CN105733023B - Composite assistant for high-density polyethylene pressure-resistant pipe, preparation method thereof and resin raw material containing composite assistant - Google Patents
Composite assistant for high-density polyethylene pressure-resistant pipe, preparation method thereof and resin raw material containing composite assistant Download PDFInfo
- Publication number
- CN105733023B CN105733023B CN201410764954.XA CN201410764954A CN105733023B CN 105733023 B CN105733023 B CN 105733023B CN 201410764954 A CN201410764954 A CN 201410764954A CN 105733023 B CN105733023 B CN 105733023B
- Authority
- CN
- China
- Prior art keywords
- density polyethylene
- composite assistant
- hdpe
- resistant pipe
- high density
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001903 high density polyethylene Polymers 0.000 title claims abstract description 138
- 239000004700 high-density polyethylene Substances 0.000 title claims abstract description 133
- 239000011347 resin Substances 0.000 title claims abstract description 91
- 229920005989 resin Polymers 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000002994 raw material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 80
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 45
- 230000032683 aging Effects 0.000 claims abstract description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 20
- 238000012545 processing Methods 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 239000000344 soap Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229920001973 fluoroelastomer Polymers 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 235000006708 antioxidants Nutrition 0.000 claims description 42
- -1 propionic acid n-octadecane alcohol ester Chemical class 0.000 claims description 36
- 239000012752 auxiliary agent Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 16
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 11
- 229920002449 FKM Polymers 0.000 claims description 10
- 235000013539 calcium stearate Nutrition 0.000 claims description 10
- 238000005453 pelletization Methods 0.000 claims description 10
- 235000019260 propionic acid Nutrition 0.000 claims description 9
- 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 claims description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 239000008116 calcium stearate Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- WTWGHNZAQVTLSQ-UHFFFAOYSA-N 4-butyl-2,6-ditert-butylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WTWGHNZAQVTLSQ-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical class C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 claims description 3
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical class C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 claims description 3
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 3
- 229940063655 aluminum stearate Drugs 0.000 claims description 3
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 claims description 3
- HIAAVKYLDRCDFQ-UHFFFAOYSA-L calcium;dodecanoate Chemical compound [Ca+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O HIAAVKYLDRCDFQ-UHFFFAOYSA-L 0.000 claims description 3
- POWRQOUEUWZUNQ-UHFFFAOYSA-N didecyl phosphite Chemical compound CCCCCCCCCCOP([O-])OCCCCCCCCCC POWRQOUEUWZUNQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- KHWQFISNNNRGLV-UHFFFAOYSA-N 2,4,6-tributylphenol Chemical class CCCCC1=CC(CCCC)=C(O)C(CCCC)=C1 KHWQFISNNNRGLV-UHFFFAOYSA-N 0.000 claims description 2
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 claims description 2
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical class CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- AXRSHKZFNKUGQB-UHFFFAOYSA-N octyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC)OC1=CC=CC=C1 AXRSHKZFNKUGQB-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 239000003017 thermal stabilizer Substances 0.000 claims 2
- 241001614291 Anoplistes Species 0.000 claims 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- QICVZJNIJUZAGZ-UHFFFAOYSA-N benzene;phosphorous acid Chemical compound OP(O)O.C1=CC=CC=C1 QICVZJNIJUZAGZ-UHFFFAOYSA-N 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 230000006353 environmental stress Effects 0.000 abstract description 8
- 230000007774 longterm Effects 0.000 abstract description 5
- 230000000087 stabilizing effect Effects 0.000 abstract 2
- 239000000843 powder Substances 0.000 description 26
- 239000000178 monomer Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 238000009826 distribution Methods 0.000 description 12
- 230000002902 bimodal effect Effects 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000003723 Smelting Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 230000006698 induction Effects 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002216 antistatic agent Substances 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229920006373 Solef Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003026 anti-oxygenic effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- AVYPEYYPGYMFDO-UHFFFAOYSA-N 1,3,5-tributylbenzene Chemical class CCCCC1=CC(CCCC)=CC(CCCC)=C1 AVYPEYYPGYMFDO-UHFFFAOYSA-N 0.000 description 1
- WIXDSJRJFDWTNY-UHFFFAOYSA-N 1,3-ditert-butyl-5-methylbenzene Chemical class CC1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1 WIXDSJRJFDWTNY-UHFFFAOYSA-N 0.000 description 1
- PZPVXSMCRLNVRD-UHFFFAOYSA-N 2,6-dibutylphenol Chemical compound CCCCC1=CC=CC(CCCC)=C1O PZPVXSMCRLNVRD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000011074 autoclave method Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical class OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- MORMPWNLQJTSOT-UHFFFAOYSA-L disodium;4-dodecyl-2-(4-sulfonatophenoxy)benzenesulfonate Chemical compound [Na+].[Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C(OC=2C=CC(=CC=2)S([O-])(=O)=O)=C1 MORMPWNLQJTSOT-UHFFFAOYSA-L 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006210 lotion 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
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- SJOCPYUKFOTDAN-ZSOIEALJSA-N methyl (4z)-4-hydroxyimino-6,6-dimethyl-3-methylsulfanyl-5,7-dihydro-2-benzothiophene-1-carboxylate Chemical compound C1C(C)(C)C\C(=N\O)C=2C1=C(C(=O)OC)SC=2SC SJOCPYUKFOTDAN-ZSOIEALJSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- GJYCVCVHRSWLNY-UHFFFAOYSA-N ortho-butylphenol Natural products CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical class OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- 241000894007 species Species 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 230000035882 stress Effects 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Rigid Pipes And Flexible Pipes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a composite additive for a high-density polyethylene pressure-resistant pipe, which comprises 30-50 parts by weight of a long-term aging-resistant additive, 10-30 parts by weight of a thermal stabilizing additive and 10-30 parts by weight of a processing additive, wherein the long-term aging-resistant additive is selected from at least one of a group consisting of hindered phenol antioxidants, amine antioxidants and phosphorus antioxidants, the thermal stabilizing additive is selected from at least one of metal soap stabilizers, and the processing additive is composed of at least one fluoroelastomer. The invention also provides a preparation method of the composite additive and a high-density polyethylene pressure-resistant pipe resin raw material containing the composite additive. The high-density polyethylene pressure-resistant pipe material containing the composite additive has excellent processing performance, and the formed pipe material has excellent environmental stress crack resistance, aging resistance and rigidity-toughness balance.
Description
Technical field
It compound is helped the present invention relates to high density polyethylene (HDPE) pressure resistant pipe material composite assistant and preparation method thereof and containing this
The high density polyethylene (HDPE) pressure resistant pipe material resin raw material of agent.
Background technology
Polyvinyl piping materials have chemical resistance outstanding, lower temperature resistance, heat-resistant antifriction, welding characteristic excellent, not dirty
The performances such as pumped (conveying) medium, service life are long, manufacture mounting cost is low are contaminated, are widely used in fuel gas transmission, water supply, row at present
The fields such as dirt, heat supply, petrochemical industry and telecommunications.
The exploitation of polyvinyl piping materials has more than 50 years history so far, and development is generally divided into three phases.First stage
Start from the 1950s, this stage occur first generation high density polyethylene (HDPE) (High Density Polyethylene,
HDPE) pressure resistant pipe material, performance is poor, is equivalent to PE63 and grade below.Second stage starts from phase late 1970s,
There is the PE80 grade special material for tube with higher long-term hydraulic pressure resistant intensity and anti-cracking performance in succession in this stage, due to
Environmental stress crack resistance is excellent, and the PE80 grades of special material for tube is in the manufacture of the polyvinyl piping materials of water supply and gas transmission and distribution system
It is widely applied.Phase III starts from late 1980s, third generation PE special material for tube occurs in this stage
PE100, the PE100 grades of pipe resin under conditions of 20 DEG C, the minimum of tubing must intensity be 10MPa, and service life
With the characteristics of 50 years.Also, PE100 grades of tubing of majority have the characteristics that bimodal molecular weight distribution, wherein low molecular weight part
The melt viscosity of resin at high shear rates can be effectively reduced, improves the mobility in material processing, ensures that material has
High crystallinity, high molecular weight moieties can then assign tubing good mechanical performance.
For example, document " PE100 grades of pipe resin structures and performance study " (elastomer, 2012,22 (4):57~60) in
Report the pressure resistant pipe material resin and its properties using the production of autoclave slurry process.Pass through the domestic material with its similar performance
And import material is compared, which shows unique performance advantage with resin, but in the publication not
The problem of referring to pressure resistant pipe material used additives aspect.
For another example, document " structure of PE100 special material for tube and rheological behaviour research " (plastics science and technology, 2011,39 (3):64
~66) basic structure performance, the rheological behaviour of three kinds of PE100 special material for tube JHMGC100S, YGH041 and P600 are reported in
And the result of study of dynamic rheological behavior.In the document, for the property of autoclave method production PE100 special material for tube JHMGC100S
The problem of in terms of technique adjustment direction when energy advantage and tubular object extruding, is summarized.However, not referring to wherein resistance to yet
The problem of pressing the auxiliary formula aspect of special material for tube.
A kind of processing aid for polychloroethylene pipes and pipe fitting is disclosed in CN102786622B and uses the processing
The poly (vinyl chloride) resin composition of auxiliary agent.The processing aid is prepared using two sections of emulsion polymerization techniques, and when emulsion polymerization adopts
Use disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate as emulsifier.First segment monomer composition accounts for 50 weights of monomer composition total amount
% is measured, second segment monomer composition accounts for 50 weight % of monomer composition total amount.Second segment monomer composition is dripped using pre-emulsification
The method added, polymerization temperature are controlled at 55~75 DEG C, prepare copolymer emulsion, and after lotion is spray-dried again, solid powder is made
Product.Wherein, it is in terms of 100% by first segment, second segment monomer composition total weight, styrene is 70~85%, and acrylonitrile is
10~20%, n-BMA is 0~10%.When using the processing aid, can significantly improve polychloroethylene pipes,
The hardness and heat-resistant stability of tubing products.
Disclosed in CN102807687A a kind of Compound stabilizer for plastic pipe, and preparation method thereof.The plastic pipe
With the group of compound stabilizer become 490~510 parts by weight of stearic acid, 120~130 parts by weight of yellow lead, 25~30 parts by weight of grey calcium,
1~2 parts by weight of acetic acid, 50~60 parts by weight of polyethylene wax, 170~185 parts by weight of tribasic lead sulfate, powdered whiting
350~360 parts by weight, 1~20 weight of 60~80 parts by weight of barium stearate, 10~20 parts by weight of dibasic lead stearate and bisphenol-A
Measure part.The compound stabilizer is suitable for plastic pipe, with that stability is good, high lubricating effect, at low cost, lead tolerance are low is excellent
Point.
In addition, disclosed in CN101638500B it is a kind of be polymerized using liquid phase noumenal method single loop reactors it is random
Polypropylene pipe timber-used composite assistant.The composite assistant is by 10~40 parts by weight of resisting ageing for long time auxiliary agent, processing aid 10
~30 parts by weight, 20~50 parts by weight of compound modifying agent and 10~30 parts by weight of weather resisting agent composition.Wherein, resisting ageing for long time helps
Agent is made of lactone stabilizer, hindered phenol anti-oxidants and nontoxic amine antioxidants, processing aid be fluoroelastomer, low point
One kind in sub- polymer arbitrarily matching several mixtures, weather resisting agent by ultra-violet absorber, organic nickel stabilizer and by
Hindered amine stabilizer forms, and compound modifying agent is compound modifying agent, the i.e. beta crystal-type nucleater for making alpha-crystal form be converted into beta crystal.It should
Composite assistant is the dedicated composite assistant of polypropylene pipe, is not suitable for polyvinyl piping materials, can make atactic copolymerized polypropene tree
Processing performance, mechanical property, environmental stress crack resistance and the resisting ageing for long time of fat significantly improve.
High density polyethylene (HDPE) pressure resistant pipe material resin has the characteristics that melt flow rate (MFR) is low, density is high.Therefore, processing is opposite
Difficulty, there is sharkskin in the outer wall of the tube wall uneven distribution, tubing that are easy to cause tubing, the inner surface of tubing rough etc. is asked
Topic.Also, since such tubing is used in the fields such as water supply, fuel gas transmission mostly, need to bear in use certain
Pressure and environmental aging, to also proposed very harsh requirement to its security performance.For this kind of requirement, typically exist
A certain amount of special compound additive is added in process, to improve the processability of high density polyethylene (HDPE) pressure resistant pipe material resin
Can, the appearance property of tubing article be improved, and assign tubing excellent environmental stress crack resistance and resistance to ag(e)ing, to meet
Requirement of the industry to high density polyethylene (HDPE) pressure resistant pipe material.
Invention content
Problems to be solved by the invention
In view of problem above, the purpose of the present invention is to provide a kind of for existing high density polyethylene (HDPE) pressure resistant pipe material
Composite assistant and preparation method thereof and resin raw material containing the composite assistant.High-density polyethylene containing the composite assistant
Alkene pressure resistant pipe material resin raw material has an excellent processing performance, tubing after forming have excellent environmental stress crack resistance,
Resistance to ag(e)ing and rigidity-toughness balanced.
Solution to the problem
The first aspect of the invention is to provide a kind of high density polyethylene (HDPE) pressure resistant pipe material composite assistant, and feature exists
In the composite assistant is by 30~50 parts by weight of resisting ageing for long time auxiliary agent, 10~30 parts by weight of thermostabilization auxiliary agent and processing aid
10~30 parts by weight form, wherein resisting ageing for long time auxiliary agent is selected from by hindered phenol anti-oxidants, amine antioxidants and phosphorus
At least one of the group of class antioxidant composition, the thermostabilization auxiliary agent in metal soap stabilizer at least one
Kind, processing aid is made of at least one fluoroelastomer.
In an embodiment of the invention, the resisting ageing for long time auxiliary agent is by hindered phenol anti-oxidants, amine
Antioxidant, phosphorus antioxidants in mass ratio 1:0.1~10:0.1~10 blends.
High density polyethylene (HDPE) pressure resistant pipe material composite assistant according to the first aspect of the invention, wherein Hinered phenols
Antioxidant is selected from by 2,6 di t butyl phenol, 2,6- di-t-butyl -4- ethyl -phenols, 2,6- di-t-butyl -4- methylbenzenes
Phenol, 2,6- di-t-butyl -4- normal-butyl phenol, 2,6- di-t-butyls-alpha, alpha-dimethyl amino paracresol, 2,4,6- tri-butyl benzenes
Phenol, β-(4- hydroxyl -3,5- di-tert-butyl-phenyls) propionic acid n-octadecane alcohol ester, styrenated phenol, butylated octylated phenol,
2,2 '-methylene bis (4- methyl-6-tert-butylphenols), 4,4 '-methylene bis(2,6-di-butyl phenol)s, four (3- (3 ', 5 '-two
Tertiary butyl -4 '-hydroxy phenyl) propionic acid) pentaerythritol ester, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane group
At at least one of group.
High density polyethylene (HDPE) pressure resistant pipe material composite assistant according to the first aspect of the invention, wherein amine antioxygen
Agent is selected from by N- phenyl-α-naphthylamines, N- phenyl-β-naphthylamines, N, N '-two-betanaphthyls p-phenylenediamine, acetaldol-alpha-naphthylamine,
At least one of the group of N- isopropyls-N '-diphenyl-para-phenylene diamine composition.
High density polyethylene (HDPE) pressure resistant pipe material composite assistant according to the first aspect of the invention, wherein Phosphorus antioxygen
Agent is selected from hard by triphenyl phosphite, phosphorous acid diphenyl monooctyl ester, trisnonyl phenyl phosphite, diphosphorous acid pentaerythrite two
Lipidol ester, phosphorous acid dilauryl, didecyl phosphite, three (2,4- di-t-butyls) phenyl-phosphites, phosphorous acid 4,4- bis- are different
Pitch at least one of the group of bis-phenol (12-14) carbon Arrcostab composition.
High density polyethylene (HDPE) pressure resistant pipe material composite assistant according to the first aspect of the invention, wherein metal soap
Heat stabilizer be selected from by calcium stearate, magnesium stearate, lithium stearate, zinc stearate, aluminum stearate, odium stearate, calcium laurate,
At least one of the group of double stearic acid aluminium composition.
High density polyethylene (HDPE) pressure resistant pipe material composite assistant according to the first aspect of the invention, wherein fluoroelastomer
Selected from least one of the group being made of FX-5911, FX-5920, FX-5924, Viton FFGB, SOLEF PVDF.
The second aspect of the invention is to provide the preparation side of above-specified high density polythene pressure pipe timber-used composite assistant
Method, which is characterized in that help 30~50 parts by weight of resisting ageing for long time auxiliary agent, 10~30 parts by weight of thermostabilization auxiliary agent and processing
After 10~30 parts by weight of agent are mixed and stirred for uniformly, extruding pelletization, to form granular composite assistant, wherein long-term resistance to old
Change property auxiliary agent in the group being made of hindered phenol anti-oxidants, amine antioxidants, phosphorus antioxidants at least one
Kind, thermostabilization auxiliary agent is selected from least one of metal soap stabilizer, and processing aid is made of at least one fluoroelastomer.
The third aspect of the invention is to provide a kind of resin raw material of manufacture high density polyethylene (HDPE) pressure resistant pipe material,
It is characterized in that, the resin raw material is involved by high density polyethylene (HDPE) pressure resistant pipe material base resin and the first aspect of the invention
High density polyethylene (HDPE) pressure resistant pipe material formed with composite assistant.
Resin raw material according to the third aspect of the present invention, wherein relative to resin raw material total amount, high density polyethylene (HDPE)
The additive amount of pressure resistant pipe material composite assistant is 0.1~1 weight %.In the preferred embodiment of the present invention, described
In resin raw material, relative to resin raw material total amount, the additive amount of high density polyethylene (HDPE) pressure resistant pipe material composite assistant is 0.4~
0.5 weight %.
The effect of invention
1) composite assistant of high density polyethylene (HDPE) pressure resistant pipe material of the invention can significantly improve the processability of resin raw material
Can, obtained hdpe pipe has excellent environmental stress crack resistance, pressure-resistant performance, resisting ageing for long time,
There are the mechanical properties such as good rigidity-toughness balanced simultaneously.
2) it after the composite assistant body of the addition present invention, can significantly improve through double kettle series connection (or in parallel) the polymerization works of slurry process
The processing difficulties that the high density polyethylene (HDPE) of skill manufacture occurs in tube extrusion, and tubing poor appearance, inner wall can be improved a little
Shape object or rough, sharkskin occur etc. problem, while will not to mechanical characteristics such as the resistance to pressures of hdpe pipe
Generate harmful effect.
Specific implementation mode
In the present invention, hdpe pipe composite assistant (hereinafter, being also referred to simply as " composite assistant ") is by long-term resistance to
30~50 parts by weight of aging auxiliary agent, 10~30 parts by weight of thermostabilization auxiliary agent and 10~30 parts by weight of processing aid composition.Its
In, resisting ageing for long time auxiliary agent is selected from the group being made of hindered phenol anti-oxidants, amine antioxidants and phosphorus antioxidants
At least one of group, the thermostabilization auxiliary agent are selected from least one of metal soap stabilizer, and the processing aid is by extremely
A kind of few fluoroelastomer composition.
In an embodiment of the invention, resisting ageing for long time auxiliary agent is to resist hindered phenol anti-oxidants, amine
Oxidant, phosphorus antioxidants in mass ratio 1:0.1~10:Compound system made of 0.1~10 blending, wherein preferably
Hindered phenol anti-oxidants, amine antioxidants, phosphorus antioxidants are 1 in mass ratio:0.2~5:0.2~5 range, into
One step is preferably 1:0.5~2:0.5~2 range.
In the present invention, hindered phenol anti-oxidants are selected from by 2,6- DI-tert-butylphenol compounds, 2,6- di-t-butyl -4- ethylo benzenes
Phenol, 2,6- di-tert-butyl-4-methy phenols, 2,6- di-t-butyl -4- normal-butyl phenol, 2,6- di-t-butyls-alpha, alpha-dimethyl amino
Paracresol, 2,4,6- tri-butyl-phenols, β-(4- hydroxyl -3,5- di-tert-butyl-phenyls) propionic acid n-octadecane alcohol ester, styrene
Change phenol, butylated octylated phenol, 2,2 '-methylene bis (4- methyl-6-tert-butylphenols), 4,4 '-methylene bis (bis- uncles of 2,6-
Butylphenol), four (3- (3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic acid) pentaerythritol esters, (2- methyl-the 4- of 1,1,3- tri-
Hydroxyl -5- tert-butyl-phenyls) butane composition at least one of group.
In the present invention, as amine antioxidants, can enumerate aromatic amine and its derivative, amides anti-aging agent,
Ketone amines antioxidants etc., wherein the preferably secondary diarylamines class antioxidant such as p-phenylenediamine.Amine antioxidants to oxygen,
The barrier propterty of ozone is good, has excellent discolouration and nonstaining property, can be used in dark product or be wanted to the color of product
Seek not high situation.In an embodiment of the invention, amine antioxidants is selected from by N- phenyl-α-naphthylamines, N- phenyl-
Beta-naphthylamine, N, N '-two-betanaphthyls p-phenylenediamine, acetaldol-alpha-naphthylamine, N- isopropyls-N '-diphenyl-para-phenylene diamine composition
At least one of group.
Phosphite antioxidant can be obviously improved high density polyethylene (HDPE) pressure pipe when being shared with phenol antioxidant
The discolouration and embrittlement characteristic of material.In the present invention, phosphorus antioxidants are selected from pungent by triphenyl phosphite, phosphorous acid diphenyl
Ester, trisnonyl phenyl phosphite, diphosphorous acid pentaerythrite distearyl alcohol ester, phosphorous acid dilauryl, didecyl phosphite, three
In the group that (2,4- di-t-butyls) phenyl-phosphite, bis- different fork bis-phenol (12-14) carbon Arrcostabs of phosphorous acid 4,4- form extremely
Few one kind.
In the hdpe pipe composite assistant of the present invention, thermostabilization auxiliary agent is metal soap stabilizer, this
Kind metal soap stabilizer is referred to as plumper, halogen-absorber again, is that common one kind adds in polyvinyl resin powder
Add agent.The activity of catalyst when in general, in order to improve olefinic polymerization or copolymerization, can introduce pole in polymerization reaction system
Property comonomer, radical initiator and Ziegler catalyst etc., it is poly- that the introducings of these substances can cause acid product to remain in
It closes in product.For example, when manufacturing olefin polymer using Ziegler catalyst, would generally be remained a small amount of (10-6 grades) in product
Chlorine-containing compound.The presence of these chlorine-containing compounds can lead to the corruption of metal-working plant (for example, drier, mold apparatus)
Erosion, while also resulting in the deterioration of the physical properties such as the changing colour of polymer product, embrittlement.At this point, the addition energy of thermostabilization auxiliary agent
Enough improve the overall performance of polymer product.In the present invention, the gold in being formed with composite assistant for hdpe pipe
Belonging to soaps heat stabilizer, there is no particular limitation, for example, it may be selected from by calcium stearate, magnesium stearate, lithium stearate, tristearin
At least one of the group of sour zinc, aluminum stearate, odium stearate, calcium laurate, double stearic acid aluminium composition.
In the present invention, fluoroelastomer is that it is poly- can to improve high density with the processing aid that fluoropolymer is basic structure
The processing fluidity of vinyl, and to playing lubricating action by the polyvinyl resin melt of mold, to improve melt
Extrusion performance and extrusion efficiency.In the present invention, as fluoroelastomer, for example, it may be selected from by FX-5911, FX-5920, FX-
5924, at least one of the group of Viton FFGB, SOLEF PVDF composition.
In the present invention, the method for preparing high density polyethylene (HDPE) pressure resistant pipe material composite assistant is limited there is no special
It is fixed, for example, it may be 30~50 parts by weight of resisting ageing for long time auxiliary agent, 10~30 parts by weight of thermostabilization auxiliary agent and processing are helped
After 10~30 parts by weight of agent are mixed and stirred for uniformly, extruding pelletization, to obtain granular composite assistant.At one of the present invention
It is by 30~50 weight of resisting ageing for long time auxiliary agent when preparing high density polyethylene (HDPE) pressure resistant pipe material composite assistant in embodiment
Amount part, 10~30 parts by weight of thermostabilization auxiliary agent and 10~30 parts by weight of processing aid are added in high speed mixing smelting machine, are stirred at room temperature
Mix, mix 5~after twenty minutes, it is transferred to powder extruder, is squeezed out under 20 DEG C~50 DEG C of cold working temperature, to make
Obtain granular composite assistant.
In the present invention, the resin raw material of manufacture high density polyethylene (HDPE) pressure resistant pipe material is by high density polyethylene (HDPE) pressure resistant pipe material
Base resin and the high density polyethylene (HDPE) pressure resistant pipe material of the present invention are formed with composite assistant.Wherein, total relative to resin raw material
Amount, the additive amount of high density polyethylene (HDPE) pressure resistant pipe material composite assistant of the invention are the range of 0.1~1 weight %, preferably
The range of 0.3~0.6 weight %, the further preferably range of 0.4~0.5 weight %.By the composite assistant of the present invention and height
After density polyethylene pressure resistant pipe material base resin is blended by certain Blend proportion, 180 DEG C~250 DEG C of processing temperatures into
Row melting mixing is granulated, then the extrusion molding in pipe extruder after being plasticized uniformly, you can obtains high density polyethylene (HDPE) pressure resistance
Tubing.
In the present invention, do not have for high density polyethylene (HDPE) pressure resistant pipe material base resin (hereinafter, being also referred to as " base resin ")
Be particularly limited to, for example, may be used Ziegler catalyst, philip catalyst or CGC/ borate esters catalyst (that is, by
Carrier loaded single-activity site catalyst), it is poly- to manufacture high density by double kettle series connection (or in parallel) polymerization techniques of slurry process
Ethylene base resin.In the present invention, as high density polyethylene (HDPE) base resin, Ziegler catalyst, CGC/ boron are preferably used
The manufacture of esters of gallic acid catalyst, by Alathon, the copolymer of vinyl monomer and other 'alpha '-olefin monomers or by ethylene homo
The copolymer blended rear high-density polyethylene resin formed of object and vinyl monomer and other 'alpha '-olefin monomers.Wherein, as second
The copolymer of alkene monomer and other 'alpha '-olefin monomers can be α-alkene that the carbon atom number of vinyl monomer and a kind or more is 3~20
The copolymer of hydrocarbon monomer, and 'alpha '-olefin monomers unit is in range of the content ratio 0.5~2.0% of copolymer entirety, preferably
In 1.0~2.0% range.The density of high-density polyethylene resin is influenced by monomer component composition, the molecular weight with resin
And it is uncorrelated.In the present invention, for the density of high-density polyethylene resin, there is no particular limitation, for example, can be in 940Kg/
m3~980Kg/m3Range, preferably 940Kg/m3~970Kg/m3Range, further preferably 940Kg/m3~960Kg/
m3Range.
In the present invention, for the molecular weight of high density polyethylene (HDPE) pressure resistant pipe material base resin, there is no particular limitation, for example,
Weight average molecular weight can 20,000~500,000 range, range of the preferable weight-average molecular weight 40,000~300,000.
The high density polyethylene (HDPE) with bimodal molecular weight distribution can be produced by the series connection of double kettles (or in parallel) polymerization technique, wherein
Lower molecular wt part makes polymerizate that there is high density characteristic, high molecular weight moieties polymerizate then to be made to have larger glue
Degree.Here, so-called high and low molecular weight is that have two kinds of ingredients in the high density polyethylene (HDPE) of bimodal molecular weight distribution phase each other
For, it is not offered as absolute numberical range.Also, the molecular weight of high-density polyethylene resin substantially with its melt index
(Melt Flow Rate, MFR) is corresponding, in general, the weight average molecular weight of resin powder is capable of the molten of reinforced resin powder when high
Body intensity, and the tubing enabled to has superior toughness and environmental stress crack resistance, but higher molecular weight
Process operation can be made to be deteriorated, add the higher pressure of man-hour requirement or temperature.In the present invention, as high-density polyethylene resin powder
The melt index of material is appropriately 0.01g/10 minutes~100g/10 minutes ranges in 230 DEG C, 21.6Kg loads, excellent
Be selected in 230 DEG C, 21.6Kg loads when for 0.1g/10 minutes~50g/10 minutes ranges, further preferably 230 DEG C,
It is 1g/10 minutes~10g/10 minutes ranges when 21.6Kg is loaded.By the molecule for controlling high-density polyethylene resin powder
Amount, can adjust the range of its melt index, so as to significantly improve its process operation.
After the composite assistant for adding the present invention in high density polyethylene (HDPE) pressure resistant pipe material base resin, pipe can significantly improve
Material the resin processing difficulties that occur and the tubing poor appearance of forming, inner wall when squeezing out have pointing object or it is rough, there is shark
The problems such as skin, while the processing performance of high density polyethylene (HDPE) pressure resistant pipe material, pressure resistance performance, resisting ageing for long time, resistance to ring can be made
Border stress cracking resistance and mechanical property significantly improve.
As needed, composite assistant of the invention can also coordinate with other well known additives is added to high-density polyethylene
In alkene pressure resistant pipe material base resin, to play the modifying function of collaboration.As these well known additives, for example, it may be
Antiblocking agent, antistatic agent, lubricant, weather resisting agent, light stabilizer, ultra-violet absorber, inorganic or organic filler, organic peroxy
Compound, neutralizer etc..In the present invention, for antiblocking agent, there is no particular limitation, specifically, talcum, oxidation can be enumerated
Inoganic solids powder such as silicon, kaolinite etc..It as antistatic agent, is not particularly limited, for example, alkylsurfuric acid can be enumerated
The nonionics such as salt form anionic antistatic agents, Quaternary Cation Antistatic Agent, polyoxyethylene sorbitan monostearate
Property antistatic agent, betaines both sexes antistatic agent etc..As lubricant, also there is no particular limitation, for example, Asia can be enumerated
The fat hydrocarbons lubricants such as ethyl double stearamide, butyl stearate, polyethylene wax, solid paraffins, higher fatty acids lubricant,
Aliphatic amide series lubricant agent, fatty acid ester type emollients etc..In the present invention, for weather resisting agent, there is no particular limitation, specifically
Ground is said, resorcin compound, salicylic acid ester type compound, benzotriazole compound, Benzophenone class chemical combination can be enumerated
Object, hindered amine compound etc..As light stabilizer, for example, hindered amine compound, benzo three can be enumerated but be not limited to
Azole compounds, compound in triazine class, Benzophenone class compound, benzoic acid salt compound etc..As ultra-violet absorber,
For example, benzotriazole compound, compound in triazine class, Benzophenone class compound etc. can be enumerated but be not limited to.As nothing
Machine filler, there is no particular limitation in the present invention, specifically, fibrous, microgranular, sheet and hollow oxygen can be enumerated
SiClx, quartz powder, bead, calcium silicates, diatomite, iron oxide, titanium oxide, alumina silicate, aluminium oxide, magnesium carbonate, silicon nitride,
The inorganic fillers such as boron nitride.As organic filler, also there is no particular limitation in the present invention, specifically, shallow lake can be enumerated
The powder of powder, producing starch, wooden slurry, chitin/chitosan class, cocoanut shell, bamboo matter powder, bark powder, kenaf etc.
Body.As organic peroxide, for example, diacyl peroxide class, peroxidating ketone, peroxidating can be enumerated but be not limited to
Hydrogen species, dialkyl peroxide class, ketal peroxide class, peroxy acid alkyl esters and peroxycarbonic acid esters etc..As neutralizer,
There is no particular limitation in the present invention, for example, various Metallic stearates, Hydrotalcite etc. can be enumerated.
Hereinafter, the present invention is described further in conjunction with the embodiments.Without saying, the present invention is not by these embodiments more
Limitation.Also, in the range of not departing from general idea of the present invention, change, deformation or variation that these embodiments are done
Etc. belonging in scope of the invention.
Hereinafter, Examples 1 to 6 is the preparation of the composite assistant for illustrating the present invention, comparative example 1 is existing for illustrating
The preparation of the polythene pressure pipe timber-used composite assistant of technology.
Embodiment 1
By 100g tetra- (3- (3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic acid) pentaerythritol ester (that is, bisphenols antioxygen
Agent 1010), 80g tri- (2,4- di-t-butyls) phenyl-phosphite (trade (brand) name：Mark2112), 60g calcium stearates, 6g fluorine elasticity
Body Viton FFGB (E.I.Du Pont Company's system) are added in mixing machine, are mixed at room temperature after five minutes, are sent into powder extruder, room temperature
Lower pressure squeezes out, and obtains granular composite assistant (GC-1).
Embodiment 2
By 100g tetra- (3- (3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic acid) pentaerythritol ester, (2,4- bis- of 100g tri-
Tertiary butyl) phenyl-phosphite, 60g calcium stearates, 7g fluoroelastomer Viton FFGB (E.I.Du Pont Company's system) be added in mixing machine,
It mixes at room temperature after ten minutes, is sent into powder extruder, force to squeeze out at room temperature, obtain granular composite assistant (GC-2).
Embodiment 3
By 100g tetra- (3- (3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic acid) pentaerythritol ester, (2,4- bis- of 120g tri-
Tertiary butyl) phenyl-phosphite, 60g calcium stearates, 8 grams of fluoroelastomer Viton FFGB (E.I.Du Pont Company's system) are added to mixing machine
In, it mixes at room temperature after twenty minutes, is sent into powder extruder, force to squeeze out at room temperature, obtain granular composite assistant (GC-3).
Embodiment 4
By 100g tetra- (3- (3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic acid) pentaerythritol ester, (2,4- bis- of 100g tri-
Tertiary butyl) phenyl-phosphite, 60g metal soap stabilizers (wherein, calcium stearate and zinc stearate are respectively 30 grams), 6g fluorine elasticity
Body Viton FFGB (E.I.Du Pont Company's system) are added in mixing machine, are mixed at room temperature after five minutes, are sent into powder extruder, room temperature
Lower pressure squeezes out, and obtains granular composite assistant (GC-4).
Embodiment 5
By 100g tetra- (3- (3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic acid) pentaerythritol ester, (2,4- bis- of 100g tri-
Tertiary butyl) phenyl-phosphite, 80g metal soap stabilizers (wherein, calcium stearate and zinc stearate are respectively 40 grams), 7g fluorine elasticity
Body Viton FFGB (E.I.Du Pont Company's system) are added in mixing machine, are mixed at room temperature after ten minutes, are sent into powder extruder, room temperature
Lower pressure squeezes out, and obtains granular composite assistant (GC-5).
Embodiment 6
By 100g tetra- (3- (3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic acid) pentaerythritol ester, (2,4- bis- of 100g tri-
Tertiary butyl) phenyl-phosphite, 100g metal soap stabilizers (wherein, calcium stearate and zinc stearate are respectively 50 grams), 8g fluorine bullets
Property body Viton FFGB (E.I.Du Pont Company's system) be added in mixing machine, mix at room temperature after twenty minutes, be sent into powder extruder, room
Temperature is lower to force to squeeze out, and obtains granular composite assistant (GC-6).
Comparative example 1
By polyethylene wax 2000g, 100g composite antioxidant, 700g metal soap stabilizers, (wherein, calcium stearate is
200g, zinc stearate 500g), 100g FX-5920 (the extraordinary fluoropolymer additive of Minnesota Mining and Manufacturing Company) are added to
It in mixing machine, mixes after twenty minutes, is sent into cone-type mixer at room temperature, force to squeeze out at room temperature, obtain granular compound help
Agent (DB-1).
Hereinafter, Production Example 1~6 is the high-density polyethylene of composite assistant GC-1~GC-6 for illustrating to have blended the present invention
The manufacture of alkene pressure resistant pipe material resin raw material and the performance evaluation after forming tubular product.It is for illustrating to blend to manufacture comparative example 1
After the manufacture of the high density polyethylene (HDPE) pressure resistant pipe material resin raw material of the composite assistant DB-1 of comparative example 1 and forming tubular product
Performance evaluation.
Production Example 1
By 300g GC-1 and 50Kg high density polyethylene (HDPE) pressure resistant pipe materials base resin, (under conditions of 5Kg loads, MFR exists
The PE100 grade pipe resins powder of 0.2~0.4g/10 minutes bimodal molecular weight distributions) it is uniformly mixed with high speed mixing smelting machine, it uses
Double screw extruder is shaped in 200 DEG C of extruding pelletizations, with single screw rod pipe extruder in 210 DEG C of crowded pipes.It is inside and outside after forming tubular product
Wall is smooth, even tube wall.Also, the oxidation induction period of tubing is more than 120 minutes, yield strength 24.1MPa, and impact strength is
55.1KJ/m2.Individual base resin is shown in table 1 and the performance of the pipe resin of GC-1 has been blended in base resin
Compare.
Production Example 2
By 250g GC-2 and 50Kg high density polyethylene (HDPE) pressure resistant pipe materials base resin, (under conditions of 5Kg loads, MFR exists
The PE100 grade pipe resins powder of 0.2~0.4g/10 minutes bimodal molecular weight distributions) it is uniformly mixed with high speed mixing smelting machine, it uses
Double screw extruder is shaped in 200 DEG C of extruding pelletizations, with single screw rod pipe extruder in 210 DEG C of crowded pipes.It is inside and outside after forming tubular product
Wall is smooth, even tube wall.Also, the oxidation induction period of tubing is more than 120 minutes, yield strength 25.2MPa, and impact strength is
54.2KJ/m2.Individual base resin is shown in table 1 and the performance of the pipe resin of GC-2 has been blended in base resin
Compare.
Production Example 3
By 200g GC-3 and 50Kg high density polyethylene (HDPE) pressure resistant pipe materials base resin, (under conditions of 5Kg loads, MFR exists
The PE100 grade pipe resins powder of 0.2~0.4g/10 minutes bimodal molecular weight distributions) it is uniformly mixed with high speed mixing smelting machine, it uses
Double screw extruder is shaped in 200 DEG C of extruding pelletizations, with single screw rod pipe extruder in 210 DEG C of crowded pipes.It is inside and outside after forming tubular product
Wall is smooth, even tube wall.Also, the oxidation induction period of tubing is more than 120 minutes, yield strength 25.3MPa, and impact strength is
53.4KJ/m2.Individual base resin is shown in table 1 and the performance of the pipe resin of GC-3 has been blended in base resin
Compare.
Production Example 4
By 300g GC-4 and 50Kg high density polyethylene (HDPE) pressure resistant pipe materials base resin, (under conditions of 5Kg loads, MFR exists
The PE100 grade pipe resins powder of 0.2~0.4g/10 minutes bimodal molecular weight distributions) it is uniformly mixed with high speed mixing smelting machine, it uses
Double screw extruder is shaped in 200 DEG C of extruding pelletizations, with single screw rod pipe extruder in 210 DEG C of crowded pipes.It is inside and outside after forming tubular product
Wall is smooth, even tube wall.Also, the oxidation induction period of tubing is more than 120 minutes, yield strength 24.8MPa, and impact strength is
55.7KJ/m2.Individual base resin is shown in table 1 and the performance of the pipe resin of GC-4 has been blended in base resin
Compare.
Production Example 5
By 250g GC-5 and 50Kg high density polyethylene (HDPE) pressure resistant pipe materials base resin, (under conditions of 5Kg loads, MFR exists
The PE100 grade pipe resins powder of 0.2~0.4g/10 minutes bimodal molecular weight distributions) it is uniformly mixed with high speed mixing smelting machine, it uses
Double screw extruder is shaped in 200 DEG C of extruding pelletizations, with single screw rod pipe extruder in 210 DEG C of crowded pipes.It is inside and outside after forming tubular product
Wall is smooth, even tube wall.Also, the oxidation induction period of tubing is more than 120 minutes, yield strength 25.9MPa, and impact strength is
53.4KJ/m2.Individual base resin is shown in table 1 and the performance of the pipe resin of GC-5 has been blended in base resin
Compare.
Production Example 6
By 200g GC-6 and 50Kg high density polyethylene (HDPE) pressure resistant pipe materials base resin, (under conditions of 5Kg loads, MFR exists
The PE100 grade pipe resins powder of 0.2~0.4g/10 minutes bimodal molecular weight distributions) it is uniformly mixed with high speed mixing smelting machine, it uses
Double screw extruder is shaped in 200 DEG C of extruding pelletizations, with single screw rod pipe extruder in 210 DEG C of crowded pipes.It is inside and outside after tube forming
Wall is smooth, even tube wall.Also, the oxidation induction period of tubing is more than 120 minutes, yield strength 24.3MPa, and impact strength is
55.4KJ/m2.Individual base resin is shown in table 1 and the performance of the pipe resin of GC-6 has been blended in base resin
Compare.
Manufacture comparative example 1
By 200g DB-1 and 50Kg high density polyethylene (HDPE) pressure resistant pipe materials base resin, (under conditions of 5Kg loads, MFR exists
The PE100 grade pipe resins powder of 0.2~0.4g/10 minutes bimodal molecular weight distributions) it is uniformly mixed with high speed mixing smelting machine, it uses
Double screw extruder is shaped in 200 DEG C of extruding pelletizations, with single screw rod pipe extruder in 210 DEG C of crowded pipes.It is inside and outside after tube forming
Wall is smooth, even tube wall.Also, the oxidation induction period of tubing is 35 minutes, yield strength 24.0MPa, and impact strength is not
Fracture.The performance for showing individual base resin in table 1 and having blended the pipe resin of DB-1 in base resin compares.
Also, Production Example 1~6 is shown in table 2 and manufactures the performance test results of the forming tube of comparative example 1.
As shown in Table 1, it is resistance to can be obviously improved the high density polyethylene (HDPE) that autoclave slurry process produces to composite assistant of the invention
Press processing performance, antioxygenic property and the mechanical property of pipe resin.Also, after the composite assistant for having blended the present invention, tubing
Oxidation induction period be more than 120 minutes, impact strength is more than 50KJ/m2.Also, as shown in Table 2, with blended the present invention
The hydrostatic index of tubing of φ 32mm × 3mm tubing of the pipe resin raw material forming of composite assistant has reached national standard.
By above example 1~6 and comparative example 1 it is found that compared with existing composite assistant DB-1, of the invention answers
The composition for closing auxiliary agent is more simple, and the dosage of constituent is also more reasonable.Also, by table 1,2 it is found that having blended the present invention
Composite assistant after, the various physical property of pipe resin are more rational, and (specific targets are melt index to the processing performance of forming tube
Front and back variation) and the pipe performances such as longitudinal welds become more excellent.Therefore, blend the present invention's in base resin
After composite assistant, the high density polyethylene (HDPE) pressure resistant pipe material resin that can solve to manufacture through autoclave slurry process occurs in extrusion molding
Processing difficulties and forming tubular product after poor appearance, inner wall have pointing object or it is rough, there is the problems such as sharkskin, also, energy
Enough make high density polyethylene (HDPE) pressure resistant pipe material that there is excellent antioxygenic property, mechanical property, environmental stress crack resistance and pressure resistance
Performance, and disclosure satisfy that the currently requirement to PE100 grades of pressure resistant pipe materials.
Claims (10)
1. a kind of high density polyethylene (HDPE) pressure resistant pipe material composite assistant, which is characterized in that
The composite assistant is helped by 30~50 parts by weight of resisting ageing for long time auxiliary agent, 10~30 parts by weight of thermostabilization auxiliary agent and processing
10~30 parts by weight of agent form, wherein
The resisting ageing for long time auxiliary agent is selected from and is made of hindered phenol anti-oxidants, amine antioxidants and phosphorus antioxidants
At least one of group,
The thermostabilization auxiliary agent is selected from least one of metal soap stabilizer,
The processing aid is made of a kind of fluoroelastomer, and the fluoroelastomer is Viton FFGB.
2. high density polyethylene (HDPE) pressure resistant pipe material composite assistant as described in claim 1, wherein the resisting ageing for long time helps
Agent is by hindered phenol anti-oxidants, amine antioxidants, phosphorus antioxidants in mass ratio 1:0.1~10:0.1~10 blending
It forms.
3. high density polyethylene (HDPE) pressure resistant pipe material composite assistant as claimed in claim 1 or 2, wherein
The hindered phenol anti-oxidants are selected from by 2,6 di t butyl phenol, 2,6- di-t-butyl -4- ethyl -phenols, 2,6- bis-
Tert-butyl-4-methyl-Phenol, 2,6- di-t-butyl -4- normal-butyl phenol, 2,6- di-t-butyls-alpha, alpha-dimethyl amino paracresol, 2,
4,6- tri-butyl-phenols, β-(4- hydroxyl -3,5- di-tert-butyl-phenyls) propionic acid n-octadecane alcohol ester, styrenated phenol, fourth
The octylatcd phenol of baseization, 2,2 '-methylene bis (4- methyl-6-tert-butylphenols), 4,4 '-methylene bis (2,6- di-tert-butyls
Phenol), four (3- (3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic acid) pentaerythritol esters, (2- methyl -4- the hydroxyls-of 1,1,3- tri-
5- tert-butyl-phenyls) butane composition at least one of group.
4. high density polyethylene (HDPE) pressure resistant pipe material composite assistant as claimed in claim 1 or 2, wherein
The amine antioxidants is selected from by N- phenyl-α-naphthylamines, N- phenyl-β-naphthylamines, N, N '-two-betanaphthyls p-phenylenediamine,
At least one of the group of acetaldol-alpha-naphthylamine, N- isopropyls-N '-diphenyl-para-phenylene diamine composition.
5. high density polyethylene (HDPE) pressure resistant pipe material composite assistant as claimed in claim 1 or 2, wherein
The phosphorus antioxidants are selected from by triphenyl phosphite, phosphorous acid diphenyl monooctyl ester, trisnonyl phenyl phosphite, two Asias
Phosphoric acid pentaerythrite distearyl alcohol ester, phosphorous acid dilauryl, didecyl phosphite, three (2,4- di-t-butyls) phosphorous acid benzene
At least one of the group of ester, bis- different fork bis-phenol (12-14) carbon Arrcostabs of phosphorous acid 4,4- composition.
6. high density polyethylene (HDPE) pressure resistant pipe material composite assistant as described in claim 1, wherein
The metal soap stabilizer be metal soap thermal stabilizers, the metal soap thermal stabilizers be selected from by calcium stearate,
In the group that magnesium stearate, lithium stearate, zinc stearate, aluminum stearate, odium stearate, calcium laurate, double stearic acid aluminium form
At least one.
7. a kind of preparation method of high density polyethylene (HDPE) pressure resistant pipe material composite assistant, is to prepare height described in claim 1
The method of density polyethylene pressure resistant pipe material composite assistant, which is characterized in that
By 10~30 weight of 30~50 parts by weight of resisting ageing for long time auxiliary agent, 10~30 parts by weight of thermostabilization auxiliary agent and processing aid
After amount part is mixed and stirred for uniformly, extruding pelletization, to form granular composite assistant, wherein
The resisting ageing for long time auxiliary agent is selected from and is made of hindered phenol anti-oxidants, amine antioxidants, phosphorus antioxidants
At least one of group,
The thermostabilization auxiliary agent is selected from least one of metal soap stabilizer,
The processing aid is made of a kind of fluoroelastomer, and the fluoroelastomer is Viton FFGB.
8. a kind of resin raw material of manufacture high density polyethylene (HDPE) pressure resistant pipe material, which is characterized in that
The resin raw material is described in any one of high density polyethylene (HDPE) pressure resistant pipe material base resin and claim 1~6
High density polyethylene (HDPE) pressure resistant pipe material is formed with composite assistant.
9. resin raw material as claimed in claim 8, wherein relative to the resin raw material total amount, the high density polyethylene (HDPE)
The additive amount of pressure resistant pipe material composite assistant is 0.1~1 weight %.
10. resin raw material as claimed in claim 9, wherein relative to the resin raw material total amount, the high density polyethylene (HDPE)
The additive amount of pressure resistant pipe material composite assistant is 0.4~0.5 weight %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410764954.XA CN105733023B (en) | 2014-12-11 | 2014-12-11 | Composite assistant for high-density polyethylene pressure-resistant pipe, preparation method thereof and resin raw material containing composite assistant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410764954.XA CN105733023B (en) | 2014-12-11 | 2014-12-11 | Composite assistant for high-density polyethylene pressure-resistant pipe, preparation method thereof and resin raw material containing composite assistant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105733023A CN105733023A (en) | 2016-07-06 |
| CN105733023B true CN105733023B (en) | 2018-08-10 |
Family
ID=56241314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410764954.XA Active CN105733023B (en) | 2014-12-11 | 2014-12-11 | Composite assistant for high-density polyethylene pressure-resistant pipe, preparation method thereof and resin raw material containing composite assistant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105733023B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108610531A (en) * | 2016-12-09 | 2018-10-02 | 中国石油天然气股份有限公司 | Polyethylene pipe composite auxiliary agent bag and preparation method thereof |
| CN109092375B (en) * | 2017-06-21 | 2021-06-22 | 中国石油化工股份有限公司 | Free radical stabilizer for preparing adipic acid by direct oxidation of cyclohexane |
| CN110100777A (en) * | 2019-03-25 | 2019-08-09 | 广东南风王科技有限公司 | A kind of cordless super strong type cultivation frame |
| CN113881151A (en) * | 2020-07-02 | 2022-01-04 | 中国石油天然气股份有限公司 | Special polybutylene resin composition for cold and hot water pipes and preparation method thereof |
| CN112898663A (en) * | 2021-01-25 | 2021-06-04 | 孙牡花 | PE composite material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9376558B2 (en) * | 2009-05-29 | 2016-06-28 | Milliken & Company | Polymer compositions, articles made from such compositons, and methods for molding such compositions |
| CN103524861B (en) * | 2012-07-05 | 2016-10-26 | 中国石油化工股份有限公司 | A kind of pressure polyethylene composition high temperature resistant, high |
-
2014
- 2014-12-11 CN CN201410764954.XA patent/CN105733023B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105733023A (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105733023B (en) | Composite assistant for high-density polyethylene pressure-resistant pipe, preparation method thereof and resin raw material containing composite assistant | |
| CN102382344B (en) | Composition for preparing polyethylene pipe with superhigh molecular weight and preparation method thereof | |
| KR101531935B1 (en) | Compositions including polytetrafluoroethylene and processes for the preparation thereof | |
| CN104140616B (en) | A kind of high resiliency environment-friendly PVC is material modified and preparation method thereof | |
| CN102634138B (en) | A kind of polyvinyl chloride (PVC) Compound of high elongation at tear | |
| CN102464832A (en) | High-temperature-resistant thermoplastic elastomer for coating vulcanized rubber hose | |
| CN102276913B (en) | Polypropylene material for MPP (modified polypropylene) jacking pipe | |
| CN102863711A (en) | Heat-resisting PVC high impact-resisting tubular product and preparation method thereof | |
| CN104327369B (en) | A kind of polypropene composition and polypropylene granules | |
| CN104292595A (en) | High-rigid linear low-density polyethylene injection moulding resin | |
| CN103382274B (en) | A kind of block copolymerization polypropylene composite additive | |
| EP2989157A1 (en) | Multimodal polypropylene composition for pipe applications | |
| CN102002191A (en) | PPR/EVOH/POE (Pentatricopeptide Repeats/Ethylene-Vinyl Alcohol/Polyolefin Elastomer) blending high-impact barrier pipe and manufacturing method thereof | |
| CN108219326A (en) | A kind of high impact PVC pipe formula and preparation method thereof | |
| JP2006193671A (en) | Polyethylene resin material and hollow molded article made thereof | |
| CN104837919A (en) | Heat aging resistant ethylene vinly acetate copolymer composition and process for producing same | |
| CN102816383A (en) | High temperature and pressure resistant filter plate of filter press | |
| CN102952330B (en) | Low-odor polypropylene resin and preparation method thereof | |
| KR20140074887A (en) | Polyethylene additive compositions and articles made from same | |
| CN103421236A (en) | Polypropylene composition and polypropylene blown film | |
| CN102295799B (en) | Polyethylene resin composition for pipes | |
| CA3008857C (en) | Partially-crosslinked polyethylene formulations and methods of making same | |
| CN104962027B (en) | A kind of elastomer alloy material and preparation method thereof | |
| CN106317546A (en) | High-density polyethylene resin for large hollow containers | |
| CN111040307A (en) | Polypropylene corrugated pipe composite material and preparation method of composite polypropylene corrugated pipe |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |