CN102888110A - Manufacturing method of polyphenylene sulfide composite granulate containing toughening materials - Google Patents
Manufacturing method of polyphenylene sulfide composite granulate containing toughening materials Download PDFInfo
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- CN102888110A CN102888110A CN2011101997502A CN201110199750A CN102888110A CN 102888110 A CN102888110 A CN 102888110A CN 2011101997502 A CN2011101997502 A CN 2011101997502A CN 201110199750 A CN201110199750 A CN 201110199750A CN 102888110 A CN102888110 A CN 102888110A
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- polyphenylene sulfide
- toughening material
- elastic body
- oxidation
- screw extruder
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 72
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000008187 granular material Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000012756 surface treatment agent Substances 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 3
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims description 30
- 238000007254 oxidation reaction Methods 0.000 claims description 30
- -1 4-epoxycyclohexyl Chemical group 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- 239000003365 glass fiber Substances 0.000 claims description 17
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 16
- 150000003568 thioethers Chemical class 0.000 claims description 16
- NWODFYYWMUKPPE-UHFFFAOYSA-N C(C(=C)C)(=O)OC(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.P(O)(O)O Chemical compound C(C(=C)C)(=O)OC(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.P(O)(O)O NWODFYYWMUKPPE-UHFFFAOYSA-N 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 12
- 238000005453 pelletization Methods 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 11
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 4
- 238000004925 denaturation Methods 0.000 abstract description 3
- 230000036425 denaturation Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000011152 fibreglass Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 235000006708 antioxidants Nutrition 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 abstract 1
- 239000000806 elastomer Substances 0.000 abstract 1
- 239000000945 filler Substances 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000012764 mineral filler Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- JRSJRHKJPOJTMS-MDZDMXLPSA-N trimethoxy-[(e)-2-phenylethenyl]silane Chemical compound CO[Si](OC)(OC)\C=C\C1=CC=CC=C1 JRSJRHKJPOJTMS-MDZDMXLPSA-N 0.000 description 3
- QHMVQKOXILNZQR-UHFFFAOYSA-N 1-methoxyprop-1-ene Chemical group COC=CC QHMVQKOXILNZQR-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- NHFDKKSSQWCEES-UHFFFAOYSA-N dihydrogen phosphate;tris(2-hydroxyethyl)azanium Chemical compound OP(O)(O)=O.OCCN(CCO)CCO NHFDKKSSQWCEES-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical class CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- UUIPAJHTKDSSOK-UHFFFAOYSA-N (2-nonylphenyl) dihydrogen phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(O)(O)=O UUIPAJHTKDSSOK-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 208000000848 Autosomal recessive primary microcephaly Diseases 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 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 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 201000001729 primary autosomal recessive microcephaly Diseases 0.000 description 1
- AMCPECLBZPXAPB-UHFFFAOYSA-N propane-1,2,3-triol;sodium Chemical compound [Na].OCC(O)CO AMCPECLBZPXAPB-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a manufacturing method of polyphenylene sulfide composite granulate containing toughening materials. The method comprises adding an anti-oxidant, micron PA6 elastomer toughening material and other fillers into the non-linear polyphenylene sulfide, fully and uniformly mixing in a high-speed mixer to obtain a premix of the polyphenylene sulfide, inputting the premix of the polyphenylene sulfide and the fiberglass treated by a surface treatment agent of beta-(3,4-epoxy cyclohexyl)ethyltrimethoxysilane (A-168) into a double-screw extruder for mixing, extruding and molding, and then cooling and cutting to form the finished composite granulates. The composite granulates obtained by the method has advantages of high thermal denaturation stability and tensile strength, and low metal corrosion, and can be widely applied in the fields of electronic appliances, machinery, chemical industry, petroleum, military industry, and aerospace.
Description
Affiliated technical field
The invention belongs to speciality polymer material Application Areas
Background technology
Polyphenylene sulfide (PPS) good heat stability, has outstanding high thermal resistance, fusing point reaches 285 ℃, other special engineering plastics that are higher than present suitability for industrialized production, the PPS composite granule has good injection processing characteristics, can be processed into the PPS composite product of all size, different shape.But in the more harsh field of some application conditions, explore and find that the more good PPS matrix material of performance is still the target that people pursue.
Introduced among the Chinese patent CN:1667044A and a kind ofly added aromatic phosphoric ester and polyphenylene oxides is the manufacture method of the polyphenyl thioether composite material of resin, its objective is at injection molding SHI and improve the heat-resistant stability of matrix material and the surface smoothness of shaped material.But the dispersion effect of aromatic phosphoric ester in polyphenylene sulfide is undesirable, easily forms the parcel phenomenon when producing under the general technology level, thereby directly have influence on high-temperature mechanical property in pellet.
Introduced among the Chinese patent CN:1253149A and a kind ofly added epoxy silane compounds and high component is inorganic, the manufacture method of the polyphenylene sulfide of organic fibre (PPS) matrix material, its objective is and want to reduce this matrix material at the overlap of injection molded.Thereby provide a kind of have good processing characteristics, the polyphenyl thioether composite material of physical strength, although the overlap behind the packing materials such as adding epoxy silane compounds when being injected into part reduces, and has but reduced resistance to impact shock and the tensile strength of polyphenyl thioether composite material.
Introduced the manufacture method that employing zinc oxide palpus crystalline substance and glass fibre or carbon fiber and polyphenylene sulfide (PPS) resin carry out polyphenylene sulfide (PPS) matrix material of blending and modifying among the Chinese patent CN:1272124A, its objective is that adopting zinc oxide is that corrosion inhibitor improves corrosion of metal, can eliminate the detrimentally affect of mechanical-physical character; But after adding zinc oxide, tensile strength and the elongation at break of the polyphenylene sulfide of making (PPS) matrix material injection forming decrease, and its resistance to impact shock also decreases.
Introduced a kind of production method that adds thermo-stabilizer and contain the polyphenyl thioether composite granulates of toughening material 3 penta isopropyl glue, phenyl alkylsulf, polystyrene, clorafin thing in Chinese patent application number NO:200710050119.x, this patent is to adopt very common method poly-p-phenylene sulfide ether resin to carry out modification to strengthen in fact.
In view of the above shortcoming of prior art, the objective of the invention is to study a kind ofly produce shock-resistant, high stabile against thermal denaturation, tensile strength is good and the polyphenyl thioether composite material that contains glass fibre low to metallic corrosion, good processability.
Summary of the invention:
Its main technique comprises:
A kind of manufacture method that contains the polyphenyl thioether composite granulates of toughening material, to add oxidation inhibitor, polyphenylene sulfide cross-linked resin Preblend behind the PA6 elastic body toughening material fully mixes in homogenizer, be shaped with glass fibre input parallel dual-screw extruding machine mixing extrusion again, through cooling, pelletizing forms composite granule, it is characterized in that, adopt following processing step: 1 is 3-5 ten thousand with weight-average molecular weight, melt flow index is that 300-600g/10min and molecular weight distribution are the linear polyphenylene sulfide resin of 2.2-2.5, adds the crosslinked 2-3h of the heat of oxidation in the crosslinked device of the heat of oxidation;
2 will be 1) in homogenizer, fully mix after adding the weighting agents such as PA6 elastic body toughening material that oxidation inhibitor, its granularity are 35-40um in the polyphenylene sulfide cross-linked resin that obtains, the weight ratio of used antioxidant phosphorous acid triphenylmethyl methacrylate in the ninth of the ten Heavenly Stems and polyphenylene sulfide is 2-2.5: 100; The weight ratio of PA6 elastic body toughening material and polyphenylene sulfide is 30-40: 100 obtain polyphenylene sulfide Preblend with this;
3 with (2) gained polyphenylene sulfide Preblend 50-55%wt again with through β-(3, the 4-epoxycyclohexyl) the 50-45%wt diameter was the glass fibre input twin screw extruder of 30-40um after ethyl trimethoxy silane (A-168) surface treatment agent was processed, and formed the finished product composite granule through the shaping of twin screw extruder mixing extrusion, cooling, pelletizing.
4 need to add PA6 elastic body toughening material in polyphenylene sulfide Preblend manufacturing processed, the overlap length of moulding is 0.3-0.5um, improve simultaneously the toughness of 60-80% polyphenyl thioether composite material, and the melt strength of polyphenyl thioether composite material improves 25-30%.
The purpose that adds PA6 elastic body toughening material in the process of the present invention is to reduce on the one hand the burr (overlap) of moulding, improve on the other hand the melt strength of matrix material in injection moulding process, the 3rd, reduce the degree of crystallinity of matrix material and the crystallization velocity of raising matrix material, can reduce so the various losses of matrix material in injection moulding process, improve the yield rate of moulding.
In homogenizer, stir 2-3h after adding polyphenylene sulfide cross-linked resin, oxidation inhibitor, PA6 elastic body toughening material, PA6 elastic body toughening material, make it be mixed into homogeneous polyphenylene sulfide mixture, then with process β-(3, the 4-epoxycyclohexyl) single fiber diameter was the glass fibre input twin screw extruder of 20-30um after ethyl trimethoxy silane (A-168) surface treatment agent was processed, form the finished product composite granule through the shaping of twin screw extruder mixing extrusion, cooling, pelletizing, pack at last, put in storage, use.
The inventive method gained composite granule has high stabile against thermal denaturation and tensile strength, and is low to the metallic corrosion rate.Can be widely used in electronic apparatus, machinery, chemical industry, oil, military project, field of aerospace.
Description of drawings:
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is the product performance table that embodiment of the invention experiment obtains.
Embodiment
Embodiment 1
Be 30,000 with weight-average molecular weight, melt flow index is that 600g/10min and molecular weight distribution are 2.5 linear polyphenylene sulfide resin, adds in the crosslinked device of the heat of oxidation the crosslinked 3h of the heat of oxidation stand-by
In homogenizer, add 67.8%wt polyphenylene sulfide cross-linked resin, 2.2%wt phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems oxidation inhibitor, the 30%wt granularity is to stir 3h behind the PA6 elastic body toughening material of 35um, make it be mixed into homogeneous polyphenylene sulfide mixture, then the Preblend of 50%wt polyphenylene sulfide and 50%wt are through β-(3, the 4-epoxycyclohexyl) single fiber diameter was the glass fibre input twin screw extruder of 30um after ethyl trimethoxy silane (A-168) surface treatment agent was processed, be shaped through the twin screw extruder mixing extrusion, cooling, pelletizing forms the finished product composite granule, at last packing, warehouse-in, use.
The various physicalies of the polyphenyl thioether composite material that obtains with aforesaid method will show in Fig. 2 table.
Embodiment 2
Be 50,000 with weight-average molecular weight, melt flow index is that 300g/10min and molecular weight distribution are 2.5 linear polyphenylene sulfide resin, adds in the crosslinked device of the heat of oxidation the crosslinked 2h of the heat of oxidation stand-by
In homogenizer, add 51.5%wt polyphenylene sulfide cross-linked resin, 2.5%wt phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems oxidation inhibitor, the 40%wt granularity is to stir 2h behind the PA6 elastic body toughening material of 40um, make it be mixed into homogeneous polyphenylene sulfide mixture, then the Preblend of 55%wt polyphenylene sulfide and 45%wt are through β-(3, the 4-epoxycyclohexyl) single fiber diameter was the glass fibre input twin screw extruder of 40um after ethyl trimethoxy silane (A-168) surface treatment agent was processed, be shaped through the twin screw extruder mixing extrusion, cooling, pelletizing forms the finished product composite granule, at last packing, warehouse-in, use.
The various physicalies of the polyphenyl thioether composite material that obtains with aforesaid method will show in Fig. 2 table.
The comparative example 1
Be 40,000 with weight-average molecular weight, melt flow index is that 430g/10min and molecular weight distribution are 2.8 linear polyphenylene sulfide resin, adds in the crosslinked device of the heat of oxidation the crosslinked 3h of the heat of oxidation stand-by
In homogenizer, stir 3h after adding 98%wt polyphenylene sulfide cross-linked resin, 2%wt phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems oxidation inhibitor, make it be mixed into homogeneous polyphenylene sulfide mixture, then the Preblend of 50%wt polyphenylene sulfide and 50%wt are through β-(3, the 4-epoxycyclohexyl) single fiber diameter was the glass fibre input twin screw extruder of 30um after ethyl trimethoxy silane (A-168) surface treatment agent was processed, form the finished product composite granule through the shaping of twin screw extruder mixing extrusion, cooling, pelletizing, pack at last, put in storage, use.
Embodiment 3
Be 40,000 with weight-average molecular weight, melt flow index is that 451g/10min and molecular weight distribution are 2.3 linear polyphenylene sulfide resin, adds in the crosslinked device of the heat of oxidation the crosslinked 3h of the heat of oxidation stand-by
In homogenizer, add 60.7%wt polyphenylene sulfide cross-linked resin, 2.3%wt phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems oxidation inhibitor, the 37%wt granularity is to stir 2.5h behind the PA6 elastic body toughening material of 33um, make it be mixed into homogeneous polyphenylene sulfide mixture, then the Preblend of 51%wt polyphenylene sulfide and 49%wt are through β-(3, the 4-epoxycyclohexyl) single fiber diameter was the glass fibre input twin screw extruder of 35um after ethyl trimethoxy silane (A-168) surface treatment agent was processed, be shaped through the twin screw extruder mixing extrusion, cooling, pelletizing forms the finished product composite granule, at last packing, warehouse-in, use.
The various physicalies of the polyphenyl thioether composite material that obtains with aforesaid method will show in Fig. 2 table.
Embodiment 4
Be 4.5 ten thousand with weight-average molecular weight, melt flow index is that 360g/10min and molecular weight distribution are 2.4 linear polyphenylene sulfide resin, adds in the crosslinked device of the heat of oxidation the crosslinked 2.8h of the heat of oxidation stand-by
In homogenizer, add 60%wt polyphenylene sulfide cross-linked resin, 1.4%wt phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems oxidation inhibitor, the 32%wt granularity is to stir 3h behind the PA6 elastic body toughening material of 36um, make it be mixed into homogeneous polyphenylene sulfide mixture, then the Preblend of 54%wt polyphenylene sulfide and 46%wt are through β-(3, the 4-epoxycyclohexyl) single fiber diameter was the glass fibre input twin screw extruder of 36um after ethyl trimethoxy silane (A-168) surface treatment agent was processed, be shaped through the twin screw extruder mixing extrusion, cooling, pelletizing forms the finished product composite granule, at last packing, warehouse-in, use.
Embodiment 5
Be 3.8 ten thousand with weight-average molecular weight, melt flow index is that 420g/10min and molecular weight distribution are 2.4 linear polyphenylene sulfide resin, adds in the crosslinked device of the heat of oxidation the crosslinked 3h of the heat of oxidation stand-by
In homogenizer, add 64.5%wt polyphenylene sulfide cross-linked resin, 1.5%wt phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems oxidation inhibitor, the 34%wt granularity is to stir 2.6h behind the PA6 elastic body toughening material of 38um, make it be mixed into homogeneous polyphenylene sulfide mixture, then the Preblend of 53%wt polyphenylene sulfide and 47%wt are through β-(3, the 4-epoxycyclohexyl) single fiber diameter was the glass fibre input twin screw extruder of 36um after ethyl trimethoxy silane (A-168) surface treatment agent was processed, be shaped through the twin screw extruder mixing extrusion, cooling, pelletizing forms the finished product composite granule, at last packing, warehouse-in, use.
The comparative example 2
Be 50,000 with weight-average molecular weight, melt flow index is that 324g/10min and molecular weight distribution are 2.0 linear polyphenylene sulfide resin, adds in the crosslinked device of the heat of oxidation the crosslinked 3h of the heat of oxidation stand-by
In homogenizer, stir 2h after adding 98.5%wt polyphenylene sulfide cross-linked resin, 1.5%wt phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems oxidation inhibitor, make it be mixed into homogeneous polyphenylene sulfide mixture, then the Preblend of 55%wt polyphenylene sulfide and 45%wt are through β-(3, the 4-epoxycyclohexyl) single fiber diameter was the glass fibre input twin screw extruder of 30um after ethyl trimethoxy silane (A-168) surface treatment agent was processed, form the finished product composite granule through the shaping of twin screw extruder mixing extrusion, cooling, pelletizing, pack at last, put in storage, use.
Can see by tabulation one among Fig. 2: behind PA6 elastic body toughening material compound, the melt strength of polyphenylene sulfide (PPS) matrix material has obviously improved, overlap length obviously reduces, impact resistance, toughness, anti-bent pleat intensity, tensile strength obviously strengthen, and elongation at break also increases significantly with same type of material.
Owing to melting mixed very even with polyphenylene sulfide after adding PA6 elastic body toughening material compound and phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems compound, can not produce parcel phenomenon or particle shape, improved the processing performance of material, so just the balanced technique intensity index that has improved polyphenylene sulfide.
Product indices and employed detection method in the table:
Tensile strength and elongation are all carried out by GB/T1040-1992, and test speed is 10mm/min; Bent pleat intensity is pressed GB/T9341-1988 and is carried out, and resistance to impact shock is pressed GB/T1843-1996 and carried out, and heat-drawn wire is pressed the regulation of GB/T1634-1979 (1989) and carried out.
Performance index by Fig. 2 can be found out, the thermostability of product improves, and commercially available Japanese firm is contained glass fibre 40% like product parallel laboratory test, and its tensile strength, elongation, the bent pleat intensity of glass, resistance to impact shock are respectively 281Mpa, 3.7%, 315Mpa and 18.4j/m
2
After also finding in the experiment to add thicker glass fibre, for example single fiber diameter 35um parallel laboratory test, its resistance to impact shock has obvious enhancing.The adding of PA6 elastic body toughening material also significantly improves the help that forward is provided to tensile strength and the elongation at break of product of the present invention.
After adding PA6 elastic body toughening material compound and phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems compound, polyphenylene sulfide (PPS) matrix material is when thermostability obviously improves, and product overlap length is reduction trend.Since after adding PA6 elastic body toughening material compound and phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems compound, molten mixed very even with polyphenylene sulfide, can not produce parcel phenomenon or particle shape yet.The improvement of all these processing condition makes some physical propertiess of product and processing performance obtain comprehensive improvement.
Although embodiments of the invention are with hexamethylene six alkane methyl alcohol polyoxy vinylbenzene ether phosphate amine salt (diethyls, three second), glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt is what provide, also can consider wider Fatty Alcohol(C12-C14 and C12-C18) polyoxy vinylbenzene ether phosphate compounds in the actual production, for example: the aliphatic alcohol polyoxyvinethene phosphate sodium salt, hexamethylene six alkane methyl alcohol polyoxy vinylbenzene ether phosphate amine salt (diethyls, three second), fatty alcohol-ether (7) phosphoric acid ester triethanolamine salt, fatty alcohol-ether (9) phosphoric acid ester triethanolamine salt, octanol phophoric ester MCPH, octanol polyoxyethylene phosphate OPEK, nonyl phenol phosphate sylvite, nonyl phenol ether phosphoric acid monoesters ethanolamine salt, Nonyl pheno (7) ether phosphoric acid, single, dibasic acid esters Nonyl pheno (4-10) ether phosphoric acid, single, dibasic acid esters, the glycerin polyoxyethylene ether phosphoric acid ester, glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt, PAPE, higher alcohols phosphoric acid ester sodium and phosphorylation Viscotrol C sodium salt, Stearinsaeure, the sulfuric ester of glycerol sodium salt, Castor Oil Phosphate Ester Salt, one or more compounds of the phosphate ester salts such as phosphorous acid triphenylmethyl methacrylate in the ninth of the ten Heavenly Stems.
The PA6 elastic body toughening material resin compound that adds in the present invention, can reduce the overlap (burr) that polyphenyl thioether composite granulates produces when injection moulded products is shaped, make the surface smoothness height of its molded article and the toughness of injection molded goods, these organoalkoxysilane resins can be vinyltrimethoxy silanes, vinyltriethoxysilane, the styryl triethoxyl silane, the styryl Trimethoxy silane, 3 monomethyl propenyloxy group propyl group methyl dimethoxysilanes, 3 monomethyl propenyloxy group propyl trimethoxy silicanes, 3 monomethyl propenyloxy group propyl group methyldiethoxysilane, 3 monomethyl propenyloxy group propyl-triethoxysilicanes, in the organoalkoxysilanes such as 3-propenyloxy group propyl trimethoxy silicane one or more, especially with vinyltrimethoxy silane, vinyltriethoxysilane, the styryl triethoxyl silane, the styryl Trimethoxy silane, PA6 elastic body toughening material is better, with the styryl triethoxyl silane, the styryl Trimethoxy silane, PA6 elastic body toughening material is best.
The objectionable impurities trapping agent that the present invention can also add is inclined to one side zincic acid/zincic acid or its esters compound, and they are: zincic acid, partially zincic acid, inclined to one side zincic acid calcium, partially zincic acid magnesium, partially zincic acid barium, zincic acid calcium, zincic acid magnesium, zincic acid barium, zinc carbonate, etc. contain the compound of zinc, with zincic acid, partially zincic acid is best, and they not only can suppress the generation of corrosives and impurity, can also replenish among the pellet as mineral filler.
Employed fiberglass surface treating agent is to adopt well-known β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (A-168) surface treatment agent among the present invention.
The mineral filler that can also add among the present invention reduces the overlap (burr) of polyphenylene sulfide resin composite material model when injection forming, these mineral fillers can be carbon blacks, nanometer grade silica, nanometer order quartz sand, glass microballon, the nanometer glass powder, Calucium Silicate powder, pure aluminium silicate, talcum, clay, mica, diatomite, the silicate such as wollastonite, ferric oxide, Nano titanium dioxide, zinc oxide, aluminum oxide, light calcium carbonate, nanometer grade calcium carbonate, magnesiumcarbonate, plaster stone, barium sulfate, silicon carbide, silicon nitride, boron nitride etc. are especially with nanometer grade calcium carbonate, nanometer grade silica, Nano titanium dioxide is best.
Claims (3)
1. manufacture method that contains the polyphenyl thioether composite granulates of toughening material, polyphenylene sulfide cross-linked resin Preblend behind adding oxidation inhibitor, the PA6 elastic body toughening material is fully mixed in homogenizer, be shaped, form composite granule through cooling, pelletizing with glass fibre input parallel dual-screw extruding machine mixing extrusion again, it is characterized in that, adopt following processing step:
1) be 3-5 ten thousand with weight-average molecular weight, melt flow index is that 300-600g/10min and molecular weight distribution are the linear polyphenylene sulfide resin of 2.2-2.5, adds the crosslinked 2-3h of the heat of oxidation in the crosslinked device of the heat of oxidation;
2) will be 1) in homogenizer, fully mix after adding the weighting agents such as oxidation inhibitor, PA6 elastic body toughening material in the polyphenylene sulfide cross-linked resin that obtains, the weight ratio of used antioxidant phosphorous acid triphenylmethyl methacrylate in the ninth of the ten Heavenly Stems and polyphenylene sulfide is 2-2.5: 100; The weight ratio of PA6 elastic body toughening material and polyphenylene sulfide is 30-40: 100 obtain polyphenylene sulfide Preblend with this;
3) with (2) gained polyphenylene sulfide Preblend 50-55%wt again with through β-(3, the 4-epoxycyclohexyl) the ethyl trimethoxy silane surface treatment agent is processed later 50-45%wt glass fibre input twin screw extruder, forms the finished product composite granule through the shaping of twin screw extruder mixing extrusion, cooling, pelletizing.
2. described a kind of manufacture method that contains the polyphenyl thioether composite granulates of toughening material according to claim 1 is characterized in that, described PA6 elastic body toughening material is micron order PA6 elastic body toughening material, and its granularity is 35-40um.
3. described a kind of manufacture method that contains the polyphenyl thioether composite granulates of toughening material according to claim 1 is characterized in that, the glass fibre single fiber diameter is 30-40um.
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| US4782105A (en) * | 1987-04-10 | 1988-11-01 | Ciba-Geigy Corporation | Long chain N,N,-dialkylhydroxylamines and stabilized compositions |
| CN101397405A (en) * | 2007-09-27 | 2009-04-01 | 四川得阳化学有限公司 | Method for manufacturing high toughness polyphenyl thioether composite pellets |
| CN101967280A (en) * | 2010-09-02 | 2011-02-09 | 中国工程物理研究院化工材料研究所 | Anti-cracking polyphenyl thioether composite material and preparation method thereof |
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