotactic polyphenylethylenes (SsPS, sulfonation degree is 8.65 moles of %) and 0.1 part of antioxidant 1010 are done above-mentioned material mixed earlier in blender, and then mixing kneading in two Luo bar forcing machines, mixing condition is: temperature is 285 ℃, and rotating speed is 75 rev/mins, and mixing time is 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.[embodiment 10]
The preparation of syndiotactic polystyrene performance comparison thing
100 parts of (weight, as follows) (weight-average molecular weight is 350,000 to syndiotactic polystyrene, between normality 97%, fusing point is 272 ℃) in, add 0.1 part of antioxidant 1010, in blender, do above-mentioned material mixed earlier, and then mixing kneading in mixing roll, mixing condition is: temperature is 285 ℃, and rotating speed is 75 rev/mins, and mixing time is 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.
The performance of embodiment 1～10 hybrid materials sees Table 1.
The performance table of table 1 syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials
*
Annotate: in the above-mentioned data, shock strength and flexural strength adopt cantilever method to measure at normal temperatures.
| Embodiment | SPS/SsPS/PA6/MTA (weight) | Shock strength (kilojoule/rice 2) | Clay dispersion phase size (nanometer) | Flexural strength (MPa) | Tensile strength (MPa) | Elongation at break (%) | ??HDT/TMA ???(℃) |
| ????1 | ????80/5/20/4 | ????16.0 | ????5.3 | ????65.3 | ????56.1 | ????6.7 | ????202 |
| ????2 | ????80/5/20/4 | ????16.1 | ????9.7 | ????65.0 | ????55.8 | ????6.4 | ????203 |
| ????3 | ????80/5/20/6 | ????16.3 | ????6.7 | ????70.7 | ????63.9 | ????6.9 | ????207 |
| ????4 | ????80/5/20/6 | ????16.2 | ????11.3 | ????68.9 | ????62.1 | ????6.7 | ????205 |
| ????5 | ????80/5/20/6 | ????16.6 | ????19.8 | ????71.3 | ????64.3 | ????6.9 | ????208 |
| ????6 | ????80/5/20/8 | ????14.8 | ????22.1 | ????71.5 | ????64.2 | ????5.4 | ????211 |
| ????7 | ????80/5/20/4 | ????13.6 | ????7.8 | ????70.6 | ????56.7 | ????5.3 | ????209 |
| ????8 | ????80/5/20/6 | ????14.0 | ????36.3 | ????71.2 | ????67.8 | ????5.1 | ????212 |
| ????9 | ????80/5/20/0 | ????15.6 | ＞10 microns | ????51.0 | ????34.7 | ????8.3 | ????176 |
| ????10 | ????100/0/0/0 | ????5.3 | ＞10 microns | ????48.6 | ????33.6 | ????1.2 | ????--- |
Among the embodiment 1～6 and 9, adopt not in and sulfonated syndiotactic polyphenylethylene be expanding material, sulfonation degree is 8.65 moles of %.
Among the embodiment 7 and 8, the sulfonated syndiotactic polyphenylethylene zinc salt is an expanding material, and sulfonation degree is 8.65 moles of %.
HDT/TMA: temperature when deformation begins to increase in temperature-inflection curves, adopt TMA to measure.
Adopt transmissioning electric mirror determining disperse phase nano-scale.
Claims (16)
1, a kind of syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials comprise following component in parts by weight:
A) syndiotactic polystyrene is 1～99 part;
B) sulfonated syndiotactic polyphenylethylene is 1～50 part;
C) polyamide resin is 1～50 part;
D) the polyamide-clay nano-complex is 1～50 part;
E) be selected from 1～50 part of the auxiliary agent of oxidation inhibitor, fire retardant, nucleator or impact modifying agent and composition thereof;
Wherein hybrid materials medium clay soil disperse phase particle diameter is 5～90 nanometers.
2, according to the described syndiotactic polyphenylethylene/polyamide of claim 1/clay nano hybrid materials, it is characterized in that in parts by weight, the syndiotactic polystyrene amount is 50～85 parts, and wherein the weight-average molecular weight of syndiotactic polystyrene is 20～700,000, and a normality is greater than 96%.
3, according to the described syndiotactic polyphenylethylene/polyamide of claim 1/clay nano hybrid materials, it is characterized in that the sulfonation degree of sulfonated syndiotactic polyphenylethylene counts 1～20% with molar percentage, in parts by weight, the sulfonated syndiotactic polyphenylethylene amount is 1～20 part.
4,, it is characterized in that polyamide resin is selected from polyamide 6, polyamide 66, polyamide 6 10, polyamide 1010, polymeric amide 4, polymeric amide 9, polymeric amide 46, polymeric amide 11, polymeric amide 12 or aromatic polyamides according to the described syndiotactic polyphenylethylene/polyamide of claim 1/clay nano hybrid materials.
5,, it is characterized in that polymeric amide is a polyamide 6 according to the described syndiotactic polyphenylethylene/polyamide of claim 4/clay nano hybrid materials.
6,, it is characterized in that in parts by weight polyamide resin amount be 5～40 parts according to the described syndiotactic polyphenylethylene/polyamide of claim 1/clay nano hybrid materials.
7,, it is characterized in that the polyamide-clay nano-complex is selected from intercal type or the exfoliated polyamide-clay nano-complex that adopts the intercalation complex method to prepare according to the described syndiotactic polyphenylethylene/polyamide of claim 1/clay nano hybrid materials.
8,, it is characterized in that the polyamide-clay nano-complex is polyamide 6/clay nano mixture according to the described syndiotactic polyphenylethylene/polyamide of claim 7/clay nano hybrid materials.
9, described according to Claim 8 syndiotactic polyphenylethylene/polyamide/clay nano hybrid materials is characterized in that in parts by weight polyamide 6/clay nano mixture amount be 3～40 parts.
10, according to the described syndiotactic polyphenylethylene/polyamide of claim 1/clay nano hybrid materials, it is characterized in that clay is selected from the silicate compound or the natural silicate clay of the synthetic with laminate structure, comprise that polynite, talcum, zeolite, vermiculite, sepiolite, synthetic mica, lithium montmorillonite, white clay, the phosphoric acid salt with laminate structure, graphite, metal oxide are or/and disulphide.
11, according to the described syndiotactic polyphenylethylene/polyamide of claim 10/clay nano hybrid materials, it is characterized in that clay is polynite, the cation exchange capacity of polynite is 40～140 mmoles/100 grams.
12, according to the described syndiotactic polyphenylethylene/polyamide of claim 11/clay nano hybrid materials, it is characterized in that polynite is an organo montmorillonite, be the product of polynite gained after organic agent is handled, organic agent is selected from the compound with following structural formula: CH
3(CH
2)
nNR
3X and/or HOOC (CH
2)
N-1NH
2, R is H or CH
3X is Cl, Br or I; N=4～60.
13,, it is characterized in that organic agent is ten monoamino-acids or ten diamino acid according to the described syndiotactic polyphenylethylene/polyamide of claim 12/clay nano hybrid materials.
14,, it is characterized in that the organo montmorillonite amount is 1～20% of a hybrid materials weight by weight percentage according to the described syndiotactic polyphenylethylene/polyamide of claim 12/clay nano hybrid materials.
15,, it is characterized in that oxidation inhibitor is selected from antioxidant 1010, PEP36, Mark Ao-30 or BHT according to the described syndiotactic polyphenylethylene/polyamide of claim 1/clay nano hybrid materials; Nucleator is selected from Sodium Benzoate or p t butylbenzoic acid aluminium; Impact modifying agent is selected from segmented copolymer, ABS or the urethane etc. of segmented copolymer, vinylbenzene and different propylene of segmented copolymer, hydrogenated styrene and the divinyl of styrene-butadiene rubber(SBR), vinylbenzene and divinyl.
16,, it is characterized in that hybrid materials medium clay soil disperse phase particle diameter is 5～50 nanometers according to the described syndiotactic polyphenylethylene/polyamide of claim 1/clay nano hybrid materials.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314730C (en) * | 2005-04-28 | 2007-05-09 | 华东理工大学 | Polyamide extruded from reaction between low dimensional nano clay and monomer of polyamide, and preparation method thereof |
| CN103642209A (en) * | 2013-11-18 | 2014-03-19 | 安徽宜万丰电器有限公司 | Waterproof temperature-resistant modified nylon material for automobile plastic members |
| CN105367978A (en) * | 2015-11-18 | 2016-03-02 | 安徽雄亚塑胶科技有限公司 | TPE composition and liquor bottle stopper prepared from TPE composition |
| CN107858019A (en) * | 2017-10-12 | 2018-03-30 | 桂林浩新科技服务有限公司 | A kind of method for preparing monolithic talcum powder |
-
2002
- 2002-04-10 CN CN 02111308 patent/CN1203124C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314730C (en) * | 2005-04-28 | 2007-05-09 | 华东理工大学 | Polyamide extruded from reaction between low dimensional nano clay and monomer of polyamide, and preparation method thereof |
| CN103642209A (en) * | 2013-11-18 | 2014-03-19 | 安徽宜万丰电器有限公司 | Waterproof temperature-resistant modified nylon material for automobile plastic members |
| CN105367978A (en) * | 2015-11-18 | 2016-03-02 | 安徽雄亚塑胶科技有限公司 | TPE composition and liquor bottle stopper prepared from TPE composition |
| CN107858019A (en) * | 2017-10-12 | 2018-03-30 | 桂林浩新科技服务有限公司 | A kind of method for preparing monolithic talcum powder |
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|---|---|
| CN1203124C (en) | 2005-05-25 |
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