CN111073119A - Assistant composition, linear medium-density polyethylene composition, preparation method thereof and polyethylene rotational molding product - Google Patents
Assistant composition, linear medium-density polyethylene composition, preparation method thereof and polyethylene rotational molding product Download PDFInfo
- Publication number
- CN111073119A CN111073119A CN201811218444.7A CN201811218444A CN111073119A CN 111073119 A CN111073119 A CN 111073119A CN 201811218444 A CN201811218444 A CN 201811218444A CN 111073119 A CN111073119 A CN 111073119A
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- China
- Prior art keywords
- antioxidant
- composition
- density polyethylene
- linear medium
- light stabilizer
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 106
- 229920001179 medium density polyethylene Polymers 0.000 title claims abstract description 69
- 239000004701 medium-density polyethylene Substances 0.000 title claims abstract description 69
- -1 polyethylene Polymers 0.000 title claims abstract description 31
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 28
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001175 rotational moulding Methods 0.000 title abstract description 36
- 239000004611 light stabiliser Substances 0.000 claims abstract description 61
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 52
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 49
- 239000002216 antistatic agent Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000004605 External Lubricant Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 13
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 12
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 12
- 239000002671 adjuvant Substances 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 9
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 6
- 239000008116 calcium stearate Substances 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 1
- 239000012188 paraffin wax Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 27
- 238000003860 storage Methods 0.000 abstract description 14
- 230000032683 aging Effects 0.000 abstract description 9
- 230000006750 UV protection Effects 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 29
- 238000012545 processing Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 11
- 239000012752 auxiliary agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 230000008676 import Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000006353 environmental stress Effects 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000005480 straight-chain fatty acid group Chemical group 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 description 1
- QVDLZEROFKISTC-UHFFFAOYSA-N 2-(octadecylamino)ethane-1,1-diol Chemical compound CCCCCCCCCCCCCCCCCCNCC(O)O QVDLZEROFKISTC-UHFFFAOYSA-N 0.000 description 1
- NKFNBVMJTSYZDV-UHFFFAOYSA-N 2-[dodecyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCCCCCCCCCN(CCO)CCO NKFNBVMJTSYZDV-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 description 1
- MWEZYKWGRQWLKM-UHFFFAOYSA-N n,n-dihydroxyicosan-3-amine Chemical compound CCCCCCCCCCCCCCCCCC(CC)N(O)O MWEZYKWGRQWLKM-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl 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])C([H])([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
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of plastics, and discloses an auxiliary composition, a linear medium density polyethylene composition containing the auxiliary composition, a preparation method of the linear medium density polyethylene composition, and a polyethylene rotational moulding storage tank product prepared from the linear medium density polyethylene composition. Based on the total weight of the auxiliary composition, the auxiliary composition comprises the following components in percentage by weight: (1) 5% -25% of a main antioxidant; (2) 5% -25% of auxiliary antioxidant; (3) 3% -15% of external lubricant; (4) 3% -15% of antistatic agent; (5) 20% -50% of light stabilizer A; (6) 15 to 45 percent of light stabilizer B. The invention improves the rotational molding processability of polyethylene, enlarges the raw material sources of rotational molding products, improves the fluidity of the raw materials, improves the production efficiency and reduces the production cost. The processed large rotational molding product has white color, easy demolding, very good inner and outer surface smoothness, uniform wall thickness, good toughness, moderate rigidity, good ultraviolet resistance and aging resistance, and meets the use requirements.
Description
Technical Field
The invention relates to an auxiliary composition, a linear medium density polyethylene composition containing the auxiliary composition, a preparation method thereof and a polyethylene rotational molding product prepared from the linear medium density polyethylene composition.
Background
Rotational molding is a very unique processing mode, and compared with injection molding and blow molding processes, the rotational molding has the outstanding advantages of low investment on equipment and molds, flexible process, almost no internal stress of products, difficult deformation, no seam and high strength, and is suitable for producing various large and complex-shaped hollow plastic products.
The domestic rotational molding industry starts at the end of the 20 th century 70 s and starts late, and in recent years, with the maturity of polyethylene powdering technology and the continuous improvement of processing equipment, the rotational molding process increasingly becomes a very competitive molding method in the plastic molding process.
The rotational molding raw material has higher requirements on rigidity, toughness, ultraviolet resistance, environmental stress resistance and demolding. CN102010542A discloses a special marble-imitated rotational molding material and a preparation method thereof, wherein the special marble-imitated rotational molding material comprises the following components in percentage by weight: 40-70% of base resin and 30-60% of marbleized resin, wherein the base resin is linear low-density polyethylene, and the marbleized resin comprises the following components in percentage by weight: 98 percent of high-density polyethylene, 0.1 to 1 percent of pigment, 0.1 to 0.5 percent of antioxidant, 0.1 to 0.5 percent of light stabilizer, 0.1 to 0.5 percent of lubricant, 0.1 to 1.0 percent of antistatic agent, 2 to 10g/10min of linear low-density polyethylene melt flow rate and 0.925 to 0.940g/cm of density3The melt flow rate of the high-density polyethylene is 0.01-2g/10min, and the density is 0.940-0.960g/cm3The antioxidant is tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester, 2, 6-di-tert-butyl-4-methylphenol or octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-hydroxy-4-N-octyloxydiphenylketone, 2- (2 ' -hydroxy-3 ', 5-di-tert-butylphenyl) -5-chlorobenzotriazole or 4-benzoyloxy-2, 2, 6, 6-tetramethylpiperidine as a light stabilizer, calcium stearate, N ' -ethylene bis-stearamide or ethylene oxide wax as a lubricant, and N, N-bis (2-hydroxyethyl) laurylamine or alkyl di (polyoxyethylene) quaternary ammonium acetate as an antistatic agent.
However, when the raw materials are used for preparing a large storage tank with the volume of more than 10 cubic meters, the problems of difficult demoulding, unsmooth product surface, easy warping deformation, insufficient product strength, long-term ultraviolet irradiation, easy aging and the like exist. It can be seen that the existing domestic polyethylene raw materials cannot be used for preparing large storage tanks of more than 10 cubic meters. At present, more than 90 percent of domestic rotational molding raw materials are polyethylene (a comonomer is butylene), more than 65 percent of required raw materials depend on import, particularly high-grade raw materials, and raw materials of a large storage tank with more than 10 cubic meters are imported completely. The shortage of raw materials seriously restricts the healthy and continuous development of the rotational molding industry in China, and the development level of the rotational molding is greatly different from that of foreign countries.
Therefore, it is very necessary for manufacturers to develop PE rotational molding raw materials to replace import.
Disclosure of Invention
The invention aims to overcome the defect that the source of rotational molding raw materials of the existing large storage tank is limited, and provides a novel rotational molding raw material which can be used for preparing the large storage tank easily through a rotational molding process.
The inventor of the invention fully researches enterprises producing rotational molding products at downstream, masters the manufacturing process of downstream enterprises, knows the problems existing in the use process of common imported materials and domestic materials, and develops the characterization, analysis and research on the physical and mechanical properties and the structure of the imported materials and high-grade raw materials according to the research and development conditions; comprehensive analysis finds that the qualified large-scale storage tank product cannot be manufactured by domestic polyethylene raw materials mainly due to the following reasons: 1) unreasonable for the adjuvant composition (adjuvant formulation) of the rotomoulding raw material; 2) the melt index and density control accuracy of linear medium density polyethylene (powder) is not sufficient, usually more than 10%, and some up to 20% or more. The large polyethylene rotational molding product is difficult to demould in the production process, the edge of the product has micro small bubbles and the product is yellow, the strength is not enough, and the product is easy to age after long-term ultraviolet irradiation.
The inventor laboratory of the invention simultaneously develops an optimization test of an additive formula, inspects the comprehensive influence of different antioxidant systems, different light stabilizers and the like on the product performance, mainly tests rigidity and toughness indexes, inspects an oxidation induction period, quickly evaluates the antioxidant effect of the antioxidant system, evaluates the effect of the light stabilizers and the like by an ultraviolet aging resistance test, and determines a final formula composition by characterizing and analyzing the processing performance, molecular weight and distribution condition of raw materials by a rheometer and a gel chromatograph.
In order to achieve the above object, the present invention provides an auxiliary composition, wherein the auxiliary composition comprises the following components in parts by weight based on the total weight of the composition:
(1) 5-25% of main antioxidant, preferably 10% -20%;
(2) auxiliary antioxidant, 5-25%, preferably 10% -20%;
(3) external lubricant, 3-15%, preferably 5% -10%;
(4) antistatic agent, 3-15%, preferably 5% -10%;
(5) 20-50% of light stabilizer A, preferably 25% -45%; the light stabilizer A is one or more of hindered amine light stabilizer and benzophenone light stabilizer with triazine skeleton;
(6) 15-45%, preferably 20% -40%, of the light stabilizer B, wherein the light stabilizer B is one or more of a hindered amine type light stabilizer and a benzotriazole type light stabilizer with an ester-based skeleton.
The second aspect of the present invention provides a linear medium density polyethylene composition, wherein the linear medium density polyethylene composition comprises: based on the total weight of the linear medium density polyethylene composition, the polyethylene composition contains 97 to 99.9 weight portions of linear medium density polyethylene and 0.1 to 3 weight portions of the auxiliary agent composition.
The third aspect of the present invention provides a method for preparing linear medium density polyethylene composition, wherein the method comprises blending 97-99.9 parts by weight of linear medium density polyethylene and 0.1-3 parts by weight of the above-mentioned adjuvant composition, and extruding and granulating.
In a fourth aspect, the present invention provides a polyethylene rotomoulded tank article made from the above linear medium density polyethylene composition.
By the technical scheme, on the basis of the existing linear medium density polyethylene powder, the invention has the following beneficial effects: on the first hand, the quality of rotational molding raw materials is improved, the raw materials are easy to grind and process, and the products have good inner and outer surface smoothness, good whiteness, good toughness, high stiffness, easy demoulding, and good environmental stress resistance and ultraviolet light aging resistance.
In the second aspect, the processing performance of rotational molding is improved, the fluidity of materials is improved, the processing time is reduced, and the energy consumption is saved.
In the third aspect, the economy is good. The composition and the prepared rotational molding product of the invention take 1 ton of material for each large storage tank as a reference, under the same processing conditions, compared with the current commercially available Korean imported material, the raw material cost is saved by nearly 1500 yuan, and the quality of the products obtained by the composition and the prepared rotational molding product is equivalent to that of imported high-end material basically.
In the fourth aspect, the raw material sources are widened, the monopoly of import materials for a long time is broken, and the price of the import materials is forced to be reduced.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, one or more new ranges of values may be obtained from combinations of values between the endpoints of each range, the endpoints of each range and the individual values, and the individual values of the points, and these ranges of values should be considered as specifically disclosed herein.
The invention provides an auxiliary composition, which is characterized by comprising the following components in percentage by weight based on the total weight of the composition:
(1) 5-25% of main antioxidant, preferably 10% -20%;
(2) auxiliary antioxidant, 5-25%, preferably 10% -20%;
(3) external lubricant, 3-15%, preferably 5% -10%;
(4) antistatic agent, 3-15%, preferably 5% -10%;
(5) 20-50% of light stabilizer A, preferably 25% -45%; the light stabilizer A is one or more of hindered amine light stabilizer and benzophenone light stabilizer with triazine skeleton;
(6) 15-45%, preferably 20% -40%, of the light stabilizer B, wherein the light stabilizer B is one or more of a hindered amine type light stabilizer and a benzotriazole type light stabilizer with an ester-based skeleton.
In the invention, the main antioxidant is used for capturing free radicals generated in the degradation process during the production, processing and use of the polymer so as to continuously exert the antioxidant effect for a long time, and the oxidation induction period of the linear medium density polyethylene composition containing the auxiliary agent composition is more than 60min measured by a DSC instrument under the oxygen atmosphere at 200 ℃. And the compatibility of the main antioxidant and polyethylene is good. As long as the antioxidant satisfying both of the above conditions is used as the main antioxidant in the present invention, it is preferably one or more selected from hindered phenol type antioxidants and hindered amine type antioxidants, preferably one or more selected from the group consisting of antioxidant 1076, antioxidant 1010, antioxidant 1790, antioxidant 330, antioxidant BHT and antioxidant 944.
In the invention, the secondary antioxidant is mainly used for decomposing hydroperoxide and peroxide generated by further degradation of plastics, thereby achieving the purpose of antioxidation, improving the thermal oxidation processing stability, and the secondary antioxidant can not be seriously aged by oxidation in the life span of products by matching with the primary antioxidant, so the antioxidant which can play the role can be used as the secondary antioxidant of the invention, preferably a reducing agent, for example, one or more selected from phosphite type antioxidants and thioester type antioxidants, preferably one or more selected from antioxidant 168, antioxidant 626, antioxidant 618, antioxidant DLTP and antioxidant DSTP.
In the present invention, the weight ratio of the primary antioxidant to the secondary antioxidant is preferably 1: 0.3-3, more preferably 1: 0.5-2. The main antioxidant eliminates free radicals, the auxiliary antioxidant decomposes peroxide, the two are used in polyethylene according to the mixture ratio, the synergistic effect is obvious, the thermal degradation and oxidative degradation of the polymer can be effectively inhibited, and the antioxidant 1076 is selected to be combined with one or more of the antioxidant 168, the antioxidant 626, the antioxidant 618, the antioxidant DLTP and the antioxidant DSTP for use in the composition, so that the best effect can be generated.
In the present invention, the external lubricant is a lubricant which improves the fluidity of extrusion of the material and improves the mold release property during the molding of the product, and therefore, any lubricant which can perform this function may be used as the external lubricant of the present invention, and is preferably selected from a long-chain fatty acid metal salt, preferably a straight-chain fatty acid metal salt having 10 to 25 carbon atoms, more preferably a straight-chain fatty acid divalent metal salt having 10 to 25 carbon atoms, and particularly preferably one or more of zinc stearate, magnesium stearate, and calcium stearate. The inventor of the invention finds that zinc stearate has a melting point closer to that of polyethylene, has better compatibility than other stearates because the zinc stearate can play a role of an acid scavenger and processing lubrication, has a better effect of external lubrication in polyethylene and is beneficial to demolding of large-scale products, so the external lubricant is particularly preferably zinc stearate.
In the present invention, the antistatic agent is used to improve the antistatic property of the article, and to guide and eliminate the accumulation of static charge caused by the friction between dusts in the pellet milling process and the article production process. Preferably one or more selected from the group consisting of ethoxylated fatty alkylamines, ethoxylated alkyl acid amines and fatty acid polyol esters, wherein the number of carbon atoms of the above-mentioned fatty alkyl, alkyl acid and fatty acid is preferably 10 to 25; further preferred is one or more of N, N-dihydroxyethyl octadecylamine, N-dimethyl laurylamine and glycerol monostearate.
In the present invention, the weight ratio of the external lubricant to the antistatic agent is preferably 1: (0.8-1.5), more preferably 1: (0.9-1.4), within which preferable range the processability of the article can be improved without affecting the mechanical properties of the article.
In the present invention, the light stabilizer a not only HAs an antioxidant effect but also HAs a long-term heat stabilizing effect on the polymer, and is preferably one or more selected from the group consisting of light stabilizers UV770, UV119, UV2020, UV944, UV3346, HA88, UV531 and UV 9.
In the invention, the light stabilizer B has better heat resistance, extraction resistance, lower volatile component and migration and excellent long-acting light aging resistance. Preferably one or more selected from the group consisting of light stabilizers UV622, UV3853, UV770, UV234, UV 329.
In the invention, the ash content of the light stabilizer A and the light stabilizer B is less than or equal to 0.1 weight percent, the impurity content is ensured to be as small as possible, and meanwhile, the volatile component is less than or equal to 0.5 weight percent, so that the residual solvent amount is minimum, the odor is reduced, and the environment is protected.
In the present invention, the combination of a long-acting light stabilizer and a light stabilizer for improving the processing stability, the synergistic effect of the long-acting light stabilizer and the light stabilizer can enable the polymer product to pass ASTM G155 detection, and the ultraviolet resistance grade reaches 6.
According to a preferred embodiment of the invention, the auxiliary composition comprises 10 to 20 wt.%, 5 to 10 wt.%, 25 to 45 wt.% and 20 to 40 wt.%, based on the total amount of the composition, of the antioxidant 1076, the antioxidant 168, zinc stearate, N-dihydroxyethyloctadecylamine, the light stabilizer UV944 and the light stabilizer UV622, respectively. The assistant composition adopting the preferred mode can further improve the demolding performance, the rigidity-toughness balance and the weather resistance of the product.
The second aspect of the present invention provides a linear medium density polyethylene composition, wherein the linear medium density polyethylene composition comprises: based on the total weight of the linear medium density polyethylene composition, the polyethylene composition contains 97 to 99.9 weight portions of linear medium density polyethylene and 0.1 to 3 weight portions of the auxiliary agent composition.
In the present invention, the composition has a melt index of 4.5 to 5.5g/10min at 190 ℃ under a load of 2.16kg and a density of 0.933 to 0.939g/cm3。
In a third aspect, the present invention provides a process for preparing a linear medium density polyethylene composition, wherein the process comprises blending 97 to 99.9 parts by weight of a linear medium density polyethylene and 0.1 to 3 parts by weight of the above adjuvant composition, and extrusion granulating to produce the linear medium density polyethylene composition.
In the invention, the linear medium density polyethylene has a melt index of 4.6-5.6g/10min at 190 ℃ under a load of 2.16kg and a density of 0.932-0.938g/cm3. The melt finger and the density of the polyethylene are controlled within the smaller range, and the polyethylene is matched with the auxiliary agent composition, so that the polyethylene is easy to grind and process, and the prepared product has the advantages of good surface smoothness, no bubbles, good whiteness, good toughness, high stiffness, easy demoulding and good environmental resistanceThe performance and the ultraviolet aging resistance can be achieved, and the performance of the polyethylene composition raw material imported from foreign countries can be achieved with lower production cost. The linear medium density polyethylene can be obtained commercially or prepared by adopting a Unipol gas phase method which is conventional in the field and combining the optimization control of process parameters.
According to a specific embodiment of the present invention, the method for preparing the linear medium density ethylene composition may comprise the steps of:
the first step is as follows: prepared by Unipol gas phase method, has a melt index of 4.6-5.6g/ml at 190 deg.C under 2.16kg load and a density of 0.932-0.938g/cm3The linear medium density polyethylene powder of (4).
The second step is that: the obtained linear medium density polyethylene is mixed with the auxiliary agent composition, and is extruded and granulated to prepare the linear medium density polyethylene composition.
Pigments may or may not be added prior to extrusion granulation as desired by the downstream customer. The phthalocyanine blue pigment is preferably added because the phthalocyanine blue pigment has bright color, strong tinting strength, light resistance and heat resistance, and is favorable for placing large-sized products outdoors for a long time. The pigments may be used in an amount of 0.1 to 1% by weight, preferably 0.4 to 0.6% by weight, based on the linear medium density polyethylene.
In the present invention, the extrusion granulation can be performed by using the methods and conditions known to those skilled in the art, preferably, the conditions of the extrusion granulation include a temperature of 190-3。
According to the invention, the auxiliary composition is prepared firstly, so that all components of the auxiliary composition are uniformly mixed, and then the auxiliary composition is mixed with linear medium density polyethylene and extruded for granulation, when the obtained polyethylene particles are used for preparing large storage tank products by a rotational molding process, the products have good inner and outer surface smoothness, good whiteness, good toughness, high stiffness, easy demoulding, good environmental stress resistance and ultraviolet aging resistance, the fluidity of materials is improved, the processing performance of rotational molding is improved, the heating time of a 25-liter incubator is reduced by 3-5min, the energy consumption is saved, and the cost of the polyethylene particles is 1500 yuan/ton lower than that of imported raw materials sold in the market at present.
In a fourth aspect the present invention provides a polyethylene rotomoulded tank article made from the above linear medium density polyethylene composition.
The invention uses the linear medium density polyethylene composition, and the linear medium density polyethylene composition is processed and molded after being color-matched and ground into powder with a certain mesh number. The prepared polyethylene rotational molding storage tank product can be determined according to the application direction of a rotational molding product of a user, and the rigidity and the toughness are considered simultaneously by adjusting the proportion.
The linear medium density polyethylene composition provided by the invention can be used for preparing a storage tank with the volume of more than 10000L.
The present invention will be described in detail below by way of examples.
Antioxidant 1076 was purchased from san Lekets, Inc. under CAS registry number 2082-79-3.
Antioxidant 168 was purchased from san Lekets, Inc. under CAS registry number 31570-04-4.
Antioxidant 626 was purchased from Beijing, Seiko chemical company under CAS registry number 26741-53-7.
Antioxidant 618 is available from Beijing, very easily available from chemical Co., Ltd, CAS number 3806-34-6.
Zinc stearate was purchased from Nanjing Chunda science Inc. under CAS registry number 557-05-1.
Calcium stearate was purchased from Ningbo Yuetyu, Inc. under CAS registry number 1592-23-0.
Antistatic agent 1800 is available from Nanjing Chunda science, Inc. under CAS registry number 10213-78-2.
Antistatic agents GMS are available from Ningbo Yuetu, Inc. under CAS registry number 621-61-4.
The antistatic agent N, N-dimethyl laurylamine is purchased from Shandong Polymer chemical Co., Ltd, and the CAS number is 203-.
Light stabilizer UV944 was purchased from Jiangsu Suqian Sidesh Chemicals, Inc. under CAS registry number 70624-18-9.
Light stabilizer UV2020 is available from Pasteur, Germany under the CAS registry number 192268-64-7.
Light stabilizer UV622 is available from Jiangsu Suqian Sichuan Chemicals, Inc. under CAS registry number 65447-77-0.
Light stabilizer UV3853 was purchased from Solvay, USA under CAS registry number 167078-06-0.
The light stabilizer UV531 is purchased from Beijing very easy chemical Co., Ltd, and the CAS registration number is 1843-05-6.
The light stabilizer UV234 was obtained from Jiangsu Suqian Co Ltd under CAS registry number 70321-86-7.
The light stabilizer UV329 is purchased from Beijing Suiko chemical Co., Ltd, and has a CAS number of 3147-75-9.
The light stabilizer UV770 is purchased from Beijing Suiko chemical Co., Ltd, and has a CAS number of 52829-07-9.
Example 1
(1) Preparation of the adjuvant composition
Based on the total weight of the assistant composition, 10 wt% of antioxidant 1076, 20 wt% of antioxidant 626, 6 wt% of zinc stearate, 10 wt% of antistatic agent GMS, 25 wt% of UV2020 and 29 wt% of UV622 are mixed to obtain the assistant composition.
(2) Production of linear medium density polyethylene compositions
(2.1) melt index 5.0g/10min at 190 ℃ under 2.16kg load and density 0.934g/cm prepared by Unipol gas phase Process3Linear medium density polyethylene (powder).
(2.2) blending 98 parts by weight of the linear medium density polyethylene obtained in the step (2.1) and 2 parts by weight of the auxiliary composition obtained in the step (1) based on the total weight of the linear medium density polyethylene composition, and obtaining linear medium density polyethylene composition particles by an extrusion granulator (model ZSK350, manufactured by CWP company of Germany, the same applies hereinafter), wherein the temperature of the extruder is 240 ℃, the power is 6600kW, and the mesh number of the filter screen of the extruder is more than 100 meshes.
(3) Production 20 cube storage tank (PT-20000L vertical flat bottom water tank)
Taking 650kg of granules of the prepared linear medium-density polyethylene composition, grinding the granules into powder of about 30 meshes, injecting the powdery material into a steel mould, directly heating the swinging rotational molding mould through open fire, and uniformly distributing the material in an inner cavity of the mould under the action of self gravity and centrifugal force and melting the material. The production of the product comprises feeding materials twice, wherein 90% of the raw materials are fed for the first time, feeding materials for the second time after the mold is completely melted, the rest 10% of the raw materials are added, the mold processing temperature is about 280 ℃, the open fire is closed to heat after the mold is completely melted, the direct firing time is about 1.5h, the hollow product S1 is obtained after natural cooling, air cooling and demolding after 3 h, and the thickness of the hollow product S1 is about 16 mm.
Example 2
(1) Preparation of the adjuvant composition
Based on the total weight of the assistant composition, 13 wt% of antioxidant 1076, 15 wt% of antioxidant 168, 6 wt% of zinc stearate, 6 wt% of antistatic agent N, N-dimethyl laurylamine, 30 wt% of UV622 and 30 wt% of UV944 are mixed to obtain the assistant composition.
(2) Production of linear medium density polyethylene compositions
(2.1) melt index of 4.9g/ml at 190 ℃ under 2.16kg load and density of 0.933g/cm prepared by Unipol gas phase process3Linear medium density polyethylene (powder).
(2.2) mixing 97 parts by weight of the linear medium density polyethylene obtained in the step (2.1) and 3 parts by weight of the auxiliary agent composition obtained in the step (1) based on the total weight of the linear medium density polyethylene composition, and obtaining linear medium density polyethylene composition particles through an extrusion granulator, wherein the temperature of the extruder is 240 ℃, the power is 6600kW, and the mesh number of the filter screen of the extruder is more than 100 meshes.
(3) Production 20 cube vertical cone bottom storage tank (CPT-20000L)
Taking 800kg of granules of the prepared linear medium-density polyethylene composition, grinding into powder of about 30-40 meshes, injecting the powdery material into a steel mould, directly heating the swinging rotational molding mould through open fire, and uniformly distributing the material in an inner cavity of the mould under the action of self gravity and centrifugal force and melting. The product is fed once, the processing temperature of the die is about 280 ℃, after the die is melted and filled, the die is closed and heated by open fire, the direct firing time is about 62min, the product is naturally cooled and air-cooled for 2 hours, and then the die is removed, so that a hollow product S2 is obtained, wherein the thickness of the product is about 18 mm.
Example 3
(1) Preparation of the adjuvant composition
Based on the total weight of the assistant composition, 20 wt% of antioxidant 1076, 10 wt% of antioxidant 618, 5 wt% of zinc stearate, 5 wt% of antistatic agent 1800, 40 wt% of UV944 and 20 wt% of UV3853 are mixed to obtain the assistant composition.
(2) Production of linear medium density polyethylene compositions
(2.1) melt index 5.1g/ml at 190 ℃ under 2.16kg load and density 0.935g/cm prepared by Unipol gas phase Process3Linear medium density polyethylene (powder).
(2.2) mixing 99 parts by weight of the linear medium density polyethylene obtained in the step (2.1) and 1 part by weight of the auxiliary agent composition obtained in the step (1) based on the total weight of the linear medium density polyethylene composition, and obtaining linear medium density polyethylene composition particles through a twin-screw extrusion granulator, wherein the temperature of an extruder is 240 ℃, the power is 6600kW, and the mesh number of the filter screen of the extruder is more than 100 meshes.
(3) Preparation of polyethylene rotomoulded articles 2 rotomoulded articles were prepared by different processes as follows
(3-1) producing a 15-cubic horizontal chemical storage tank (LT-15000L). Taking 500kg of granules of the prepared linear medium density polyethylene composition, grinding the granules into powder of about 30-40 meshes, injecting the powdery material into a steel mould, directly heating the swinging rotational molding mould through open fire, and uniformly distributing the material in an inner cavity of the mould under the action of self gravity and centrifugal force and melting the material. The once feeding of the product is carried out, the processing temperature of the die is about 280-300 ℃, after the die is fully melted, the open fire is closed for heating, the direct firing time is about 50min, the natural cooling and air cooling are carried out for 1.5 hours totally, and then the demoulding is carried out, so that a hollow product S3-1 is obtained, and the thickness of the product is about 16 mm.
(3-2) 25L incubator. Adding 0.5 wt% of phthalocyanine blue powder into the prepared linear medium-density polyethylene composition, performing extrusion granulation to obtain granules with required downstream colors, grinding the granules into powder with about 40-50 meshes, weighing 8kg of powdery material, injecting the powdery material into an aluminum mould, putting the mould into an oven, heating the mould, swinging, rolling and rotating a longitudinal shaft and a transverse shaft, and uniformly distributing the material in an inner cavity of the mould under the action of self gravity and centrifugal force and melting the material. The processing temperature of the furnace chamber is about 280-300 ℃, after the furnace chamber is melted and the mould is filled, the open fire is closed and the heating is carried out, the total time is 17min, the natural cooling and the air cooling are carried out, the demoulding is carried out after about 10min, and the hollow product S3-2 is obtained, the thickness of the product is about 5-7mm, and the thickness is uniform.
Example 4
A25-liter incubator was constructed as in example 3, except that the external lubricant, zinc stearate, was replaced with the same weight of calcium stearate, to give a hollow article S4.
Example 5
A25-liter incubator was fabricated by following the procedure of example 3, except that the antioxidant 1076 was replaced with the same weight of the antioxidant 1010, to obtain a hollow product S5.
Example 6
A25-liter incubator was fabricated by following the procedure of example 3, except that the antioxidant 1076 was replaced with the same weight of the antioxidant 330, to obtain a hollow product S6.
Example 7
A25 liter incubator was constructed as in example 3, except that the light stabilizer UV944 was replaced with the same weight of light stabilizer UV9 to provide a hollow article S7.
Comparative example 1
A 25-liter incubator was fabricated by following the procedure of example 3, except that the linear medium-density polyethylene composition pellets obtained in step (2) were directly replaced with korean imported brand No. UR644, to obtain a hollow article D1.
Comparative example 2
A25 liter incubator was constructed as in example 3, except that Thailand import M3204RU was used directly in place of the linear medium density polyethylene composition particles obtained in step (2), yielding hollow article D2.
Comparative example 3
A25 liter incubator was constructed as in example 3, except that the antioxidant 1076 was replaced with the same weight of the antioxidant 168, to give a hollow article D3.
Comparative example 4
A25 liter incubator was constructed as in example 3, except that the light stabilizer UV944 was replaced with the same weight of light stabilizer UV622 to give a hollow article D4.
Comparative example 5
A25 liter incubator was fabricated by following the procedure of example 3, except that the auxiliary composition was prepared without adding the light stabilizer UV944, but was prepared by mixing and granulating in the step (2) together with a linear medium density polyethylene powder, grinding into powder, and separately stirring and adding UV944 to give a hollow article D5.
Comparative example 6
A25 liter incubator was constructed as in example 3, except that the linear medium density polyethylene had a melt index of 5.0. + -. 1.0g/10min at 190 ℃ under a load of 2.16kg, and the fluctuation of the melt index was relatively large, to give a hollow article D6.
Test example
And (3) testing the odor: the product obtained during and after production was subjected to sensory testing by 10 persons, 2 persons considered to be odorous were scored as odorous, otherwise, the product was scored as odorless.
Surface smoothness: the smoothness of the inner and outer surfaces of the product is comprehensively evaluated by observing the flatness and smoothness of the surface by naked eyes, including whether a small amount of small bubbles are contained or not, and combining the feeling of hand touch with the same product made of the imported standard rod material. The product is obviously smooth, does not contain small bubbles, has relatively flat hand feeling and is marked as excellent; the appearance is smooth, the hand feeling is smooth, and the edges have occasional small bubbles which are marked as good; the feeling of smoothness was insufficient, the hand was not smooth, and the edge had a small number of small bubbles, and was recorded as "middle".
Heating time: the time for the period of time from the start of heating to the completion of melting in step (3) to the start of cooling for mold release was in minutes.
Demolding property: the unified operation worker judges and directly gives three grades of easy, medium and difficult.
Aging resistance: the product is filled with water, the water amount is increased by 10% compared with the normal water amount (the water amount with 90% of volume is filled under the normal condition), the product is placed in the air for more than 2 years in east China, ultraviolet irradiation is carried out for a long time, the fine crack condition of the product is observed by a magnifying glass, no fine crack is marked as excellent, a small amount of fine crack is marked as good, and a large amount of fine crack is marked as medium.
Weather resistance: when the air temperature difference is large (mainly the early and late time in winter and summer, the temperature difference is larger than about 20 ℃), measuring the outer diameter of the product, and investigating the load-bearing weather-resistant deformation condition, the product is marked as excellent weather resistance when the outer diameter changes by less than 5%, and is marked as good when the outer diameter changes by 5-10%, and is marked as medium when the outer diameter changes by more than 10%.
Toughness: 1) in winter, the product is filled with water, after the water is frozen, the hammer is used for knocking and observing the damage condition, the damage cannot be seen and is marked as excellent, the damage cannot be seen obviously and is marked as good, and the damage can be seen obviously and is marked as medium.
2) A100L container is simultaneously manufactured in a trial mode from the downstream, the container falls from a height of 10 meters, the damage condition is observed, the damage cannot be seen and is marked as excellent, the damage cannot be seen obviously and is marked as good, and the damage can be seen obviously and is marked as medium.
Material consumption: the weight of the raw materials used in step 3) is kg.
The cases of the above examples and comparative examples are listed in the following table 1.
As can be seen from the results in Table 1, the product prepared by the example of the invention has better appearance, good processing performance, better smoothness of the inner and outer surfaces of the product, and equivalent toughness, environmental stress cracking resistance and ultraviolet aging resistance. Compared with imported high-end materials, the high-end material has higher economic benefit and social benefit, and simultaneously, the product can better meet the product requirements of manufacturers in all aspects of performance.
Under the same processing conditions, the heating time of the 25L insulation can product in the example is saved by about 13% at most, and is reduced from the original heating time of 20min to 17min, so that the energy is saved and the consumption is reduced in the rotational molding process, and meanwhile, the performance of the base resin is protected to a certain extent.
Moreover, the raw material cost can be saved by at least about 15 ten thousand yuan, not counting the energy consumption saving, under the same processing condition, calculated by the average dosage of the linear medium density polyethylene composition per month in a downstream plant of 100 tons.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. An auxiliary composition, which is characterized by comprising the following components in percentage by weight based on the total weight of the composition:
(1) 5-25% of main antioxidant, preferably 10% -20%;
(2) auxiliary antioxidant, 5-25%, preferably 10% -20%;
(3) external lubricant, 3-15%, preferably 5% -10%;
(4) antistatic agent, 3-15%, preferably 5% -10%;
(5) 20-50% of light stabilizer A, preferably 25% -45%; the light stabilizer A is one or more of hindered amine light stabilizer and benzophenone light stabilizer with triazine skeleton;
(6) 15-45%, preferably 20% -40%, of the light stabilizer B, wherein the light stabilizer B is one or more of a hindered amine type light stabilizer and a benzotriazole type light stabilizer with an ester-based skeleton.
2. The auxiliary composition according to claim 1,
the primary antioxidant is selected from one or more of hindered phenol type antioxidants and hindered amine type antioxidants, preferably one or more of antioxidant 1076, antioxidant 1010, antioxidant 330, antioxidant 1790, antioxidant BHT and antioxidant 944;
the auxiliary antioxidant is selected from one or more of phosphite type antioxidant and thioester type antioxidant, preferably one or more of antioxidant 168, antioxidant 626, antioxidant 618, antioxidant DLTP and antioxidant DSTP;
the external lubricant is selected from one or more of stearate, paraffin and fatty acid, preferably one or more of zinc stearate, magnesium stearate and calcium stearate;
the antistatic agent is selected from one or more of ethoxylated fatty alkylamine, ethoxylated alkyl amine and fatty acid polyol ester, preferably one or more of N, N-dihydroxyethyl octadecyl amine, N-dimethyl lauryl amine and trioctal monostearate;
the light stabilizer A is selected from one or more of light stabilizers UV770, UV119, UV2020, UV944, UV3346, HA88, UV531 and UV 9;
the light stabilizer B is selected from one or more of light stabilizers UV622, UV3853, UV770, UV234 and UV 329.
3. The auxiliary composition according to claim 1 or 2, wherein the weight ratio of the primary antioxidant to the secondary antioxidant is 1 (0.3-3).
4. The auxiliary composition according to any one of claims 1 to 3, wherein the weight ratio of the external lubricant to the antistatic agent is 1 (0.8 to 1.5).
5. The auxiliary composition according to any of claims 1 to 4, wherein the light stabilizer A and the light stabilizer B have an ash content of 0.1% by weight or less and a volatile content of 0.5% by weight or less.
6. A linear medium density polyethylene composition comprising a linear medium density polyethylene and the adjuvant composition of any of claims 1 to 5, wherein the linear medium density polyethylene is present in an amount of 97 to 99.9 parts by weight and the adjuvant composition is present in an amount of 0.1 to 3 parts by weight, based on the total weight of the linear medium density polyethylene composition.
7. The linear medium density polyethylene composition according to claim 6, wherein the composition has a melt index of 4.5 to 5.5g/10min at 190 ℃ under a 2.16kg load and a density of 0.933 to 0.939g/cm3。
8. A process for the production of a linear medium density polyethylene composition, wherein the process comprises blending 97 to 99.9 parts by weight of a linear medium density polyethylene and 0.1 to 3 parts by weight of the adjuvant composition according to any of claims 1 to 5, and extrusion granulating.
9. The preparation method according to claim 8, wherein the linear medium density polyethylene has a melt index of 4.6 to 5.6g/10min at 190 ℃ under a 2.16kg load and a density of 0.932 to 0.938g/cm3。
10. The linear medium density polyethylene composition produced by the method of producing of claim 8 or 9.
11. A polyethylene rotomoulded article made from the linear medium density polyethylene composition of claim 6 or 7 or 10.
12. The article of claim 11, wherein the article is a tank having a volume greater than 10000L.
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