CN114702755A - Functional master batch suitable for thin-wall high-length-diameter-ratio polypropylene ribbon and preparation method and application thereof - Google Patents
Functional master batch suitable for thin-wall high-length-diameter-ratio polypropylene ribbon and preparation method and application thereof Download PDFInfo
- Publication number
- CN114702755A CN114702755A CN202210522053.4A CN202210522053A CN114702755A CN 114702755 A CN114702755 A CN 114702755A CN 202210522053 A CN202210522053 A CN 202210522053A CN 114702755 A CN114702755 A CN 114702755A
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- functional
- master batch
- lubricant
- lubricants
- 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.)
- Granted
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 110
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 86
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 86
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000314 lubricant Substances 0.000 claims abstract description 62
- 229920001577 copolymer Polymers 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000002216 antistatic agent Substances 0.000 claims abstract description 21
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 239000002667 nucleating agent Substances 0.000 claims abstract description 15
- 239000002250 absorbent Substances 0.000 claims abstract description 11
- 230000002745 absorbent Effects 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 26
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 238000001125 extrusion Methods 0.000 claims description 16
- 238000005469 granulation Methods 0.000 claims description 15
- 230000003179 granulation Effects 0.000 claims description 15
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 12
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 12
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 8
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 7
- 239000012964 benzotriazole Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- 239000012170 montan wax Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 4
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 claims description 4
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- 238000001035 drying Methods 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
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical group CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- FUVVCZPEOKAHJS-UHFFFAOYSA-N 1-dodecoxy-3-(2-hydroxyethylamino)propan-2-ol Chemical compound CCCCCCCCCCCCOCC(O)CNCCO FUVVCZPEOKAHJS-UHFFFAOYSA-N 0.000 claims description 2
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 claims description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 2
- PSKABHKQRSJYCQ-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)-6-[[3-(2H-benzotriazol-4-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]methyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)C=2C=3N=NNC=3C=CC=2)O)=C(O)C=1C1=CC=CC2=C1N=NN2 PSKABHKQRSJYCQ-UHFFFAOYSA-N 0.000 claims description 2
- BITAPBDLHJQAID-MDZDMXLPSA-N 2-[2-hydroxyethyl-[(e)-octadec-9-enyl]amino]ethanol Chemical compound CCCCCCCC\C=C\CCCCCCCCN(CCO)CCO BITAPBDLHJQAID-MDZDMXLPSA-N 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- WTSAKMSVTHDBCS-UHFFFAOYSA-N benzoic acid;hydrazine Chemical compound [NH3+]N.[O-]C(=O)C1=CC=CC=C1 WTSAKMSVTHDBCS-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- CDWDDCFBDRKNLE-UHFFFAOYSA-N dihydrogen phosphate;2-hydroxyethyl-dimethyl-[3-(octadecanoylamino)propyl]azanium Chemical compound OP(O)([O-])=O.CCCCCCCCCCCCCCCCCC(=O)NCCC[N+](C)(C)CCO CDWDDCFBDRKNLE-UHFFFAOYSA-N 0.000 claims description 2
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 claims description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 2
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims description 2
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 claims description 2
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims description 2
- TYTUEXPNTQGSDO-UHFFFAOYSA-N hydrazine 2-hydroxybenzoic acid Chemical compound NN.OC1=C(C(=O)O)C=CC=C1 TYTUEXPNTQGSDO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical group S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- ITFGZZGYXVHOOU-UHFFFAOYSA-N n,n-dimethylmethanamine;methyl hydrogen sulfate Chemical compound C[NH+](C)C.COS([O-])(=O)=O ITFGZZGYXVHOOU-UHFFFAOYSA-N 0.000 claims description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 2
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims 2
- SBZUEZTWHOASHE-UHFFFAOYSA-N 1-(4-octadecanoylpiperazin-1-yl)octadecan-1-one Chemical compound CCCCCCCCCCCCCCCCCC(=O)N1CCN(C(=O)CCCCCCCCCCCCCCCCC)CC1 SBZUEZTWHOASHE-UHFFFAOYSA-N 0.000 claims 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims 1
- HEUUBWQOIYCBCI-UHFFFAOYSA-N 2h-benzotriazole;copper Chemical compound [Cu].C1=CC=CC2=NNN=C21 HEUUBWQOIYCBCI-UHFFFAOYSA-N 0.000 claims 1
- 239000005639 Lauric acid Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000000199 molecular distillation Methods 0.000 claims 1
- 238000001746 injection moulding Methods 0.000 abstract description 17
- 238000012545 processing Methods 0.000 abstract description 12
- 239000000843 powder Substances 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 26
- 239000000203 mixture Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000004033 plastic Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000006750 UV protection Effects 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000013538 functional additive Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 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 3
- HCYSJBICYOIBLS-UHFFFAOYSA-N 2-(dodecylamino)ethanol Chemical compound CCCCCCCCCCCCNCCO HCYSJBICYOIBLS-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010137 moulding (plastic) Methods 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YWEWWNPYDDHZDI-JJKKTNRVSA-N (1r)-1-[(4r,4ar,8as)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C1=C(C)C(C)=CC=C1C1O[C@H]2[C@@H]([C@H](O)CO)OC(C=3C=C(C)C(C)=CC=3)O[C@H]2CO1 YWEWWNPYDDHZDI-JJKKTNRVSA-N 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- PIYNPBVOTLQBTC-UHFFFAOYSA-N 1-[8-propyl-2,6-bis(4-propylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound O1C2C(CCC)OC(C=3C=CC(CCC)=CC=3)OC2C(C(O)CO)OC1C1=CC=C(CCC)C=C1 PIYNPBVOTLQBTC-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- XSXYESVZDBAKKT-UHFFFAOYSA-N 2-hydroxybenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1O XSXYESVZDBAKKT-UHFFFAOYSA-N 0.000 description 1
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 1
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 1
- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
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- 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 description 1
- MBAUOPQYSQVYJV-UHFFFAOYSA-N octyl 3-[4-hydroxy-3,5-di(propan-2-yl)phenyl]propanoate Chemical compound OC1=C(C=C(C=C1C(C)C)CCC(=O)OCCCCCCCC)C(C)C MBAUOPQYSQVYJV-UHFFFAOYSA-N 0.000 description 1
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- ZCSNFGCDVJGPDD-YGJXXQMASA-M sodium;(1r,4as,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthrene-1-carboxylate Chemical compound [Na+].[O-]C(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 ZCSNFGCDVJGPDD-YGJXXQMASA-M 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
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Classifications
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- C08J3/223—Packed additives
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/08—Copolymers of ethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2427/06—Homopolymers or copolymers of vinyl chloride
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Abstract
The invention discloses a functional master batch suitable for a thin-wall high-length-diameter ratio polypropylene ribbon, and a preparation method and application thereof, wherein the functional master batch comprises an ethylene-octene copolymer, a first functional auxiliary agent and a second functional auxiliary agent; the first functional auxiliary agent comprises a lubricant, an antioxidant and a nucleating agent, and the second functional auxiliary agent comprises at least one selected from an ultraviolet absorbent, an antistatic agent and a copper resisting agent; the functional master batch is prepared by mixing all components, extruding and granulating, and controlling the processing temperature to partially melt the solid ethylene-octene copolymer, wherein the ethylene-octene copolymer coats other components in the prepared functional master batch; the master batch can be directly mixed with polypropylene to be injected into a thin-wall polypropylene ribbon with high length-diameter ratio, so that not only can multiple times of hot processing of the polypropylene be avoided, but also the auxiliary agent powder can be well dispersed in the system in the injection molding process, and the system is endowed with excellent low-temperature resistance, mechanical (mechanical) performance and other functional properties.
Description
Technical Field
The invention belongs to the technical field of polymer materials and processing, particularly relates to a thin-wall high-length-diameter-ratio plastic product, and particularly relates to a functional master batch suitable for a thin-wall high-length-diameter-ratio polypropylene ribbon, and a preparation method and application thereof.
Background
Thin-walled plastic molding technology is a relative concept, and the definition in the industry is generally divided into three cases:
(1) the injection molding with the ratio L/T of the flow length to the thickness of more than 100 or 150 is thin-wall high-length-diameter ratio injection molding, L is the flow length from the melt entering a mold to the farthest point of a cavity which must be filled with the melt, and T is the corresponding average wall thickness;
(2) the thickness of the formed plastic part is less than 1mm, and the projection area of the plastic part is 50cm2The above injection molding method;
(3) injection molding in which the wall thickness of the molded article is less than 1mm (or 1.5mm), or t/d (the thickness t of the molded article, the diameter d of the molded article, for a disk-shaped molded article) is 0.05 or less is defined as thin-wall injection molding.
At present, the application of domestic thin-wall plastic molding technology in the fields of food containers, medicine boxes, cosmetics, stationery and the like belongs to thin-wall small-length-diameter-ratio injection molding. In the aspect of thin-wall high-length-diameter-ratio injection molding, due to the thin-wall high-length-diameter-ratio injection molding technology, not only higher requirements are put forward on equipment and an injection molding process, but also higher requirements are put forward on high fluidity of raw materials, and the thin-wall low-length-diameter-ratio injection molding has lower requirements on the fluidity of the raw materials.
The polypropylene is a thermoplastic resin prepared by polymerizing propylene, and has wide application value because the polypropylene has excellent mechanical property, good heat resistance, stress cracking resistance and rigidity, and is easy to process and mold. Polypropylene, which is the fastest growing variety in general thermoplastic plastics, is increasingly important in economic construction and people's life, and has wide application in the aspects of automobile industry, household appliances, electronics, packaging, building materials, furniture and the like.
Thin-walled high aspect ratio articles are an important class of applications in plastics, with a more typical article being a cable tie. The ribbon serving as a first-class line product is extremely widely applied to production and life of the nation, particularly to popularization of application in civil and building industries, and the ribbon demand is increased year by year at the rate of 12-15%. At present, more than 90% of the bandages on the market are nylon products, and compared with polypropylene, nylon has the defects of high price, high moisture absorption and the like. In particular, the moisture absorption performance of nylon causes the tripping force of the cable tie to gradually decrease along with the increase of the environmental humidity under different use conditions. And polypropylene has no hygroscopicity, and the mechanical property of the product is hardly influenced by the relative humidity of the working condition. Therefore, the application of polypropylene in the binding belt field is developed, and the application field of the binding belt is beneficial to further expanding.
However, due to the uniqueness of the polypropylene structure, the polypropylene has the defects of poor low-temperature toughness and low notch impact strength, cannot resist ultraviolet irradiation and is easy to generate static accumulation; meanwhile, in the process of manufacturing the thin-wall high-length-diameter ratio ribbon, in order to improve the flowability of polypropylene and shorten the molding period, a nucleating agent is usually required to be added during the formula design so as to improve the crystallization rate of the polypropylene and reduce the crystal size, and the addition of the nucleating agent improves the crystallization behavior of the polypropylene and also brings the problems of poorer low-temperature toughness and lower notch impact strength of the polypropylene; in addition, the preparation of the cable tie needs to prepare the polypropylene composition firstly and then to be injection molded into the cable tie, namely, polypropylene needs to be subjected to multiple times of hot processing, so that the potential risk of reducing the physical and mechanical properties of the thin-wall high-length-diameter ratio polypropylene cable tie exists, and the application of the polypropylene cable tie is limited.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming one or more defects in the prior art and providing a novel functional master batch suitable for preparing a polypropylene ribbon, wherein the functional master batch and a polypropylene resin matrix can be directly mixed and injected to prepare the thin-wall polypropylene ribbon with high length-diameter ratio, so that not only is multiple hot processing of the polypropylene resin matrix avoided, but also auxiliary agent powder can be well dispersed in a system in the injection process and is not easy to phase separate, and the system is endowed with excellent low-temperature resistance, mechanical (mechanical) performance and other functionalities.
The invention also provides a preparation method of the functional master batch.
The invention also provides application of the functional master batch in preparation of the thin-wall polypropylene ribbon with high length-diameter ratio.
In order to solve the technical problems, the invention adopts a technical scheme as follows:
the functional master batch suitable for preparing the polypropylene ribbon comprises the following components in percentage by mass:
80-95% of ethylene-octene copolymer
0.22 to 9 percent of first functional auxiliary agent
0.1 to 15 percent of second functional auxiliary agent;
the first functional auxiliary agent is different from the second functional auxiliary agent, and the first functional auxiliary agent comprises the following components in percentage by mass: 0.2 to 5 percent of lubricant, 0.01 to 2 percent of antioxidant and 0.01 to 2 percent of nucleating agent;
the second functional auxiliary agent comprises one or more of ultraviolet absorbent, antistatic agent and copper resisting agent;
the functional master batch is prepared by mixing the components through an internal mixer, and then extruding and granulating; and in the preparation process, the mixing and extrusion granulation temperatures are controlled so as to partially melt the solid ethylene-octene copolymer, and the prepared functional master batch is coated with other components by the ethylene-octene copolymer.
In the invention, the temperature of the mixing and the extrusion granulation is controlled to ensure that the solid ethylene-octene copolymer is partially melted, namely the ethylene-octene copolymer is in a melting-like non-melting state, so that the phenomenon of complete melting of the ethylene-octene copolymer is avoided, and specifically, the temperature of the mixing and the extrusion granulation is controlled to ensure that in the ethylene-octene copolymer, a chain segment without forming aggregation nodes in an amorphous area is in a high-elasticity and flowable state, the microstructures of the aggregation nodes and a crystallization area are still maintained, the aggregation nodes and crystals are used as nodes under the shearing action of a rotor of an internal mixer, and the high-elasticity chain segment is used as a bridge to form a multidimensional structural network; under the action of the rotor, the matrix resin ethylene-octene copolymer gradually coats and disperses the processing aid in the matrix resin through continuous stretching deformation and shearing action.
Further, in the preparation process, a double-rotor continuous internal mixer can be adopted as the internal mixer.
According to some preferred aspects of the present invention, the melting point of the ethylene-octene copolymer is denoted by T, and the temperature for controlling the mixing and the extrusion granulation during the preparation process is respectively less than T +10 ℃ (in the art, the melting of the resin generally requires energy input and time input, and the melting rate of the resin can be controlled under the condition of reasonably controlled energy input and time input, so that the general processing temperature is higher than the melting point of the resin, generally 10-30 ℃, and a certain time window is given).
Further, in the preparation process, the mixing temperature and the extrusion granulation temperature are controlled to be T +/-5 ℃.
At the temperature, the matrix resin is partially melted, the partially melted resin and the low-melting-point functional additive are effectively mixed under the banburying condition, the high-melting-point functional additive still exists in a solid state and is dispersed into the mixture of the matrix resin (ethylene-octene copolymer) and the low-melting-point processing additive in a solid filling form, so that the melting phenomenon of most processing additives is avoided, the phase separation caused by compatibility is further avoided, the effective distribution of various functional additives is realized, and the smooth preparation of master batches is also ensured.
According to a particular aspect of the present invention, the ethylene-octene copolymer is available from Dow chemical (China) Inc., USA under the trade name 8401, and has a melting temperature of about 80 deg.C, and the mixing and extrusion granulation temperatures are controlled to be less than 90 deg.C respectively during the preparation process.
Further, in the preparation process, the mixing temperature is controlled to be 80 +/-2 ℃, and the extrusion granulation temperature is controlled to be 80 +/-2 ℃.
According to the present invention, if ethylene-octene copolymer matrix resins of different melting point grades are selected, the working temperature is adjusted accordingly.
According to some preferred aspects of the present invention, the ethylene-octene copolymer has a melt index of 15 to 50g/10 min.
According to some preferred and specific aspects of the present invention, the second functional assistant comprises an ultraviolet absorber, an antistatic agent and a copper-resistant agent, and the mass ratio of the ultraviolet absorber, the antistatic agent and the copper-resistant agent is 1: 0.5-2.
According to some preferred aspects of the present invention, the ultraviolet absorber is at least two selected from the group consisting of a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber and an amino-based ultraviolet absorber, and the benzophenone-based ultraviolet absorber is a combination of one or more selected from the group consisting of (2, 4-dihydroxyphenyl) phenyl ketone, 2-hydroxy-4-n-octyloxybenzophenone and (2-hydroxy-4-methoxyphenyl) phenyl ketone.
According to some preferred aspects of the present invention, the benzotriazole-based ultraviolet absorber is selected from the group consisting of 2- (2 '-hydroxy-3', 5 '-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -bis (a, a-dimethylbenzyl) phenyl) benzotriazole, bis (3-benzotriazolyl-2-hydroxy-5-tert-octylphenyl) methane, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, 2- [ 2-hydroxy-3, 5-bis (1, 1-dimethylpropylphenyl) ] -2H-benzotriazole and 2- [ 2-hydroxy-5- (1,1,3, 3-tetramethylbutyl) phenyl ] benzotriazole.
According to some preferred aspects of the present invention, the amino-based ultraviolet absorber is poly { [6- [ (1,1,3, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4- [ (2,2,6,6, -tetramethyl-piperidyl) imino ] -1, 6-hexamethylene [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] }.
In some preferred embodiments of the present invention, the UV absorber is a mixture of 2-hydroxy-4-n-octoxybenzophenone and 2- [ 2-hydroxy-3, 5-bis (1, 1-dimethylpropylphenyl) ] -2H-benzotriazole in a feed mass ratio of about 1-2: 1.
In some preferred embodiments of the invention, the UV absorber is a mixture of 2- (2' hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole and poly { [6- [ (1,1,3, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4- [ (2,2,6,6, -tetramethyl-piperidyl) imino ] -1, 6-hexadiene [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] }, the charge mass ratio being about 1-2: 1.
In some preferred embodiments of the present invention, the UV absorber is a mixture of 2- (2' hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole and 2- [ 2-hydroxy-3, 5-bis (1, 1-dimethylpropylphenyl) ] -2H-benzotriazole in an amount of about 1: 1-2 by mass.
In some preferred embodiments of the present invention, the UV absorber is a mixture of 2-hydroxy-4-n-octyloxybenzophenone and poly { [6- [ (1,1,3, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4- [ (2,2,6,6, -tetramethyl-piperidyl) imino ] -1, 6-hexadiene [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] }, in a feed mass ratio of about 1: 1-2.
According to the invention, the researches and the analyses of technical personnel believe that the polypropylene ribbon can be used in a high-humidity environment due to the characteristics of small polarity, poor water absorption and the like of polypropylene molecules, but has negative effects, namely the polypropylene ribbon has poor antistatic performance, is easy to accumulate static electricity, is difficult to lead and discharge and has potential safety hazards. In the practical process, the following specific antistatic properties or the combination thereof are selected to realize excellent antistatic performance.
According to some preferred aspects of the present invention, the antistatic agent is at least two selected from the group consisting of octadecyl amidopropyl dimethyl- β -hydroxyethyl quaternary ammonium nitrate, (3-lauric aminopropyl) trimethyl ammonium methylsulfate, stearamidopropyl dimethyl- β -hydroxyethyl ammonium dihydrogen phosphate, antistatic agent 68, oleyl bis (2-hydroxyethyl) amine, N- (3-dodecyloxy-2-hydroxypropyl) ethanolamine, N-bis (2-hydroxyethyl) alkylamine, molecularly distilled glycerol monostearate, octylphenol polyoxyethylene ether, polyoxyethylene stearate, and antistatic agent Pelestat 230.
In some preferred embodiments of the invention, the antistatic agent is a mixture of stearyl amidopropyl dimethyl-beta-hydroxyethyl quaternary ammonium nitrate and antistatic agent Antistat 68, dosed in a mass ratio of about 1.5-3.0: 1.
In some preferred embodiments of the present invention, the antistatic agent is a mixture of ammonium methyl (3-lauric aminopropyl) trimethyl sulfate and N, N-bis (2-hydroxyethyl) dodecylamide, dosed in a mass ratio of about 1: 0.8 to about 1.2.
In some preferred embodiments of the present invention, the antistatic agent is a mixture of ammonium (3-lauric aminopropyl) trimethyl sulfate methyl ester and the antistatic agent Antistat 68, and the mass ratio of the feeds is about 1-2: 1.
In some preferred embodiments of the invention, the antistatic agent is a mixture of stearyl amidopropyl dimethyl-beta-hydroxyethyl quaternary ammonium nitrate and N, N-bis (2-hydroxyethyl) dodecylamide, dosed at a mass ratio of about 1-2: 1.
According to the present invention, since polypropylene contains a large amount of tertiary carbon atoms and thus is not resistant to ultraviolet radiation, and once the polypropylene is in contact with copper for a long time in use, the polypropylene is damaged by copper, which causes post-shrinkage of products, and is easy to age, deform and embrittle, in the prior art, although the ultraviolet resistance of polypropylene can be improved by adding zinc oxide, carbon black or similar opalescent fillers, the polypropylene is lost in transparency due to the addition of the substances, and downstream customers have certain requirements on the transparency of products. In accordance with the practice of the present invention, the addition of certain copper inhibiting agents to the present system reduces or even avoids the "copper hazard" that may result from contact with copper.
According to some preferred aspects of the present invention, the copper inhibitor is a combination of one or more selected from the group consisting of benzotriazole-based copper inhibitors, oxalic acid dihydrazide, hydrazine benzoate, hydrazine salicylate, oxalic acid aniline-based copper inhibitors, condensates of salicylaldehyde and hexamethylenediamine, and condensates of furfural and hexamethylenediamine.
In some preferred embodiments of the present invention, the copper inhibitor is a mixture of benzoyl hydrazine and a condensate of salicylaldehyde and hexamethylene diamine, and is dosed at a mass ratio of about 1: 1 to about 3.
In some preferred embodiments of the present invention, the copper inhibitor is a mixture of salicyloyl hydrazine and a condensate of furfural and hexamethylene diamine, and is dosed at a mass ratio of about 1-2: 1.
In some preferred embodiments of the present invention, the copper inhibitor is a mixture of a condensate of salicylaldehyde and hexamethylenediamine and a condensate of furfural and hexamethylenediamine, and the mass ratio of the materials is about 0.8-1.2: 1.
In some preferred embodiments of the present invention, the copper inhibitor is a mixture of a condensation product of benzoyl hydrazine, furfural and hexamethylene diamine in a feed mass ratio of about 0.8 to 1.2: 1.
According to some preferences of the inventionIn one aspect, the lubricant is selected from the group consisting of hydrocarbon lubricants, amide lubricants, ester lubricants, organic salt lubricants, fluorine-containing lubricants, C8-30At least two of an alcohol lubricant and other types of lubricants.
Further, the lubricant is composed of ester lubricant and lubricant selected from amide lubricant, hydrocarbon lubricant, organic salt lubricant, fluorine-containing lubricant, C8-30Alcohol lubricants and other types of lubricants.
According to some preferred and specific aspects of the present invention, the ester lubricant is present in an amount of 20 to 60% by mass of the lubricant.
Further, the ester lubricant is composed of a combination of montan wax and optionally one or more selected from the group consisting of glycerol monooleate, pentaerythritol stearate, ester lubricant G16, and ester lubricant G60.
According to some preferred aspects of the invention, the hydrocarbon lubricant is a low density polyethylene formulation SA13-9 and/or a polyethylene wax.
According to some preferred aspects of the invention, the amide lubricant is a combination of one or more selected from the group consisting of N, N' -diethylenebisstearamide, oleamide, and amide wax.
According to some preferred aspects of the invention, C is8-30The alcohol lubricant is stearyl alcohol.
According to some preferred aspects of the present invention, the organic salt-based lubricant is a combination of one or more selected from the group consisting of calcium stearate, magnesium stearate, and sodium stearate.
According to some preferred aspects of the present invention, the fluorine-containing lubricant is a non-ionic fluorocarbon surfactant.
According to some preferred aspects of the invention, the other lubricant is molybdenum disulfide and/or oxidized polyethylene wax.
In some preferred embodiments of the present invention, the lubricant is comprised of montan wax, ester lubricant G16, and polyethylene wax, and is dosed at a mass ratio of about 1: 0.8 to about 1.2.
In some preferred embodiments of the present invention, the lubricant is composed of montan wax and polyethylene wax, and the mass ratio of the materials is about 1: 0.5-2.0.
In some preferred embodiments of the present invention, the lubricant is comprised of montan wax, N' -diethylene bis stearamide in a feed mass ratio of about 1: 1.5 to about 3.0.
According to some specific aspects of the invention, the antioxidant is a hindered phenolic antioxidant selected from one or more of Irganox 1076, Irganox 1135, Irganox 1520, Irganox 565, 2, 6-di-tert-butyl-p-cresol, Irganox2246, Irganox259, Irganox245, Irganox1081, Irganox1035, Irganox MD-1024, Irganox 1019, Irganox1010, Irganox1330, Irganox3114, Cyanox1010, and/or a phosphite antioxidant selected from one or more of Irg afos 168, Ultr anox 626, Mark PEP36, Cyanox2777, sandd Stab PEP Q, Pho phosphate a.
According to some specific aspects of the present invention, the nucleating agent is an inorganic nucleating agent and/or an organic nucleating agent.
In some embodiments of the invention, the inorganic nucleating agent is a combination of one or more selected from talc, mica and silica.
In some embodiments of the invention, the organic nucleating agent is a combination of one or more selected from the group consisting of adipate, diphenylmethylene sorbitol and derivatives thereof, sodium bis (2, 4-tert-butylphenyl) phosphate and derivatives thereof, benzoate, cinnamate, sodium tert-butylbenzoate, and sodium dehydroabietate. In some embodiments of the invention, the diphenylmethylene sorbitol and derivatives thereof may be Millad3988, Millad NX8000, etc., and the sodium bis (2, 4-tert-butylphenyl) phosphate and derivatives thereof may be NA-10, NA-11, NA-21, etc.
In some embodiments of the present invention, the nucleating agent is composed of an inorganic nucleating agent and an organic nucleating agent according to a feeding mass ratio of 1: 0.1-10, preferably according to a feeding mass ratio of 1: 0.2-5.
The invention provides another technical scheme that: the preparation method of the functional master batch suitable for preparing the polypropylene ribbon comprises the following steps: weighing the components according to the formula, mixing, extruding and granulating by a single screw, and drying to obtain the product.
The invention provides another technical scheme that: the utility model provides a thin wall high draw ratio polypropylene ribbon, the raw materials of polypropylene ribbon include above-mentioned be applicable to the functional master batch of preparation polypropylene ribbon, by the mass percent content, the functional master batch accounts for the mass percent content of the raw materials of polypropylene ribbon is 5% -20%.
In some embodiments of the present invention, the polypropylene ribbon comprises the following raw materials by mass percent: 80-95% of polypropylene material and 5-20% of the functional master batch.
In some embodiments of the present invention, the polypropylene material selected in the embodiments has a melting peak temperature of 155-170 ℃, a melting enthalpy of 60-100J/g, a crystallization peak temperature of 110-135 ℃, and a crystallization enthalpy of 70-105J/g.
According to some specific aspects of the present invention, the polypropylene material is a combination of one or more selected from block co-polypropylene and random co-polypropylene having an ethylene content of 7% to 15%.
In some embodiments of the invention, the polypropylene cable tie is made by mixing, injection molding, raw materials; wherein the injection molding temperature (zone 1-4) is: 125 ℃ temperature, 195 ℃ temperature, 220 ℃ temperature, 230 ℃ temperature and 220 ℃ temperature, 230 ℃ temperature.
The functional master batch can improve the fluidity of the polypropylene material relative to a mould, so that the mould is quickly filled in a limited space and time, and a thin-wall polypropylene ribbon with high length-diameter ratio can be manufactured; and can also have functionality such as antistatic, ultraviolet resistance, copper resistance, and the like.
In the present invention, the thin wall means a wall thickness of less than 1.5mm, or t/d (a plastic thickness t, a plastic diameter d, for a disk-shaped plastic) of 0.05 or less. High aspect ratio means that the ratio L/T of the flow length to the thickness, i.e. the ratio of the flow length L from the melt entering the mould to the furthest point of the cavity that the melt has to fill, to the corresponding average wall thickness T, is above 100, in particular the ratio of the length to the thickness of the article is above 100.
In the present invention, the melt index is measured at a temperature of 230 ℃ and a load of 2.16kg (measured according to the national standard: GB/T3682-2000).
In the present invention, the melting peak temperature, the melting enthalpy, the crystallization peak temperature, and the crystallization enthalpy are respectively measured by Differential Scanning Calorimetry (DSC).
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention provides a novel functional master batch for a polypropylene ribbon, which innovatively takes an ethylene-octene copolymer as a resin coating layer, on one hand, in the preparation process, the novel functional master batch can coat other functional powder auxiliaries to form a stable master batch form, and can directly mix the functional master batch with a polypropylene material in the later period, so that the novel functional master batch can be directly injected into the thin-wall high-length-ratio polypropylene ribbon without adding other auxiliaries, thereby avoiding multiple hot processing of the polypropylene material, and compared with the conventional mode of directly mixing the functional auxiliaries with the polypropylene material, the novel functional master batch is easier to disperse uniformly, is not easy to cause the phase separation phenomenon of powder and resin, and is favorable for ensuring the stability of the overall performance; on the other hand, the ethylene-octene copolymer provided by the invention can be used as an independent phase in a polypropylene ribbon to form a mutually blended uniform structure, so that the excellent compatibilization and toughening effect is achieved, the internal stress can be absorbed when the polypropylene ribbon is impacted, particularly under low-temperature impact, the low-temperature tolerance of the polypropylene ribbon is improved, and the polypropylene ribbon also has excellent mechanical (mechanical) properties.
In addition, the functional master batch can also improve the fluidity of the polypropylene material relative to a mould, so that the mould is quickly filled in a limited space and time, and the thin-wall high-length-diameter ratio polypropylene ribbon can be conveniently manufactured; and can also have functionality such as antistatic, ultraviolet resistance, copper resistance, and the like.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
In the following, all starting materials are either commercially available or prepared by conventional methods in the art, unless otherwise specified.
The block copolymer polypropylene has a melting peak temperature of 163 ℃ and a melting enthalpy of 79.9J/g, a crystallization peak temperature of 123 ℃, a crystallization enthalpy of 91.7J/g, and a melt index of 58g/10min, and is purchased from Bolu plastics (Shanghai) Co., Ltd.
Other raw material sources are as in table 1:
TABLE 1
Preparation of salicylaldehyde condensate with hexamethylenediamine: adding 60mL of salicylaldehyde and 300mL of absolute ethyl alcohol into a reaction vessel provided with a reflux condensing device and a stirring device, adding 78mL of hexamethylenediamine under stirring, heating to 75 ℃, continuously stirring for 1 hour, cooling the reaction liquid to room temperature after the reaction is finished, removing the solvent of the absolute ethyl alcohol, and drying the solid to obtain a light yellow solid for later use.
Preparation of the condensate of furfural with hexamethylenediamine: adding 65mL of furfural and 300mL of absolute ethanol into a reaction vessel provided with a reflux condensing device and a stirring device, adding 78mL of hexamethylenediamine under stirring, heating to 75 ℃, continuously stirring for 1 hour, cooling the reaction liquid to room temperature after the reaction is finished, removing the solvent of the absolute ethanol, and drying the solid to obtain a light yellow solid for later use.
Examples 1 to 4
Preparation of ethylene-octene copolymer powder: cooling the ethylene-octene copolymer to-70 ℃ in a precooling bin, transferring the material into a main machine grinding chamber through spiral conveying, grinding the material to about 75 micrometers (200 meshes) in particle size at-70 ℃, and collecting the powder through a cyclone separator.
The functional master batch suitable for preparing the polypropylene cable tie provided by the embodiments is shown in the following table 2.
TABLE 2
The preparation method of the functional master batch suitable for preparing the polypropylene ribbon comprises the following steps: weighing the raw materials according to the formula, mixing, and mixing by a double-rotor continuous internal mixer at the mixing temperature of 80 +/-2 ℃ and the rotor rotating speed of 300 r/min. The discharge port of the double-rotor continuous internal mixer is connected with a single screw extruder for extrusion granulation, the extrusion temperature is 80 +/-2 ℃, and the screw rotation speed is 60 r/min.
Comparative example 1
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: in the process of preparing the functional master batch, the temperature of mixing and the temperature of extrusion granulation are respectively controlled to be 65 ℃, in the process, the ethylene-octene copolymer is not melted, and the combination of different components is only carried out by depending on the bonding effect of the melting of the low-melting-point auxiliary agent. In the scheme, the prepared master batch is loose and not compact, the particle strength is low, and practices show that the master batch is easy to break in the later-stage carrying or mixing process, so that the mixing is not uniform, the performance distribution of the prepared ribbon is not uniform, the defective rate is high, and the negative influence is obvious; meanwhile, in the processing process, the rotor of the bicontinuous internal mixer has large torque and high current, and the single-screw granulation equipment has large torque and high processing current and is easy to cause die orifice blockage.
Comparative example 2
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: and in the process of preparing the functional master batch, controlling the mixing temperature and the extrusion granulation temperature to be 145 ℃ respectively, and melting all meltable components. In the scheme, the prepared master batch is easy to generate a phase separation phenomenon, a phenomenon that part of the auxiliary agent migrates to the surface of the master batch exists, and particularly, the auxiliary agent with a low melting point is easy to migrate to the surface of the master batch to form a film adhesion layer to cause the product particles to be bonded and agglomerated; and the high-melting-point additive migrates to the surface of the product particles to form small particles which are adhered to the surface of the particles and are easy to fall off, so that the processing additive is not uniformly dispersed, the product performance is unstable and the defective rate is high in later application.
Examples 5 to 8
The examples provide polypropylene ties having the raw material formulations shown in table 3 below.
TABLE 3
The preparation method of the polypropylene ribbon comprises the following steps: weighing the raw materials according to the formula, mixing, and performing injection molding to obtain the product; the injection temperature (zones 1-4) was: 130 deg.C, 200 deg.C, 225 deg.C.
Comparative examples
The polypropylene ribbon is prepared by injection molding of a polypropylene composition, and the polypropylene composition comprises the following components in parts by mass: 90 parts of block copolymer polypropylene, 8.68 parts of ethylene-octene copolymer, 0.3 part of lubricant, 0.2 part of ultraviolet absorbent, 0.12 part of antistatic agent, 0.2 part of copper inhibitor, 0.2 part of antioxidant and 0.3 part of nucleating agent; wherein the components of the block copolymer polypropylene, the ethylene-octene copolymer, the lubricant, the ultraviolet absorber, the antistatic agent, the copper inhibitor, the antioxidant and the nucleating agent are the same as those of example 1.
Preparation: weighing the raw materials according to the formula, then carrying out extrusion granulation (extrusion temperature: 1 zone 80 ℃,2 zone 120 ℃,3 zone 160 ℃, 4-10 zone 185 ℃, 11 zone 190 ℃ and die orifice 185 ℃), and then carrying out injection molding according to the injection molding conditions of the embodiment 5 to prepare the polypropylene ribbon.
Performance testing
The polypropylene ties obtained from examples 5 to 8 and comparative examples above were subjected to the following performance tests, the results of which are shown in Table 4. (the test bandage size is 4.8X 250mm series products)
Wherein, the low temperature drop hammer test (embodying toughness), the service temperature test at-25 ℃ and the tripping force test (embodying comprehensive mechanical property) refer to the standard UL 62275.
The low-temperature bending test method is that a sample is placed for 48 hours in an environment with the temperature of 23 +/-2 ℃ and the relative humidity of 50 percent, then is placed in a low-temperature test box with a specific temperature, is frozen for 4 hours, is quickly folded in half in the low-temperature test box, and passes the test without fracture. And (4) performing ten times of tests on each test item, if one test fails, performing ten times of tests again, if all tests succeed, passing the tests, and otherwise, judging that the tests are unqualified (the passing rate reaches 95 percent and judging that the tests are qualified).
The ultraviolet resistance test is carried out according to GB/T14522-93, the temperature during ultraviolet irradiation is 60 +/-2 ℃, the relative humidity is 50%, and the irradiation time is 1000 hours. The retention of the release force after 1000 hours of ultraviolet irradiation was more than 80%, and the product was acceptable.
Antistatic test reference: antistatic evaluation refers to surface resistivity test results, and the test refers to GB/T1410-: 1980.
copper resistance, low copper sensitivity test reference: GB/T11547-2008, the test medium is 10% copper chloride solution, the test temperature is 60 ℃, the time of the silver streak and the crack of the test sample is observed, and the change of the tripping force of the tie after being soaked for 168 hours is observed, and the retention rate of the tripping force exceeds 80% after the test is qualified.
Yellow index: the test was performed with reference to ASTM D6290 standard.
TABLE 4
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
1. The functional master batch is suitable for preparing a polypropylene ribbon and is characterized by comprising the following components in percentage by mass:
80-95% of ethylene-octene copolymer
0.22 to 9 percent of first functional auxiliary agent
0.1 to 15 percent of second functional auxiliary agent;
the first functional auxiliary agent is different from the second functional auxiliary agent, and the first functional auxiliary agent comprises the following components in percentage by mass: 0.2 to 5 percent of lubricant, 0.01 to 2 percent of antioxidant and 0.01 to 2 percent of nucleating agent;
the second functional auxiliary agent comprises one or more of ultraviolet absorbent, antistatic agent and copper resisting agent;
the functional master batch is prepared by mixing the components through an internal mixer, and then extruding and granulating; and in the preparation process, the mixing and extrusion granulation temperatures are controlled so as to partially melt the solid ethylene-octene copolymer, and the prepared functional master batch is coated with other components by the ethylene-octene copolymer.
2. The functional master batch suitable for preparing the polypropylene ribbon as claimed in claim 1, wherein the melting point of the ethylene-octene copolymer is represented by T, and the mixing temperature and the extrusion granulation temperature are controlled to be less than T +10 ℃ respectively during the preparation process.
3. The functional master batch suitable for preparing the polypropylene ribbon as claimed in claim 2, wherein the mixing temperature and the extrusion granulation temperature are controlled to be T +/-5 ℃ during the preparation process.
4. The functional masterbatch suitable for use in the preparation of polypropylene tie according to claim 1, wherein the ethylene-octene copolymer has a melt index of 15-50g/10 min.
5. The functional master batch suitable for preparing the polypropylene ribbon as claimed in claim 1, wherein the second functional auxiliary comprises an ultraviolet absorber, an antistatic agent and a copper resisting agent, and the mass ratio of the ultraviolet absorber to the antistatic agent to the copper resisting agent is 1: 0.5-2;
the ultraviolet absorbent is at least two selected from benzophenone ultraviolet absorbent, benzotriazole ultraviolet absorbent and amino ultraviolet absorbent, the benzophenone ultraviolet absorbent is one or a combination of more selected from (2, 4-dihydroxyphenyl) phenyl ketone, 2-hydroxy-4-n-octoxybenzophenone and (2-hydroxy-4-methoxyphenyl) phenyl ketone, and the benzotriazole ultraviolet absorbent is selected from 2- (2 'hydroxy-3', 5 '-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -bis (a, a-dimethylbenzyl) phenyl) benzotriazole, bis (3-benzotriazolyl-2-hydroxy-5-tert-octylphenyl) methane, methyl methacrylate, ethyl methacrylate, methyl methacrylate, ethyl methacrylate, and the like, A combination of one or more of 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, 2- [ 2-hydroxy-3, 5-bis (1, 1-dimethylpropylphenyl) ] -2H-benzotriazole and 2- [ 2-hydroxy-5- (1,1,3, 3-tetramethylbutyl) phenyl ] benzotriazole, the amino ultraviolet absorbent is poly { [6- [ (1,1,3, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4- [ (2,2,6,6, -tetramethyl-piperidyl) imino ] -1, 6-hexamethylene [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] };
the antistatic agent is at least two selected from octadecanamido propyl dimethyl-beta-hydroxyethyl quaternary ammonium nitrate, (3-lauric acid aminopropyl) trimethyl ammonium methyl sulfate salt, stearamidopropyl dimethyl-beta-hydroxyethyl ammonium dihydrogen phosphate, the antistatic agent 68, oleyl bis (2-hydroxyethyl) amine, N- (3-dodecyloxy-2-hydroxypropyl) ethanolamine, N-bis (2-hydroxyethyl) alkylamine, molecular distillation glycerol monostearate, octyl phenol polyoxyethylene ether, polyoxyethylene stearate and the antistatic agent Pelestat 230;
the copper inhibitor is one or more of benzotriazole copper inhibitor, oxalic acid dihydrazide, hydrazine benzoate, hydrazine salicylate, oxalic anilide copper inhibitor, condensate of salicylaldehyde and hexamethylene diamine, and condensate of furfural and hexamethylene diamine.
6. The masterbatch suitable for use in preparing a polypropylene cable tie according to claim 1, wherein the lubricant is selected from the group consisting of hydrocarbon lubricants, amide lubricants, ester lubricants, organic salt lubricants, fluorine-containing lubricants, C8-30At least two of an alcohol lubricant and other types of lubricants.
7. The masterbatch suitable for use in preparing a polypropylene cable tie according to claim 6, wherein the lubricant is selected from the group consisting of ester lubricants, amide lubricants, hydrocarbon lubricants, organic salt lubricants, fluorine lubricants, and C8-30Alcohol lubricants and other types of lubricants.
8. The functional masterbatch suitable for use in preparing a polypropylene tie according to claim 7, wherein the ester lubricant is comprised of a combination of montan wax and optionally one or more selected from the group consisting of glycerol monooleate, pentaerythritol stearate, ester lubricant G16, and ester lubricant G60;
the hydrocarbon lubricant is low-density polyethylene compound SA13-9 and/or polyethylene wax;
the amide lubricant is one or more of N, N' -diethylene bis stearamide, oleamide and amide wax;
said C is8-30The alcohol lubricant is stearyl alcohol;
the organic salt lubricant is one or more of calcium stearate, magnesium stearate and sodium stearate;
the fluorine-containing lubricant is a non-ionic fluorocarbon surfactant;
the other lubricant is molybdenum disulfide and/or oxidized polyethylene wax.
9. The preparation method of the functional master batch suitable for preparing the polypropylene ribbon according to any one of claims 1 to 8, wherein the preparation method comprises the following steps: weighing the components according to the formula, mixing by an internal mixer, extruding and granulating by a single screw, and drying to obtain the finished product.
10. The thin-wall high-length-diameter ratio polypropylene cable tie is characterized in that the raw materials of the polypropylene cable tie comprise the functional master batch suitable for preparing the polypropylene cable tie as claimed in any one of claims 1 to 8, and the functional master batch accounts for 5 to 20 percent of the raw materials of the polypropylene cable tie in percentage by mass.
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