KR102608214B1 - Method for preparing polyethylene having low density - Google Patents
Method for preparing polyethylene having low density Download PDFInfo
- Publication number
- KR102608214B1 KR102608214B1 KR1020180161295A KR20180161295A KR102608214B1 KR 102608214 B1 KR102608214 B1 KR 102608214B1 KR 1020180161295 A KR1020180161295 A KR 1020180161295A KR 20180161295 A KR20180161295 A KR 20180161295A KR 102608214 B1 KR102608214 B1 KR 102608214B1
- Authority
- KR
- South Korea
- Prior art keywords
- polyethylene
- butyl
- weight
- cross
- average temperature
- Prior art date
Links
- -1 polyethylene Polymers 0.000 title claims description 42
- 239000004698 Polyethylene Substances 0.000 title claims description 39
- 229920000573 polyethylene Polymers 0.000 title claims description 39
- 238000000034 method Methods 0.000 title description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 68
- 229920003020 cross-linked polyethylene Polymers 0.000 claims abstract description 51
- 239000004703 cross-linked polyethylene Substances 0.000 claims abstract description 51
- 238000004132 cross linking Methods 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims description 79
- 239000003607 modifier Substances 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 24
- 239000005977 Ethylene Substances 0.000 claims description 24
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- CARSMBZECAABMO-UHFFFAOYSA-N 3-chloro-2,6-dimethylbenzoic acid Chemical compound CC1=CC=C(Cl)C(C)=C1C(O)=O CARSMBZECAABMO-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 claims description 4
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims description 4
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 claims description 4
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 claims description 3
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- RAWISQFSQWIXCW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)CC RAWISQFSQWIXCW-UHFFFAOYSA-N 0.000 claims description 2
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 claims description 2
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 claims description 2
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 claims description 2
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 claims description 2
- ZGPBOPXFOJBLIV-UHFFFAOYSA-N butoxycarbonyloxy butyl carbonate Chemical compound CCCCOC(=O)OOC(=O)OCCCC ZGPBOPXFOJBLIV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- JETQIUPBHQNHNZ-OAYJICASSA-N sulbenicillin Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)C(S(O)(=O)=O)C1=CC=CC=C1 JETQIUPBHQNHNZ-OAYJICASSA-N 0.000 claims description 2
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 claims description 2
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 claims description 2
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- FSRYENDEMMDKMT-UHFFFAOYSA-N butoxy ethaneperoxoate Chemical compound CCCCOOOC(C)=O FSRYENDEMMDKMT-UHFFFAOYSA-N 0.000 claims 1
- 229920001684 low density polyethylene Polymers 0.000 abstract description 71
- 239000004702 low-density polyethylene Substances 0.000 abstract description 71
- 240000005572 Syzygium cordatum Species 0.000 abstract description 22
- 235000006650 Syzygium cordatum Nutrition 0.000 abstract description 22
- 230000000704 physical effect Effects 0.000 abstract description 13
- 230000000052 comparative effect Effects 0.000 description 27
- 230000008569 process Effects 0.000 description 9
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- VSAVVYSIMLTIHK-UHFFFAOYSA-N benzene;1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound C1=CC=CC=C1.CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C VSAVVYSIMLTIHK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- 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
-
- 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
- C08K5/14—Peroxides
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Abstract
본 발명에서는 우수한 물성을 가지며, 가교 폴리에틸렌의 제조에 적용시 수트리 특성과 가교 특성을 개선시킬 수 있는, 저밀도 폴리에틸렌의 제조방법이 제공된다.The present invention provides a method for producing low-density polyethylene, which has excellent physical properties and can improve water tree properties and cross-linking properties when applied to the production of cross-linked polyethylene.
Description
본 발명은 우수한 물성을 가지며, 가교 폴리에틸렌의 제조에 적용시 수트리 특성과 가교 특성을 개선시킬 수 있는, 저밀도 폴리에틸렌의 제조방법에 관한 것이다.The present invention relates to a method for producing low-density polyethylene, which has excellent physical properties and can improve water tree properties and cross-linking properties when applied to the production of cross-linked polyethylene.
가교 폴리에틸렌은 폴리에틸렌의 뛰어난 절연 재료로서의 성질을 살려서 열에 약한 결점을 개량한 것으로, 선형 폴리에틸렌과는 달리 3차원적인 망상구조를 가진다. 가교 폴리에틸렌은 특히 내열성, 내구성, 내화학성, 유연성 등이 뛰어난 것으로 알려져 있으며, 이러한 특성으로 인하여 전력 케이블 전기 절연용으로 널리 사용되고 있다. Cross-linked polyethylene takes advantage of polyethylene's excellent insulating material properties and improves its weakness to heat. Unlike linear polyethylene, it has a three-dimensional network structure. Cross-linked polyethylene is known to be particularly excellent in heat resistance, durability, chemical resistance, and flexibility, and due to these characteristics, it is widely used for electrical insulation of power cables.
일반적으로, 전력 케이블 제조시 폴리에틸렌을 가교제 및 산화방지제 등과 혼합하여 이를 압출 성형하여 제조하고 있다. 압출 성형 과정에서 폴리에틸렌의 가교화가 진행된다. Generally, when manufacturing power cables, polyethylene is mixed with a cross-linking agent and antioxidant and then extruded. Crosslinking of polyethylene occurs during the extrusion molding process.
한편, 상기 가교 폴리에틸렌의 제조에 사용되는 저밀도 폴리에틸렌은 1000 기압(bar) 이상의 고압 튜블러(tubular) 또는 오토클레이브(autoclave) 반응기에서 자유 라디칼 개시 반응으로 중합되는 에틸렌 단일 중합체이거나, 또는 100 기압(bar) 이하의 저압하에서 지글러 나타 촉매 또는 메탈로센 촉매를 사용하여 제조되었다.Meanwhile, the low-density polyethylene used in the production of the cross-linked polyethylene is an ethylene homopolymer polymerized by a free radical initiation reaction in a high-pressure tubular or autoclave reactor at 1000 bar or more, or 100 bar. ) was prepared using a Ziegler-Natta catalyst or a metallocene catalyst under low pressure below.
그러나, 자유 라디칼 개시 반응을 이용한 중합의 경우, 주로 고온 및 고압 반응으로 제조되는데, 이에 따라 공정 운전시 리스크가 있다. 또, 가교 폴리에틸렌의 베이스로 적용되는 경우 고청정 특성이 요구되기 때문에, 촉매 사용이 불가능하다. However, in the case of polymerization using a free radical initiation reaction, it is mainly produced through high temperature and high pressure reactions, which poses risks during process operation. In addition, when applied as a base for cross-linked polyethylene, it is impossible to use a catalyst because highly clean properties are required.
이에 따라 촉매 사용없이 저압 공정에서 저밀도 폴리에틸렌을 생산할 수 있는 공정 기술의 개발이 필요하다.Accordingly, there is a need to develop process technology that can produce low-density polyethylene in a low-pressure process without the use of catalysts.
본 발명은 상기와 같은 과제를 해결하고자 하는 것으로, 낮은 압력하에서도 종래 고온 고압의 조건에서 제조한 저밀도 폴리에틸렌과 비교하여 동등 수준 이상의 우수한 물성을 가지며, 가교 폴리에틸렌의 제조에 적용시 수트리 특성과 가교 특성을 개선시킬 수 있는 저밀도 폴리에틸렌을 제조하는 방법을 제공하기 위한 것이다.The present invention is intended to solve the problems described above, and has excellent physical properties at a level equivalent to or better than that of low-density polyethylene manufactured under conventional high-temperature and high-pressure conditions even under low pressure, and when applied to the production of cross-linked polyethylene, it has water tree properties and cross-linking properties. The purpose is to provide a method for producing low-density polyethylene whose properties can be improved.
또 본 발명은 상기한 제조방법에 따라 제조된 저밀도 폴리에틸렌을 이용한 가교 폴리에틸렌의 제조방법을 제공한다. Additionally, the present invention provides a method for producing cross-linked polyethylene using low-density polyethylene produced according to the above-mentioned production method.
상기와 같은 문제를 해결하기 위해서 본 발명의 일 구현예에 따르면, According to one embodiment of the present invention to solve the above problem,
개시제의 존재 하에 에틸렌 단량체를 오토클레이브(autoclave) 반응기에 넣고, 개질제를 투입하며 1700kg/cm2 이하의 압력하에서 중합시키는 단계를 포함하며,Putting ethylene monomer into an autoclave reactor in the presence of an initiator, adding a modifier, and polymerizing it under a pressure of 1700 kg/cm 2 or less,
상기 반응기는 3단 이상의 반응영역을 포함하고, 최상단으로부터 1단 이상의 제1 반응영역의 평균 온도를 T1, 최하단으로부터 1단 이상의 제2 반응영역의 평균 온도 T2, 그리고 그 사이에 있는 1단 이상의 제3 반응영역의 평균 온도를 T3이라 할 때, T2>T3>T1의 온도 조건을 충족하며, T3과 T1의 차이(ΔT1)가 50 내지 65℃이고, T2와 T3의 차이(ΔT2)가 50 내지 70℃이며,The reactor includes three or more reaction zones, and the average temperature of the first reaction zone of one or more stages from the top is T1, the average temperature of the second reaction zones of one or more stages from the bottom is T2, and the average temperature of the second reaction zones of one or more stages between them is T2. 3 When the average temperature of the reaction zone is T3, the temperature condition T2>T3>T1 is satisfied, the difference between T3 and T1 (ΔT1) is 50 to 65°C, and the difference between T2 and T3 (ΔT2) is 50 to 65°C. It is 70℃,
상기 개질제는 에틸렌 단량체 100중량부에 대하여 1.5중량부 이상의 함량으로 투입되는, 0.94 g/cm3 이하의 밀도를 갖는 폴리에틸렌의 제조방법을 제공한다. The modifier is added in an amount of 1.5 parts by weight or more based on 100 parts by weight of ethylene monomer, and provides a method for producing polyethylene having a density of 0.94 g/cm 3 or less.
또 발명의 다른 일 구현예에 따르면, 상기 제조방법에 따라 0.94 g/cm3 이하의 밀도를 갖는 폴리에틸렌을 제조하는 단계, 및 상기 폴리에틸렌을 가교제 및 산화방지제와 혼합하고, 혼련 및 압출하여 가교시키는 단계를 포함하는, 가교 폴리에틸렌의 제조방법을 제공한다.According to another embodiment of the invention, preparing polyethylene having a density of 0.94 g/cm 3 or less according to the above production method, and mixing the polyethylene with a crosslinking agent and an antioxidant, kneading and extruding the polyethylene to crosslink it. It provides a method for producing cross-linked polyethylene, including.
본 발명의 제조방법에 따르면, 1700kg/cm2 이하의 낮은 압력하에서도 종래 고온 고압 공정에 의해 제조된 폴리에틸렌과 동등 수준 이상의 우수한 물성을 갖는 저밀도 폴리에틸렌을 제조할 수 있다.According to the manufacturing method of the present invention, low-density polyethylene having excellent physical properties equivalent to or better than that of polyethylene manufactured by a conventional high temperature and high pressure process can be manufactured even under a low pressure of 1700 kg/cm 2 or less.
또, 상기 제조방법에 따라 제조된 저밀도 폴리에틸렌은 좁은 분자량 분포(MWD)을 갖고, SCB(short chain branch)가 증가되면서도 고분자량 부분을 충분히 포함하여, 가교 폴리에틸렌의 제조에 사용시 수트리 특성과 가교 특성을 개선시킬 수 있다. In addition, the low-density polyethylene produced according to the above production method has a narrow molecular weight distribution (MWD) and contains sufficient high molecular weight portions while increasing the short chain branch (SCB), so that when used in the production of cross-linked polyethylene, water tree properties and cross-linking properties are maintained. can be improved.
도 1은 실험예에서 수트리 길이를 측정하기 위한 가속 수트리 열화장치를 개략적으로 도시한 도면이다.
도 2는 실험예에서 수트리 길이를 측정하기 위한 바늘 삽입기를 개략적으로 도시한 도면이다.Figure 1 is a diagram schematically showing an accelerated water tree deterioration device for measuring water tree length in an experimental example.
Figure 2 is a diagram schematically showing a needle insertion device for measuring the sutree length in an experimental example.
본 명세서에서 사용되는 용어는 단지 예시적인 실시예들을 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도는 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 명세서에서, "포함하다", "구비하다" 또는 "가지다" 등의 용어는 실시된 특징, 단계, 구성 요소 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 단계, 구성 요소, 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as “comprise,” “comprise,” or “have” are intended to designate the presence of implemented features, steps, components, or a combination thereof, and are intended to indicate the presence of one or more other features or steps, It should be understood that the existence or addition possibility of components or combinations thereof is not excluded in advance.
본 명세서에 있어서 특별한 언급이 없는 한, "실온"이란 23±2℃, 구체적으로는 25℃의 온도를 의미한다. In this specification, unless otherwise specified, “room temperature” means a temperature of 23 ± 2°C, specifically 25°C.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 특정 실시예들을 예시하고 하기에서 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.Since the present invention can be subject to various changes and can take various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosed form, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.
본 발명에서 사용되는 용어 '저밀도 폴리에틸렌'은, 본 발명에서 제조하고자 하는 가교 폴리에틸렌의 주성분으로, 통상 'LDPE(low density polyethylene)'라고도 불리는 물질이다. 구체적으로는, ASTM D1505의 방법에 따라 측정한 밀도가 0.94 g/cm3 이하, 보다 구체적으로는 0.87 내지 0.94 g/cm3인 폴리에틸렌을 의미한다.The term 'low density polyethylene' used in the present invention is the main component of cross-linked polyethylene to be manufactured in the present invention, and is also commonly called 'LDPE (low density polyethylene)'. Specifically, it means polyethylene having a density measured according to the method of ASTM D1505 of 0.94 g/cm 3 or less, more specifically 0.87 to 0.94 g/cm 3 .
이하 발명의 구체적인 구현예에 따른 저밀도 폴리에틸렌의 제조방법 및 상기 제조방법에 따라 제조된 저밀도 폴리에틸렌을 이용한 가교 폴리에틸렌의 제조방법 등에 대하여 보다 상세하게 설명하기로 한다.Hereinafter, a method for producing low-density polyethylene according to specific embodiments of the invention and a method for producing cross-linked polyethylene using low-density polyethylene produced according to the above production method will be described in more detail.
본 발명은 오토클레이브 반응기를 이용한 저밀도 폴리에틸렌의 제조시, 1700kg/cm2 이하의 저압의 조건에 대해 반응기 내 반응영역에 따른 온도 및 반응영역 간 온도차를 최적화하여 제어하고, 또 개질제를 투입함으로써, 제조되는 폴리에틸렌의 분자량 분포가 과도하게 커지는 것을 방지하고, 동시에 SCB를 증가시키고, 고분자량 부분이 충분히 형성되도록 하였다. 이에 따라, 본 발명의 제조방법에 의해 제조되는 저밀도 폴리에틸렌은 좁은 MWD와 함께 SCB의 증가, 그리고 고분자량 부분을 충분히 포함함으로써, 우수한 물성을 나타내며, 가교 폴리에틸렌의 제조에 사용시 수트리 특성과 가교 특성을 개선시킬 수 있다.In the present invention, when manufacturing low-density polyethylene using an autoclave reactor, the temperature according to the reaction zone in the reactor and the temperature difference between reaction zones are optimized and controlled under low pressure conditions of 1700 kg/cm 2 or less, and a modifier is added. The molecular weight distribution of polyethylene was prevented from becoming excessively large, and at the same time, the SCB was increased and the high molecular weight portion was sufficiently formed. Accordingly, the low-density polyethylene produced by the production method of the present invention exhibits excellent physical properties by having a narrow MWD, an increase in SCB, and sufficient high molecular weight portions, and when used in the production of cross-linked polyethylene, it has water tree properties and cross-linking properties. It can be improved.
구체적으로 본 발명의 일 구현예에 따른 저밀도 폴리에틸렌의 제조방법은,Specifically, the method for producing low-density polyethylene according to an embodiment of the present invention,
개시제의 존재 하에 에틸렌 단량체를 오토클레이브(autoclave) 반응기에 넣고, 개질제를 투입하며 1700kg/cm2 이하의 압력하에서 중합시키는 단계를 포함하며,Putting ethylene monomer into an autoclave reactor in the presence of an initiator, adding a modifier, and polymerizing it under a pressure of 1700 kg/cm 2 or less,
상기 반응기는 3단 이상의 반응영역을 포함하고, 최상단으로부터 1단 이상의 제1 반응영역의 평균 온도를 T1, 최하단으로부터 1단 이상의 제2 반응영역의 평균 온도 T2, 그리고 그 사이에 있는 1단 이상의 제3 반응영역의 평균 온도를 T3이라 할 때, T2>T3>T1의 온도 조건을 충족하며, T3과 T1의 차이(ΔT1)가 50 내지 65℃이고, T2와 T3의 차이(ΔT2)가 50 내지 70℃이며, The reactor includes three or more reaction zones, and the average temperature of the first reaction zone of one or more stages from the top is T1, the average temperature of the second reaction zones of one or more stages from the bottom is T2, and the average temperature of the second reaction zones of one or more stages between them is T2. 3 When the average temperature of the reaction zone is T3, the temperature condition T2>T3>T1 is satisfied, the difference between T3 and T1 (ΔT1) is 50 to 65°C, and the difference between T2 and T3 (ΔT2) is 50 to 65°C. It is 70℃,
상기 개질제는 에틸렌 단량체 100중량부에 대하여 1.5중량부 이상의 함량으로 투입된다.The modifier is added in an amount of 1.5 parts by weight or more based on 100 parts by weight of ethylene monomer.
발명의 일 구현예에 따른 저밀도 폴리에틸렌의 제조 방법에 있어서, 에틸렌 단량체의 중합 반응은 150 내지 320℃, 보다 구체적으로는 160 내지 300℃의 온도 범위에서 수행될 수 있다. 이에 따라, 반응기내 반응영역의 최저 온도는 150℃, 또는 160 ℃이고, 최고 온도는 320℃ 또는 300℃일 수 있다. 상기한 온도 범위 내에서 수행시 미반응 또는 과반응에 대한 우려없이 우수한 전환율로 저밀도 폴리에틸렌을 제조할 수 있다. 중합 반응 온도가 150 ℃ 미만이면, 반응 초기 초고분자량 사슬 형성으로 겔이 형성될 우려가 있고, 320℃를 초과하면, 반응 폭주 또는 폴리에틸렌의 분해반응이 일어날 우려가 있다. In the method for producing low-density polyethylene according to an embodiment of the invention, the polymerization reaction of ethylene monomer may be performed in a temperature range of 150 to 320°C, more specifically, 160 to 300°C. Accordingly, the minimum temperature of the reaction area within the reactor may be 150°C or 160°C, and the maximum temperature may be 320°C or 300°C. When carried out within the above-mentioned temperature range, low-density polyethylene can be manufactured with excellent conversion rate without concern about unreacted or over-reacted. If the polymerization reaction temperature is less than 150°C, there is a risk that a gel may be formed due to the formation of ultra-high molecular weight chains at the initial stage of the reaction, and if it exceeds 320°C, there is a risk of reaction runaway or decomposition reaction of polyethylene.
또, 상기 반응기는 3단 이상의 반응영역을 포함할 수 있으며, 최상단으로부터 1단 이상의 제1 반응영역의 평균 온도를 T1, 최하단으로부터 1단 이상의 제2 반응영역의 평균 온도 T2, 그리고 그 사이에 있는 1단 이상의 제3 반응영역의 평균 온도를 T3이라 할 때, T2>T3>T1의 조건을 충족한다. In addition, the reactor may include three or more reaction zones, and the average temperature of the first reaction zone of one or more stages from the top is T1, the average temperature of the second reaction zones of one or more stages from the bottom is T2, and When the average temperature of the third reaction zone of one or more stages is T3, the condition T2>T3>T1 is satisfied.
반응기가 3단 미만의 반응영역을 가질 경우, 제조되는 저밀도 폴리에틸렌의 MWD가 지나치게 좁아 가공성이 저하될 우려가 있고, 또 적정 수준의 SCB 형성이 용이하지 않다. If the reactor has a reaction area of less than three stages, the MWD of the low-density polyethylene produced is too narrow, which may reduce processability, and it is not easy to form SCB at an appropriate level.
반응기를 구성하는 반응단의 개수 제어에 의한 저밀도 폴리에틸렌 물성 구현을 고려할 때, 상기 반응기는 보다 구체적으로 7단의 반응영역을 포함할 수 있다. 이 경우, 반응기의 최상단에서부터 최하단까지를 1단에서 7단으로 순차 정의할 때, 상기 T1은 최상단으로부터 2개 단의 반응영역, 즉 1단과 2단을 포함하는 반응영역의 온도이고, T2는 최하단으로부터 2개 단의 반응영역, 즉 6단과 7단을 포함하는 반응영역의 온도이며, T3는 그 사이의 3개 단의 반응영역, 즉 3단에서부터 5단까지를 포함하는 반응영역의 온도일 수 있다. Considering the realization of low-density polyethylene physical properties by controlling the number of reaction stages constituting the reactor, the reactor may include more specifically 7 reaction zones. In this case, when sequentially defining stages from 1 to 7 from the top to the bottom of the reactor, T1 is the temperature of the reaction region of the two stages from the top, that is, the first and second stages, and T2 is the temperature of the reaction region from the bottom. T3 is the temperature of the two-stage reaction zone, that is, the reaction zone including the 6th and 7th stages, and T3 can be the temperature of the three-stage reaction zone in between, that is, the reaction zone including the 3rd to 5th stages. there is.
또, 상기 반응기 내 반응영역은 T2>T3>T1의 온도 조건을 충족한다.Additionally, the reaction area within the reactor satisfies the temperature condition of T2>T3>T1.
상기 반응기를 이용한 저밀도 폴리에틸렌의 중합시 에틸렌 단량체는, 제1 반응영역으로 투입된 후, 제2 반응영역 및 제3 반응영역을 순차로 통과하며 중합되게 된다. 이때 상기와 같이 반응기의 최하단으로 갈수록 온도가 높아짐으로써 보다 우수한 효율로 저밀도 폴리에틸렌을 제조할 수 있으며, 동시에 물성 구현이 용이하다. 만약 최하단으로 갈수록 온도가 낮아질 경우 제조되는 폴리에틸렌에 있어서 LCB (long chain branch)가 과도하게 발생될 우려가 있고, 또 제2 반응영역에서의 온도가 제1 및 제3 반응영역보다 높을 경우, 제조되는 폴리에틸렌에 있어서 미반응 단량체가 많아 불균일한 제품이 생산될 우려가 있다. When polymerizing low-density polyethylene using the reactor, ethylene monomer is introduced into the first reaction zone and then sequentially passes through the second reaction zone and the third reaction zone to be polymerized. At this time, as the temperature increases toward the bottom of the reactor as described above, low-density polyethylene can be manufactured with greater efficiency, and at the same time, it is easy to realize physical properties. If the temperature decreases toward the bottom, there is a risk of excessive occurrence of LCB (long chain branch) in the produced polyethylene, and if the temperature in the second reaction zone is higher than the first and third reaction zones, the produced polyethylene In polyethylene, there is a risk of producing non-uniform products because there are many unreacted monomers.
또, 상기 반응기에 있어서, 반응영역간 온도 차(△T)를 높임으로써, 제조되는 저밀도 폴리에틸렌 내 SCB 및 LCB의 분포를 증가시킬 수 있다. 그러나, △T가 지나치게 커질 경우 제조되는 저밀도 폴리에틸렌 내 저분자량 부분이 증가하게 되고, 그 결과로서 MWD가 과도하게 커질 수 있다. 이에 따라, 본 발명에서는 T3과 T1의 차이(ΔT1)가 50 내지 65℃이고, T2와 T3의 차이(ΔT2)가 50 내지 70℃이 되도록 한다. 상기한 반응영역간의 온도차 조건을 충족함으로써, 제조되는 저밀도 폴리에틸렌이 좁은 MWD를 나타내면서도 증가된 SCB를 포함할 수 있다. 보다 구체적으로는 T3과 T1의 차이(ΔT1)가 55 내지 65℃이고, T2와 T3의 차이(ΔT2)가 55 내지 70℃이 되도록 한다.Additionally, in the reactor, by increasing the temperature difference (ΔT) between reaction zones, the distribution of SCB and LCB in the low-density polyethylene produced can be increased. However, if ΔT becomes excessively large, the low molecular weight portion in the manufactured low-density polyethylene increases, and as a result, the MWD may become excessively large. Accordingly, in the present invention, the difference (ΔT1) between T3 and T1 is 50 to 65°C, and the difference (ΔT2) between T2 and T3 is 50 to 70°C. By satisfying the above-mentioned temperature difference conditions between reaction zones, the produced low-density polyethylene can include increased SCB while exhibiting narrow MWD. More specifically, the difference (ΔT1) between T3 and T1 is 55 to 65°C, and the difference (ΔT2) between T2 and T3 is 55 to 70°C.
보다 구체적으로, 발명의 일 구현예에 따른 저밀도 폴리에틸렌의 제조시, 상기한 반응영역간 온도 차 범위를 충족하는 조건 하에, 상기 반응기 내 T3이 220 내지 250℃이고, T1 및 T2가 T2>T3>T1의 조건을 충족하는 온도이거나, 또는 T1이 160 내지 180℃이고, T2가 280 내지 300℃이며, T3이 T2>T3>T1의 온도 조건을 충족하는 온도일 수 있다. 이와 같이 반응기 내 위치에 따라 최적화된 온도 범위에서 수행함으로써, MWD의 증가를 방지하고, SCB를 증가시켜 고분자량 부분을 충분히 형성되도록 할 수 있다.More specifically, when producing low-density polyethylene according to an embodiment of the invention, under conditions that meet the temperature difference range between reaction zones, T3 in the reactor is 220 to 250°C, and T1 and T2 are T2>T3>T1 It may be a temperature that satisfies the conditions, or T1 may be 160 to 180°C, T2 may be 280 to 300°C, and T3 may be a temperature that satisfies the temperature conditions of T2>T3>T1. In this way, by performing the reaction in an optimized temperature range depending on the location within the reactor, an increase in MWD can be prevented and SCB can be increased to sufficiently form a high molecular weight portion.
한편, 상기 반응기의 각 반응영역에서의 온도는 해당 영역에 설치된 열전대(thermocouple)에 의해 측정될 수 있으며, 본 발명에서는 각 반응영역에 해당하는 반응단들의 온도를 각각 측정한 후 그 평균값으로 나타내었다. 일례로, 7단으로 이루어진 반응기에서 최상단에서부터 최하단까지를 1단에서 7단으로 순차 정의할 때, T1은 제1단과 제2단에서 각각 측정한 온도의 평균 온도이고, T2는 제6단과 제7단에서 각각 측정한 온도의 평균 온도이며, T3은 제3단, 제4단 및 제5단에서 각각 측정한 온도의 평균 온도이다. Meanwhile, the temperature in each reaction zone of the reactor can be measured by a thermocouple installed in the corresponding zone. In the present invention, the temperature of the reaction stages corresponding to each reaction zone is measured and expressed as the average value. . For example, when defining the 1st to 7th stages from the top to the bottom in a 7-stage reactor, T1 is the average temperature measured in the 1st and 2nd stages, and T2 is the 6th and 7th stages. It is the average temperature of the temperatures measured in each stage, and T3 is the average temperature of the temperatures measured in the 3rd, 4th, and 5th stages, respectively.
또, 발명의 일 구현예에 따른 저밀도 폴리에틸렌의 제조 방법에 있어서, 에틸렌 단량체의 중합은 저압 조건에서 수행된다. 구체적으로, 상기 오토클레이브 반응기의 압력은 1700kg/cm2 이하, 보다 구체적으로는 1500 내지 1700 kg/cm2 일 수 있다. 상기한 범위의 압력하에서 수행됨으로써, 고분자량 부분의 감소를 방지하고, SCB를 증가시킬 수 있다. 그러나, 반응기내 압력이 1700 kg/cm2 를 초과하면 중합체 제조를 위한 운전시 risk 발생의 우려가 높고, 또 상기 반응기내 최적화된 온도 조건에서 반응기내 압력이 1700 kg/cm2 를 초과할 경우 제조되는 저밀도 폴리에틸렌 내 고분자량 부분이 크게 감소할 우려가 있다. Additionally, in the method for producing low-density polyethylene according to one embodiment of the invention, polymerization of ethylene monomer is performed under low pressure conditions. Specifically, the pressure of the autoclave reactor is 1700 kg/cm 2 or less, more specifically 1500 to 1700 kg/cm 2 It can be. By performing the process under the pressure in the above range, reduction of the high molecular weight portion can be prevented and SCB can be increased. However, the pressure inside the reactor was 1700 kg/cm 2 If it exceeds, there is a high risk of risk occurring during operation for polymer production, and the pressure within the reactor is 1700 kg/cm 2 under the optimized temperature conditions within the reactor. If it exceeds, there is a risk that the high molecular weight portion of the manufactured low-density polyethylene will be greatly reduced.
한편, 본 발명에 있어서 상기 반응기의 압력은 반응기 내부 압력 센서에 의해 측정된 압력을 의미한다. Meanwhile, in the present invention, the pressure of the reactor refers to the pressure measured by a pressure sensor inside the reactor.
또, 발명의 일 구현예에 따른 저밀도 폴리에틸렌의 제조 방법에 있어서, 상기 에틸렌 단량체는 기체상으로 투입되는데, 이때 상기 오토클레이브 반응기 내로 투입되는 단량체의 온도는 10 내지 60℃, 보다 구체적으로는 30 내지 60℃일 수 있다. In addition, in the method for producing low-density polyethylene according to one embodiment of the invention, the ethylene monomer is introduced in the gas phase, and at this time, the temperature of the monomer introduced into the autoclave reactor is 10 to 60 ° C., more specifically 30 to 30 ° C. It may be 60℃.
상기 에틸렌 단량체의 중합시, 개시제로는 통상 저밀도 폴리에틸렌의 제조에 사용되는 것이라면 특별히 한정되지 않는다. 구체적으로는, DIPND(1,4-di(2-neodecanoylperoxyisopropyl)benzene), CUPND(Cumylperoxy neodecanoate), SBPC(Di(sec-butyl) peroxydicarbonate), NBPC(Di(n-butyl)peroxydicarbonate), EHP(Di(2-ethylhexyl) peroxydicarbonate), TAPND(Tert-amylperoxyneodecanoate) TBPND(Tert-butyl peroxyneodecanoate), TAPPI(Tert-amylperoxy pivalate), TBPP(Tert-butylperoxy pivalate), INP(Di(3,5,5-trimethylhexanoyl) peroxide), TAPEH(Tert-amylperoxy 2-ethylhexanoate), TBPEH(Tert-butylperoxy 2-ethylhexanoate), TBPIB(Tert-butylperoxy-isobutyrate), TBPIN(Tert-butylperoxy-3,5,5-trimethylhexanoate) 또는 TBPA(Tert-butylperoxyacetate) 등의 유기 과산화물이 사용될 수 있으며, 상기 예시된 화합물 중 어느 하나 또는 둘 이상의 혼합물이 사용될 수 있다. When polymerizing the ethylene monomer, the initiator is not particularly limited as long as it is commonly used in the production of low-density polyethylene. Specifically, DIPND (1,4-di(2-neodecanoylperoxyisopropyl)benzene), CUPND (Cumylperoxy neodecanoate), SBPC (Di(sec-butyl) peroxydicarbonate), NBPC (Di(n-butyl)peroxydicarbonate), EHP(Di (2-ethylhexyl) peroxydicarbonate), TAPND (Tert-amylperoxyneodecanoate) TBPND (Tert-butyl peroxyneodecanoate), TAPPI (Tert-amylperoxy pivalate), TBPP (Tert-butylperoxy pivalate), INP (Di(3,5,5-trimethylhexanoyl) peroxide), Tert-amylperoxy 2-ethylhexanoate (TAPEH), Tert-butylperoxy 2-ethylhexanoate (TBPEH), Tert-butylperoxy-isobutyrate (TBPIB), Tert-butylperoxy-3,5,5-trimethylhexanoate (TBPIN), or Tert-butylperoxy-3,5,5-trimethylhexanoate (TBPA). Organic peroxides such as -butylperoxyacetate) can be used, and any one or a mixture of two or more of the compounds exemplified above can be used.
상기 개시제의 투입량은 반응조건에 따라 달라질 수 있기 때문에, 발명의 일 구현예에 따른 저밀도 폴리에틸렌의 제조방법에 있어서 개시제의 투입량이 특별히 한정되는 것은 아니다. 다만, 개시제의 투입량이 지나치게 적을 경우 반응이 충분히 일어나지 않을 우려가 있고, 지나치게 많을 경우 비이상 반응에 의한 폭주 반응이 발생할 수 있다. 이에 반응조건에 따라 그 함량을 적절히 결정하는 것이 바람직하다. 일례로 상술한 반응 조건에서의 수행시 개시제는 에틸렌 단량체 총 중량에 대하여 100 ppm 이상, 또는 200 ppm 이상, 또는 300 ppm 이상이면서, 2000 ppm 이하, 또는 1800 ppm 이하, 또는 1600 ppm 이하의 양으로 투입될 수 있다. Since the amount of the initiator added may vary depending on reaction conditions, the amount of the initiator added in the method for producing low-density polyethylene according to an embodiment of the invention is not particularly limited. However, if the amount of initiator added is too small, there is a risk that the reaction will not sufficiently occur, and if it is too large, a runaway reaction due to an abnormal reaction may occur. Therefore, it is desirable to appropriately determine the content depending on the reaction conditions. For example, when performing the reaction under the above-described reaction conditions, the initiator is added in an amount of 100 ppm or more, 200 ppm or more, or 300 ppm or more, and 2000 ppm or less, or 1800 ppm or less, or 1600 ppm or less based on the total weight of ethylene monomer. It can be.
또, 상기 개시제는 용액상으로 투입될 수 있는데, 구체적으로는 20 내지 80 중량%, 또는 30 내지 70 중량%의 농도로 탄화수소 용매에 희석된 용액상으로 투입될 수 있다. 이때, 탄화수소 용매로는 예를 들어, n-데칸(n-decane), n-옥탄(n-octane), iso-도데칸(iso-dodecane), 및 iso-옥탄(iso-octane)으로 이루어진 군에서 선택된 1종 이상을 사용하거나, 탄화수소 혼합 상용 제품인 Isopar 계열의 용매를 사용할 수 있다.Additionally, the initiator may be added in the form of a solution, specifically, in a solution diluted in a hydrocarbon solvent at a concentration of 20 to 80% by weight, or 30 to 70% by weight. At this time, the hydrocarbon solvent includes, for example, n-decane, n-octane, iso-dodecane, and iso-octane. You can use one or more types selected from , or use a solvent of the Isopar series, which is a commercial product mixed with hydrocarbons.
또, 상기 에틸렌 단량체의 중합시 개질제로서 프로필렌, 1-부텐, 이소부텐, 펜텐, 펜텐 이성질체, 핵센, 핵센 이성질체, 헵텐, 헵텐 이성질체, 옥텐, 옥텐 이성질체 등의 탄소수 3 내지 12의 올레핀계 탄화수소류가 사용될 수 있으며, 이들 중에서도 개선 효과의 우수함을 고려할 때, 프로필렌이 사용될 수 있다.In addition, as a modifier during the polymerization of the ethylene monomer, olefinic hydrocarbons having 3 to 12 carbon atoms such as propylene, 1-butene, isobutene, pentene, pentene isomers, hexene, hexene isomers, heptene, heptene isomers, octene, and octene isomers. Among these, considering its excellent improvement effect, propylene can be used.
상기 개질제 투입을 통해 LCB (Long chain branch), SCB (Short chain branch) 특성 및 분자량을 제어함으로써, 가교 폴리에틸렌에 대한 저밀도 폴리에틸렌의 가교 특성 및 수트리 특성을 더욱 개선시킬 수 있다. 또 그 투입량의 제어를 통해 이 같은 효과를 더욱 증진시킬 수 있다. By controlling the long chain branch (LCB) and short chain branch (SCB) properties and molecular weight through the addition of the modifier, the crosslinking properties and water tree properties of low-density polyethylene relative to crosslinked polyethylene can be further improved. In addition, this effect can be further enhanced by controlling the input amount.
구체적으로 상기 개질제는 에틸렌 단량체 100중량부에 대하여 1.5 중량부 이상으로 투입될 수 있다. 개질제의 투입량이 1.5중량부 미만이면 가교특성 저하의 우려가 있다. 다만 개질제의 투입량이 3중량부를 초과하더라도 더 이상의 가교특성이 개선 효과는 없으므로, 보다 구체적으로는 에틸렌 단량체 100중량부에 대하여 1.5 내지 3중량부의 양으로 투입될 수 있다. 투입량 대비 가교도 개선 효과의 우수함을 고려할 때, 상기 개질제는 에틸렌 단량체 100중량부에 대하여 보다 더 구체적으로는 1.5 내지 2.5중량부로 투입될 수 있다.Specifically, the modifier may be added in an amount of 1.5 parts by weight or more based on 100 parts by weight of ethylene monomer. If the amount of modifier added is less than 1.5 parts by weight, there is a risk of deterioration in crosslinking characteristics. However, even if the amount of the modifier added exceeds 3 parts by weight, there is no further improvement in crosslinking characteristics, so more specifically, it can be added in an amount of 1.5 to 3 parts by weight based on 100 parts by weight of ethylene monomer. Considering the excellent effect of improving the degree of crosslinking relative to the amount added, the modifier may be added in an amount of 1.5 to 2.5 parts by weight, more specifically, based on 100 parts by weight of ethylene monomer.
또, 상기 중합 반응시, 중합 반응의 효율 및 제조되는 폴리에틸렌의 물성을 저해하지 않는 범위 내에서 산화방지제, UV 안정제, 중화제, 안티 블로킹제, 슬힙제, 핵제 등의 첨가제가 1종 이상 더 투입될 수 있다. In addition, during the polymerization reaction, one or more additives such as antioxidants, UV stabilizers, neutralizers, anti-blocking agents, slip agents, and nucleating agents may be added within the range that does not impair the efficiency of the polymerization reaction and the physical properties of the polyethylene produced. You can.
상술한 바와 같이, 저압의 조건에서 오토클레이브 반응기 내 위치에 따른 온도 조건 및 개질제의 투입을 제어함으로써, 종래 고압 공정 하에서 제조된 폴리에틸렌과 동등 수준 이상의 우수한 물성, 구체적으로 좁은 분자량 분포 및 SCB 그리고 충분한 고분자량 부분을 포함하는 저밀도 폴리에틸렌이 제조될 수 있다. As described above, by controlling the temperature conditions and the input of the modifier according to the position in the autoclave reactor under low pressure conditions, excellent physical properties equivalent to or higher than those of polyethylene manufactured under a conventional high pressure process, specifically narrow molecular weight distribution and SCB, and sufficient high Low density polyethylene comprising a molecular weight portion can be produced.
이에 따라 본 발명에 다른 일 구현예에 따르면, 상기 제조방법에 의해 제조되는 저밀도 폴리에틸렌이 제공된다.Accordingly, according to another embodiment of the present invention, low-density polyethylene produced by the above production method is provided.
구체적으로, 상기 저밀도 폴리에틸렌은 0.94 g/cm3 이하, 보다 구체적으로는 0.87 내지 0.94 g/cm3, 또는 0.92 내지 0.92 g/cm3의 저밀도(ASTM D1505의 방법에 따라 측정)를 나타낸다.Specifically, the low density polyethylene is 0.94 g/cm 3 Hereinafter, more specifically, it indicates a low density of 0.87 to 0.94 g/cm 3 , or 0.92 to 0.92 g/cm 3 (measured according to the method of ASTM D1505).
또, 상기 저밀도 폴리에틸렌은 분자 내 구조 제어로 상기한 범위의 저밀도와 함께 6.05 이하, 보다 구체적으로는 5 내지 6.05, 또는 5.8 내지 6.04의 좁은 분자량 분포(MWD)를 나타내며, 또 15,000 내지 30,000 g/mol, 보다 구체적으로는 18,000 내지 22,000 g/mol, 또는 18,500 내지 20,000 g/mol의 수평균 분자량(Mn); 및 100,000 내지 150,000 g/mol, 또는 105,000 내지 130,000 g/mol의 중량평균 분자량(Mw)을 나타낼 수 있다. 이와 같이 저밀도와 함께, 좁은 분자량 분포 및 종래 대비 높은 중량평균 분자량을 가짐으로써, 가교 폴리에틸렌 제조를 위한 베이스 수지로서 적용시 가교 특성, 고온 신율 특성 및 수트리 특성을 동시에 발란스 좋게 개선시킬 수 있다.In addition, the low-density polyethylene exhibits a low density in the above range due to intramolecular structure control and a narrow molecular weight distribution (MWD) of 6.05 or less, more specifically 5 to 6.05, or 5.8 to 6.04, and 15,000 to 30,000 g/mol. , more specifically a number average molecular weight (Mn) of 18,000 to 22,000 g/mol, or 18,500 to 20,000 g/mol; and a weight average molecular weight (Mw) of 100,000 to 150,000 g/mol, or 105,000 to 130,000 g/mol. In this way, by having a low density, a narrow molecular weight distribution, and a higher weight average molecular weight than before, when applied as a base resin for producing cross-linked polyethylene, cross-linking properties, high-temperature elongation properties, and water tree properties can be improved in a well-balanced manner at the same time.
한편, 본 발명에 있어서, 상기 저밀도 폴리에틸렌의 분자량 분포(MWD, 중량평균 분자량(Mw), 및 수평균 분자량(Mn)은, 겔투과 크로마토그래피 (GPC)를 이용하여 중량평균 분자량(Mw) 및 수평균 분자량(Mn)을 각각 측정한 후, 수평균 분자량에 대한 중량평균 분자량의 비(Mw/Mn)로 분자량 분포를 결정할 수 있다. 구체적으로는 Polymer Laboratories PLgel MIX-B 300mm 길이 칼럼을 이용하여 Waters PL-GPC220 기기를 이용하여 측정할 수 있으며. 이때, 평가 온도는 140℃이고, 1,2,4-트리클로로벤젠을 용매로서 사용하며, 유속은 1mL/min로 한다. 또 샘플은 10mg/10mL의 농도로 조제한 다음, 200μL의 양으로 공급한다. 폴리스티렌 표준을 이용하여 형성된 검정 곡선을 이용하여 Mw 및 Mn의 값을 유도한다. 이때 폴리스티렌 표준품의 분자량(g/mol)은 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000의 9종을 사용하였다.Meanwhile, in the present invention, the molecular weight distribution (MWD, weight average molecular weight (Mw), and number average molecular weight (Mn) of the low-density polyethylene are determined by measuring the weight average molecular weight (Mw) and number average molecular weight (Mn) using gel permeation chromatography (GPC). After measuring the average molecular weight (Mn), the molecular weight distribution can be determined by the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn). Specifically, using the Polymer Laboratories PLgel MIX-B 300 mm long column, Waters It can be measured using a PL-GPC220 device. At this time, the evaluation temperature is 140℃, 1,2,4-trichlorobenzene is used as a solvent, and the flow rate is 1mL/min. The sample is 10mg/10mL. Prepared at a concentration of , then supplied in an amount of 200 μL. The values of Mw and Mn are derived using a calibration curve formed using a polystyrene standard. At this time, the molecular weight (g/mol) of the polystyrene standard is 2,000 / 10,000 / 30,000 / Nine types of 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000 were used.
또, 발명의 다른 일 구현예에 따르면 상기한 제조방법에 의해 제조된 저밀도 폴리에틸렌을 이용한 가교 폴리에틸렌의 제조방법 및 이에 따라 제조된 가교 폴리에틸렌을 제공한다.In addition, according to another embodiment of the invention, a method for producing cross-linked polyethylene using low-density polyethylene produced by the above-mentioned production method and cross-linked polyethylene produced thereby are provided.
구체적으로 상기 가교 폴리에틸렌의 제조방법은, 상기 제조방법에 의해 제조한 저밀도 폴리에틸렌을, 가교제 및 산화방지제와 혼합하고, 혼련 및 압출하는 단계를 포함한다.Specifically, the method for producing cross-linked polyethylene includes the steps of mixing low-density polyethylene produced by the above production method with a cross-linking agent and an antioxidant, kneading, and extruding.
상기 저밀도 폴리에틸렌은 상술한 제조방법에 의해 제조되며, 이에 따라 발명의 일 구현예에 따른 상기 가교 폴리에틸렌 제조방법은 상기 저밀도 폴리에틸렌 제조를 위한 제조 공정을 더 포함할 수 있다.The low-density polyethylene is manufactured by the above-described manufacturing method. Accordingly, the method for manufacturing cross-linked polyethylene according to an embodiment of the invention may further include a manufacturing process for manufacturing the low-density polyethylene.
한편, 상기 가교제는 저밀도 폴리에틸렌의 압출시 가교 반응을 유도하기 위한 것으로, 가교 폴리에틸렌의 제조에 사용되는 것이면 특별히 제한되지 않는다. 일례로 디큐밀 퍼옥사이드(dicumyl peroxide, DCP), 벤조일 퍼옥사이드(benzoyl peroxide), 라우릴 퍼옥사이드(lauryl peroxide), t-부틸 큐밀 퍼옥사이드(tert-butyl cumyl peroxide), 디(t-부틸 퍼옥시이소프로필)벤젠(di(tert-butyl peroxy isopropyl) benzene), 2,5-디메틸-2,5-디(t-부틸 퍼옥시)헥산(2,5-dimethyl-2,5-di(tert-butyl peroxy)hexane), 또는 디-t-부틸 퍼옥사이드(di-tert-butyl peroxide) 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 혼합물이 사용될 수 있다.Meanwhile, the cross-linking agent is intended to induce a cross-linking reaction during extrusion of low-density polyethylene, and is not particularly limited as long as it is used in the production of cross-linked polyethylene. For example, dicumyl peroxide (DCP), benzoyl peroxide, lauryl peroxide, t-butyl cumyl peroxide (tert-butyl cumyl peroxide), di(t-butyl peroxide) Oxyisopropyl) benzene (di(tert-butyl peroxy isopropyl) benzene), 2,5-dimethyl-2,5-di(t-butyl peroxy)hexane (2,5-dimethyl-2,5-di(tert) -butyl peroxy)hexane), or di-tert-butyl peroxide (di-tert-butyl peroxide), and any one or a mixture of two or more of these may be used.
상기 가교제는 상기 저밀도 폴리에틸렌 100 중량부 대비 0.1 내지 10 중량부, 보다 구체적으로는 1.0 내지 3.0 중량부로 포함될 수 있다. 가교제의 함량이 0.1 중량부 미만이면 충분한 가교 결합이 형성되기 어렵고 또 10중량부를 초과하면 장기 노화특성 저하의 우려가 있다.The cross-linking agent may be included in an amount of 0.1 to 10 parts by weight, more specifically, 1.0 to 3.0 parts by weight, based on 100 parts by weight of the low-density polyethylene. If the content of the cross-linking agent is less than 0.1 parts by weight, it is difficult to form sufficient cross-linking, and if it exceeds 10 parts by weight, there is a risk of deterioration of long-term aging characteristics.
또, 상기 산화방지제로는 통상 가교 폴리에틸렌의 제조에 사용되는 것이면 특별히 제한되지 않는다. 일례로 4,4'-티오비스(2-t-부틸-5-메틸페놀), 4,6-비스(옥틸티오메틸)-o-크레졸, 2,2'-티오 디에틸 비스-[3-(3,5-디-t-부틸-4-하이드록시페닐)-프로피오네이트], 펜타에리트리틸-테트라키스-[3-(3,5-디-t-부틸-4-하이드록시페닐)-프로피오네이트], 4,4'-티오비스(2-메틸-6-t-부틸페놀), 2,2'-티오비스(6-t-부틸-4-메틸페놀), 옥타데실-[3-(3,5-디-t-부틸-4-하이드록시페닐)-프로피오네이트], 트리에틸렌글리콜-비스-[3-(3-t-부틸-4-하이드록시-5-메틸페놀)프로피오네이트], 티오디에틸렌 비스[3-(3,5-디-t-부틸-4-하이드록시페닐)프로피오네이트], 6,6'-디-t-부틸-2,2'-티오디-p-크레졸, 1,3,5-트리스(4-t-부틸-3-하이드록시-2,6-크실릴)메틸-1,3,5-트리아진-2,4,6-(1H,3H,5H)-트리온 또는 디옥타데실 3,3'-티오디프로피오네이트 등과 같은 힌더드 페놀계 산화방지제가 사용될 수 있으며, 이들 중 어느 하나 또는 둘 이상의 혼합물이 사용될 수 있다.Additionally, the antioxidant is not particularly limited as long as it is commonly used in the production of cross-linked polyethylene. For example, 4,4'-thiobis(2-t-butyl-5-methylphenol), 4,6-bis(octylthiomethyl)-o-cresol, 2,2'-thio diethyl bis-[3- (3,5-di-t-butyl-4-hydroxyphenyl)-propionate], pentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl )-propionate], 4,4'-thiobis(2-methyl-6-t-butylphenol), 2,2'-thiobis(6-t-butyl-4-methylphenol), octadecyl- [3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate], triethylene glycol-bis-[3-(3-t-butyl-4-hydroxy-5-methyl phenol)propionate], thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 6,6'-di-t-butyl-2,2 '-thiodi-p-cresol, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-xylyl)methyl-1,3,5-triazine-2,4, Hindered phenolic antioxidants such as 6-(1H,3H,5H)-trione or dioctadecyl 3,3'-thiodipropionate may be used, and any one or a mixture of two or more of these may be used. there is.
상기 산화방지제는 상기 저밀도 폴리에틸렌 100 중량부 대비 0.1 내지 1.0 중량부, 보다 구체적으로는 0.2 내지 0.5중량부로 포함될 수 있다. 산화방지제의 함량이 0.1 중량부 미만이면 산화방지제 사용에 따른 개선 효과가 미미하고, 1.0중량부를 초과할 경우 가교특성 저하의 우려가 있다.The antioxidant may be included in an amount of 0.1 to 1.0 parts by weight, more specifically 0.2 to 0.5 parts by weight, based on 100 parts by weight of the low-density polyethylene. If the content of the antioxidant is less than 0.1 part by weight, the improvement effect due to the use of the antioxidant is minimal, and if it exceeds 1.0 part by weight, there is a risk of deterioration of the crosslinking characteristics.
또, 상기 저밀도 폴리에틸렌과 가교제 및 산화방지제의 혼합시, 가교 촉진제, 트리억제제 등과 같은 1종 이상의 첨가제가 선택적으로 더 투입될 수 있다.In addition, when mixing the low-density polyethylene with a crosslinking agent and antioxidant, one or more additives such as a crosslinking accelerator, a tree inhibitor, etc. may be optionally added.
상기 가교 촉진제는 저밀도 폴리에틸렌의 가교 정도를 개선하여 첨가제의 이행(migration)을 보다 억제할 수 있다. 상기 가교 촉진제로는, 구체적으로 2,4-디페닐-4-메틸-1-펜텐(2,4-diphenyl-4-methyl-1-pentene) 또는 1,4-하이드로퀴논(1,4-hydroquinone) 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 혼합물이 사용될 수 있다.The crosslinking accelerator can improve the degree of crosslinking of low-density polyethylene and further inhibit migration of additives. The crosslinking accelerator is specifically 2,4-diphenyl-4-methyl-1-pentene or 1,4-hydroquinone. ), etc., and any one or a mixture of two or more of these may be used.
상기 가교 촉진제는, 상기 저밀도 폴리에틸렌 100 중량부에 대하여 0.1 내지 5 중량부, 보다 구체적으로는 0.1 내지 1.0 중량부로 포함될 수 있다. 가교 촉진제의 함량이 0.1중량부 미만이면 가교 촉진제 사용에 따른 개선 효과가 미미하고, 5중량부를 초과할 경우 장기 노화특성 저하의 우려가 있다. The crosslinking accelerator may be included in an amount of 0.1 to 5 parts by weight, more specifically 0.1 to 1.0 parts by weight, based on 100 parts by weight of the low-density polyethylene. If the content of the cross-linking accelerator is less than 0.1 parts by weight, the improvement effect due to the use of the cross-linking accelerator is minimal, and if it exceeds 5 parts by weight, there is a risk of deterioration of long-term aging characteristics.
상기 트리 억제제는 첨가제의 이행(migration)을 억제하는 작용을 하는 것으로, 구체적으로는 중량평균 분자량(Mw)이 5,000 내지 70,000 g/mol인 폴리에틸렌 글리콜이 사용될 수 있다. 상기 트리 억제제는 상기 저밀도 폴리에틸렌 100 중량부에 대하여 0.1 내지 5 중량부, 보다 구체적으로는 0.1 내지 1.0 중량부로 사용될 수 있다.The tri-inhibitor acts to inhibit migration of additives, and specifically, polyethylene glycol with a weight average molecular weight (Mw) of 5,000 to 70,000 g/mol may be used. The tree inhibitor may be used in an amount of 0.1 to 5 parts by weight, more specifically, 0.1 to 1.0 parts by weight, based on 100 parts by weight of the low-density polyethylene.
상기 저밀도 폴리에틸렌, 가교제, 산화방지제 및 선택적으로 첨가제를 혼합하고, 혼련 및 압출하여 가교시킨다.The low-density polyethylene, cross-linking agent, antioxidant, and optionally additives are mixed, kneaded, and extruded to cross-link.
상기 혼련 및 압출은 통상적인 가교 폴리에틸렌 조성물의 혼련 및 압출 방법인 경우 특별히 제한되지 않으며, 일례로 저밀도 폴리에틸렌을 제외한 나머지 성분들을 포함하는 마스터배치를 제조한 다음 저밀도 폴리에틸렌 등과 함께 또는 별도로 압출기에 투입하여 실시할 수 있다.The kneading and extrusion are not particularly limited in the case of a typical kneading and extrusion method of a cross-linked polyethylene composition. For example, a masterbatch containing the remaining components except low-density polyethylene is prepared and then put into an extruder together with low-density polyethylene or separately. can do.
상기 가교는 일례로 압출된 압출물(예를 들어, 펠렛 형태)을 이축 혼련기 등을 이용하여 필요에 따라 가교제와 혼합한 다음, 이렇게 혼합된 혼합물을 소정 온도 및 시간 동안 압출기로 압출 성형하는 것일 수 있다. 상기 압출기는 일례로 이축 압출기(twin extruder) 또는 혼련 기능이 부여된 1축 압출기 등일 수 있다.The crosslinking is, for example, mixing the extruded extrudate (for example, in the form of pellets) with a crosslinking agent as needed using a twin-screw kneader, and then extruding the mixed mixture with an extruder for a predetermined temperature and time. You can. The extruder may be, for example, a twin extruder or a single-screw extruder equipped with a kneading function.
상기 압출물에 대한 가교는 가교제의 분해 온도보다 높은 온도에서 수행될 수 있다. Crosslinking of the extrudate may be performed at a temperature higher than the decomposition temperature of the crosslinking agent.
상기한 제조방법에 의해 제조되는 가교 폴리에틸렌은 높은 가교도와 함께 우수한 고온 신율 및 짧은 수트리 길이를 나타낸다.Cross-linked polyethylene manufactured by the above-described manufacturing method exhibits a high degree of cross-linking, excellent high-temperature elongation, and short water tree length.
구체적으로 상기 가교 폴리에틸렌은 80% 이상, 또는 80 내지 90%의 가교도를 나타내며, 100% 이하, 또는 50 내지 100%의 고온 신율, 그리고 300㎛ 미만, 또는 260㎛ 이하의 짧은 수트리 길이를 나타낸다.Specifically, the crosslinked polyethylene exhibits a crosslinking degree of 80% or more, or 80 to 90%, a high temperature elongation of 100% or less, or 50 to 100%, and a short water tree length of less than 300 μm, or less than 260 μm.
본 발명에 있어서, 가교 폴리에틸렌의 가교도는, 가교 폴리에틸렌을 포함하는 수지 조성물을 이용하여 제조한 시트를 얇게 자른 후, 끓는 자이렌(xylene) 용액에 얇게 자른 0.2~0.3g의 시편을 넣고 24시간 동안 환류시킨 후 남은 시편의 무게 측정하고, 이를 이용하여 하기 수학식 1에 따라 가교도를 계산할 수 있다.In the present invention, the crosslinking degree of crosslinked polyethylene is determined by cutting a sheet manufactured using a resin composition containing crosslinked polyethylene into thin pieces and placing a 0.2 to 0.3 g thinly cut specimen in a boiling xylene solution for 24 hours. After refluxing, the weight of the remaining specimen can be measured and used to calculate the degree of cross-linking according to Equation 1 below.
[수학식 1][Equation 1]
가교도(%)=[(측정 전 시편 무게-측정 후 시편 무게)/측정 전 시편 무게] X 100Degree of crosslinking (%) = [(Weight of specimen before measurement - Weight of specimen after measurement)/Weight of specimen before measurement]
또, 가교 폴리에틸렌의 고온 신율은, IEC 811에 개시된 방법에 따라 측정할 수 있으며, 구체적으로 200℃/15분 및 20 N/cm2 하중의 조건에서 측정된 시편 길이의 변화 값을 %로 나타낸다. In addition, the high temperature elongation of cross-linked polyethylene can be measured according to the method disclosed in IEC 811, and specifically, the change in specimen length measured under the conditions of 200°C/15 minutes and 20 N/cm 2 load is expressed as %.
또, 가교 폴리에틸렌의 수트리 특성은 ASTM D6097에 따라 측정할 수 있으며, 구체적으로는 30일일 간 시간 경과에 따른 수트리 성장 길이를 측정하고 그 결과로부터 평가할 수 있다.In addition, the water tree properties of cross-linked polyethylene can be measured according to ASTM D6097, and specifically, the water tree growth length over time for 30 days can be measured and evaluated from the results.
이에 따라 전력 케이블, 포장재, 전선피복재, 전기절연제품, 테이프, 접착제, 각종 시트류, 그리고 태양전지와 같은 광전소자의 보호 필름이나 봉지재 등에 사용될 수 있으며, 특히 우수한 절연 특성과 함께 고온 신율 및 우수한 수트리 특성이 요구되는 전력 케이블의 제조에 유용할 수 있다.Accordingly, it can be used in power cables, packaging materials, wire covering materials, electrical insulation products, tapes, adhesives, various sheets, and protective films or encapsulation materials for photoelectric devices such as solar cells. In particular, it has excellent insulation properties and high temperature elongation and excellent It may be useful in the manufacture of power cables where water tree properties are required.
이에 따라 본 발명의 다른 일 구현예에 따르면 상기한 저밀도 폴리에틸렌을 포함하는 성형품, 보다 구체적으로는 전력 케이블을 제공한다.Accordingly, according to another embodiment of the present invention, a molded article containing the above-described low-density polyethylene, more specifically, a power cable, is provided.
발명을 하기의 실시예에서 보다 상세하게 설명한다. 단, 하기의 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기의 실시예에 의하여 한정되는 것은 아니다. The invention is explained in more detail in the following examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.
<저밀도 폴리에틸렌의 제조><Manufacture of low-density polyethylene>
실시예 1-1 내지 1-4, 및 비교예 1-1 내지 1-8Examples 1-1 to 1-4, and Comparative Examples 1-1 to 1-8
7단의 반응기를 포함하는 오토클레이브 반응기(최상단에서부터 제1단~제2단 반응기: 상단부(T1), 제3단~제5단 반응기: 중간부(T3), 제6단~제7단의 반응기: 하단부(T2)로 구분)를 준비하고, 하기 표 1에 기재된 바와 같이, 150 내지 300℃의 온도 범위 내에서 T2>T3>T1의 순서로 온도가 낮아지도록 각 반응기의 온도를 설정하였다. 기체상의 에틸렌 단량체를 10,000kg/h의 속도로 제1단으로 투입하고, 개질제로서 프로필렌을 하기 표 1에 기재된 양으로 상기 에틸렌 단량체와 함께 투입하였으며, 개시제로서 TBPP를 각각의 반응기의 선단 주입구를 통해 투입하였다. 하기 표 1에 기재된 바와 같은 조건으로 에틸렌 단량체를 중합 반응시켜 저밀도 폴리에틸렌을 제조하였다. Autoclave reactor containing 7 stages of reactor (from the top, 1st to 2nd stage reactors: top part (T1), 3rd to 5th stage reactors: middle part (T3), 6th to 7th stages Reactors (divided into lower parts (T2)) were prepared, and the temperature of each reactor was set so that the temperature was lowered in the order of T2>T3>T1 within the temperature range of 150 to 300°C, as shown in Table 1 below. Gaseous ethylene monomer was introduced into the first stage at a rate of 10,000 kg/h, propylene as a modifier was added together with the ethylene monomer in the amount shown in Table 1 below, and TBPP as an initiator was introduced through the tip inlet of each reactor. It was put in. Low-density polyethylene was prepared by polymerizing ethylene monomer under the conditions shown in Table 1 below.
하기 표 1에서 개질제의 투입량은 에틸렌 단량체 100중량부를 기준으로 한다.In Table 1 below, the amount of modifier added is based on 100 parts by weight of ethylene monomer.
(kg/cm2)reactor pressure
(kg/ cm2 )
(중량부)Modifier input amount
(part by weight)
온도
(℃)reactor
temperature
(℃)
(상단)1st stage
(Top)
(상단)2nd stage
(Top)
(중단)3rd stage
(stop)
(중단)4th Dan
(stop)
(중단)5th dan
(stop)
(하단)6th Dan
(lower)
(하단)7th Dan
(lower)
(T1)top average
(T1)
(T3)interrupted average
(T3)
(T2)Bottom average
(T2)
(T3-T1)△T1
(T3-T1)
(T2-T3)△T2
(T2-T3)
<가교 폴리에틸렌 수지 조성물의 제조><Manufacture of cross-linked polyethylene resin composition>
실시예 2-1 내지 2-4, 및 비교예 2-1 내지 2-8Examples 2-1 to 2-4, and Comparative Examples 2-1 to 2-8
상기 실시예 및 비교예에서 제조한 저밀도 폴리에틸렌 100중량부에 대하여 산화방지제로서 4,4'-티오비스(2-t-부틸-5-메틸페놀) 0.4 중량부 투입하고, 120℃ 온도의 압출기에서 펠렛 형태로 압출 가공한 후, 이를 밤바리 믹서에서 넣고 가교제로서 디큐밀 퍼옥사이드 2 중량부와 혼련하였다. 혼련된 혼합물을 180℃에서 10분 동안 압축 성형하여 시트 상의 가교 폴리에틸렌 수지 조성물을 제조하였다.0.4 parts by weight of 4,4'-thiobis(2-t-butyl-5-methylphenol) was added as an antioxidant to 100 parts by weight of low-density polyethylene prepared in the above examples and comparative examples, and extruded in an extruder at a temperature of 120°C. After extrusion processing into pellet form, it was placed in a Bambari mixer and kneaded with 2 parts by weight of dicumyl peroxide as a cross-linking agent. The kneaded mixture was compression molded at 180°C for 10 minutes to prepare a sheet-like crosslinked polyethylene resin composition.
실험예Experiment example
상기에서 제조한 실시예 및 비교예에서 제조한 저밀도 폴리에틸렌(PE) 및 가교 폴리에틸렌 수지 조성물에 대해 하기 방법으로 물성을 측정하고, 그 결과를 표 2에 나타내었다.The physical properties of the low-density polyethylene (PE) and cross-linked polyethylene resin compositions prepared in the examples and comparative examples above were measured by the following method, and the results are shown in Table 2.
(1) 수평균 분자량(Mn), 중량평균 분자량(Mw) 및 분자량 분포(MWD): 겔투과 크로마토그래피 (GPC) 를 이용하여 실시예 및 비교예에서 제조한 저밀도 폴리에틸렌의 Mw 및 Mn 을 측정 후 Mw/Mn의 비로 결정하였다. 구체적으로는 Polymer Laboratories PLgel MIX-B 300mm 길이 칼럼을 이용하여 Waters PL-GPC220 기기를 이용하여 측정하였다. 이때, 평가 온도는 140℃이며, 1,2,4-트리클로로벤젠을 용매로서 사용하였으며, 유속은 1mL/min이었다. 샘플은 10mg/10mL의 농도로 조제한 다음, 200 μL의 양으로 공급하였다. 폴리스티렌 표준을 이용하여 형성된 검정 곡선을 이용하여 Mw 및 Mn 의 값을 유도하였다. 폴리스티렌 표준품의 분자량(g/mol)은 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000의 9종을 사용하였다.(1) Number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (MWD): After measuring Mw and Mn of low-density polyethylene prepared in Examples and Comparative Examples using gel permeation chromatography (GPC) It was determined by the ratio of Mw/Mn. Specifically, it was measured using a Waters PL-GPC220 instrument using a Polymer Laboratories PLgel MIX-B 300 mm long column. At this time, the evaluation temperature was 140°C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was 1 mL/min. The sample was prepared at a concentration of 10 mg/10 mL and then supplied in an amount of 200 μL. The values of Mw and Mn were derived using a calibration curve formed using polystyrene standards. Nine types of molecular weights (g/mol) of polystyrene standards were used: 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.
(2) 밀도: ASTM D1505의 방법에 따라 실시예 및 비교예에서 제조한 저밀도 폴리에틸렌의 밀도를 측정하였다.(2) Density: The density of low-density polyethylene prepared in Examples and Comparative Examples was measured according to the method of ASTM D1505.
(3) 고온 신율(Hot-elongation) (%): 상기 실시예 및 비교예에서 제조한 가교 폴리에틸렌 수지 조성물에 대해 IEC 811에 개시된 방법에 따라 200 ℃/15분, 20 N/cm2 하중에서 측정된 시편 길이의 변화 값을 %로 나타내었다.(3) Hot-elongation (%): Measured at 200°C/15 minutes and 20 N/cm 2 load according to the method disclosed in IEC 811 for the cross-linked polyethylene resin compositions prepared in the above examples and comparative examples. The change in specimen length was expressed as a percentage.
(4) 가교도(%): (4) Crosslinking degree (%):
상기 실시예 및 비교예에서 제조한 가교 폴리에틸렌 수지 조성물의 시트를 얇게 자른 후, 끓는 자이렌(xylene) 용액에 얇게 자른 0.2~0.3g의 시편을 넣고 24시간 동안 환류시켰다. 남은 시편의 무게 측정하고, 하기 수학식 1에 의하여 가교도를 계산하였다.The sheets of the cross-linked polyethylene resin composition prepared in the above examples and comparative examples were cut into thin pieces, and then 0.2 to 0.3 g of the thinly cut specimens were placed in a boiling xylene solution and refluxed for 24 hours. The weight of the remaining specimen was measured, and the degree of crosslinking was calculated using Equation 1 below.
[수학식 1][Equation 1]
가교도(%)=[(측정 전 시편 무게-측정 후 시편 무게)/측정 전 시편 무게] X 100Degree of crosslinking (%) = [(Weight of specimen before measurement - Weight of specimen after measurement)/Weight of specimen before measurement]
(5) 수트리 길이(Water Tree Length) (㎛): ASTM D6097에 따라 일정한 시간(30일) 경시에 따른 수트리 성장 길이를 측정하였다. (5) Water Tree Length (㎛): Water tree growth length was measured over a certain period of time (30 days) according to ASTM D6097.
도 1에서와 같은 가속 수트리 열화 장치를 사용하여, 시트상으로 성형된 시료를 도 2에서와 같이 원추형 바늘을 삽입할 수 있는 바늘 삽입기에 삽입하고, 시편 끝으로부터 3.2mm 떨어진 위치에 도달할 때까지 삽입한 후 180℃에서 프레스하여 가교된 수트리 측정용 시편을 제조하였다. 이 때 사용된 바늘의 바늘각은 60°이고 바늘 끝의 곡률 반경은 3㎛이었다. 상기 과정을 거쳐 제조된 시편에 0.01M의 염화나트륨(NaCl) 용액을 붓고 50mm의 백금 선을 꼽은 후 5kV 교류 전압을 720시간 동안 측정하였다. 성장된 수트리 길이 측정은 시편을 얇게 잘라 광학 현미경을 이용하여 최종 성장한 수트리 길이를 측정하였다. 이 때 측정된 수트리 길이는 측정한 총 시편의 평균값이다.Using the accelerated water tree degradation device as shown in Figure 1, the sample molded into a sheet is inserted into a needle inserter capable of inserting a conical needle as shown in Figure 2, and when it reaches a position 3.2 mm away from the end of the specimen, After inserting until the crosslinked sutri measurement specimen was manufactured by pressing at 180°C. The needle angle of the needle used at this time was 60° and the radius of curvature of the needle tip was 3㎛. A 0.01 M sodium chloride (NaCl) solution was poured into the specimen prepared through the above process, a 50 mm platinum wire was connected, and a 5 kV alternating current voltage was measured for 720 hours. To measure the length of the grown tree, the specimen was cut into thin pieces and the final grown tree length was measured using an optical microscope. At this time, the measured water tree length is the average value of the total measured specimens.
(g/cm3)density
(g/ cm3 )
실시예 1-1 내지 1-4에 따라 제조한 저밀도 폴리에틸렌은 저압 하에서의 중합 공정 수행에도 불구하고, 반응기내 온도 제어를 통해 고압 하에서의 중합 공정에 의해 제조된 비교예 1-1의 저밀도 폴리에틸렌과 비교하여 동등 수준 이상의 우수한 물성적 특징을 나타내었으며, 또 이를 이용하여 제조한 실시예 2-1 내지 2-4의 가교 폴리에틸렌 역시 80% 이상의 높은 가교도와 함께 우수한 고온 신율 및 수트리 특성을 나타내었다. Although the low-density polyethylene prepared according to Examples 1-1 to 1-4 was performed under low pressure, compared to the low-density polyethylene of Comparative Example 1-1 prepared by the polymerization process under high pressure through temperature control in the reactor. It showed excellent physical properties at the same level or higher, and the cross-linked polyethylene of Examples 2-1 to 2-4 manufactured using it also showed excellent high-temperature elongation and water tree properties along with a high cross-linking degree of more than 80%.
또 반응기내 온도 조건은 비교예 1-1와 동일하지만, 본 발명과 같이 저압 하에 중합 공정을 수행한 비교예 1-2의 경우, 제조되는 저밀도 폴리에틸렌의 Mw가 낮아졌으며, 또 동등량의 개질제가 투입된 실시예 1-3과 비교하여 상대적으로 낮은 Mw 및 증가된 MWD를 나타내었다. 그 결과 가교 폴리에틸렌 제조에 적용시 가교 폴리에틸렌의 가교도가 크게 낮아지고, 고온 신율 특성 및 수트리 특성이 크게 저하되었다. 이로부터 종래의 반응기 조건에서 반응 압력을 낮출 경우, 제조되는 폴리에틸렌의 물성이 저하되고, 이를 이용하여 제조한 가교 폴리에틸렌의 특성 또한 저하됨을 확인할 수 있다. In addition, the temperature conditions in the reactor were the same as Comparative Example 1-1, but in Comparative Example 1-2, in which the polymerization process was performed under low pressure as in the present invention, the Mw of the low-density polyethylene produced was lowered, and an equivalent amount of modifier was used. Compared to Examples 1-3, which were introduced, relatively low Mw and increased MWD were exhibited. As a result, when applied to the manufacture of cross-linked polyethylene, the cross-linking degree of cross-linked polyethylene was significantly lowered, and the high-temperature elongation characteristics and water tree properties were greatly reduced. From this, it can be seen that when the reaction pressure is lowered under conventional reactor conditions, the physical properties of the polyethylene produced deteriorate, and the properties of the cross-linked polyethylene produced using it also deteriorate.
또, 저압 하에 반응기내 반응 영역에 따른 온도 조건 T2>T3>T1을 충족하지만, 상단의 온도가 낮아져 T3과 T1의 반응 영역간 온도차이 △T1 가 본 발명에서 한정한 범위를 충족하지 않는 비교예 1-3의 경우, 동등량의 개질제가 투입된 실시예 1-3과 비슷하여 제조되는 저밀도 폴리에틸렌의 Mw는 상대적으로 증가하고, Mn은 감소하였으며, 그 결과로서 MWD가 증가하였다. 이에 따라 가교 폴리에틸렌 제조에 적용시 고온 신율 특성이 크게 저하되었다. In addition, Comparative Example 1 satisfies the temperature condition T2>T3>T1 according to the reaction zone in the reactor under low pressure, but the temperature at the top is lowered so that the temperature difference △T1 between the reaction zones T3 and T1 does not meet the range limited in the present invention. In the case of -3, the Mw of the low-density polyethylene produced was similar to Example 1-3 in which an equivalent amount of the modifier was added, and the Mn was relatively increased, and the Mn was decreased, and as a result, the MWD increased. Accordingly, when applied to the manufacture of cross-linked polyethylene, the high-temperature elongation characteristics were significantly reduced.
또, 저압 하에 반응기내 각 반응 영역에서의 온도 조건 및 반응 영역에 따른 온도 조건 T2>T3>T1은 충족하지만, T3과 T1의 반응 영역간 온도차이 △T1 가 본 발명에서 한정한 범위를 충족하지 않는 비교예 1-4의 경우에도, 동등량의 개질제가 투입된 실시예 1-3과 비슷하여 제조되는 저밀도 폴리에틸렌의 Mw는 상대적으로 증가하고, Mn은 감소하였으며, 그 결과로서 MWD가 보다 증가하였다. 이에 따라 이를 이용하여 제조한 가교 폴리에틸렌의 가교도 및 고온 신율 특성이 저하되었다. In addition, under low pressure, the temperature condition in each reaction zone in the reactor and the temperature condition T2>T3>T1 according to the reaction zone are satisfied, but the temperature difference △T1 between the reaction zones T3 and T1 does not meet the range limited in the present invention. In Comparative Example 1-4, Mw of the low-density polyethylene produced was similar to Example 1-3 in which an equivalent amount of modifier was added, and Mn was relatively increased and Mn was decreased, and as a result, MWD increased. Accordingly, the crosslinking degree and high-temperature elongation characteristics of the crosslinked polyethylene manufactured using this were reduced.
또, 저압 하에 반응기내 반응 영역에 따른 온도 조건 T2>T3>T1을 충족하지만, T3과 T1의 반응 영역간 온도차이 △T1의 조건을 충족하지 않고, 또 하단 평균 온도 T2가 높은 비교예 1-5의 경우, 동등량의 개질제가 투입된 실시예 1-2 및 1-4와 비슷하여 제조되는 저밀도 폴리에틸렌의 Mn이 감소하고, Mw가 증가하면서 MWD가 크게 증가하였다. 그 결과 가교 폴리에틸렌 제조에 적용시 수트리 특성이 크게 저하되었다.In addition, under low pressure, the temperature condition T2>T3>T1 according to the reaction region in the reactor is met, but the temperature difference between the reaction regions of T3 and T1 is not satisfied, △T1, and the bottom average temperature T2 is high. Comparative Example 1-5 In the case of low-density polyethylene produced similarly to Examples 1-2 and 1-4 in which an equivalent amount of modifier was added, the Mn decreased, and the MWD increased significantly as the Mw increased. As a result, when applied to the manufacture of cross-linked polyethylene, the water tree properties were significantly reduced.
또, 상단(T1) 및 하단(T2)의 평균 온도가 낮고, 특히 T2의 온도가 낮아 T2와 T3의 온도차이 △T2 조건을 벗어난 비교예 1-6의 경우, 동등량의 개질제가 투입된 실시예 1-1과 비교하여 제조되는 저밀도 폴리에틸렌의 Mn이 상대적으로 저하되면서 MWD가 증가하였다. 그 결과 가교 폴리에틸렌 제조에 적용시 가교 폴리에틸렌의 가교도가 낮아지고, 고온 신율 특성 및 수트리 특성이 저하되었다.In addition, in the case of Comparative Examples 1-6, where the average temperature of the top (T1) and bottom (T2) is low, and especially the temperature of T2 is low, and the temperature difference between T2 and T3 is outside the △T2 condition, an equal amount of modifier is added. Compared to 1-1, the MWD of the manufactured low-density polyethylene was relatively decreased and the MWD increased. As a result, when applied to the manufacture of cross-linked polyethylene, the cross-linking degree of cross-linked polyethylene was lowered, and the high-temperature elongation characteristics and water tree properties were deteriorated.
또, 상단(T1) 및 하단(T2)의 평균온도가 낮고, 특히 T2의 평균 온도가 높아 T2와 T3의 온도차이 △T2 조건을 크게 벗어난 비교예 1-7의 경우, 동등량의 개질제가 투입된 실시예 1-1과 비교하여 제조되는 저밀도 폴리에틸렌의 Mn과 Mw 둘 모두 증가하였으며. 그 결과 가교 폴리에틸렌 제조에 적용시 고온 신율 특성이 저하되었다.In addition, in the case of Comparative Example 1-7, where the average temperature of the top (T1) and bottom (T2) is low, and the average temperature of T2 is especially high, the temperature difference between T2 and T3 is greatly outside the △T2 condition, an equal amount of modifier was added. Compared to Example 1-1, both Mn and Mw of the manufactured low-density polyethylene increased. As a result, high temperature elongation characteristics were deteriorated when applied to the production of cross-linked polyethylene.
또, 개질제의 투입량이 1.3중량부로 작은 비교예 1-8의 경우, 동일한 반응기의 온도 및 압력 조건에서 수행한 실시예 1-1과 비교하여, 제조되는 저밀도 폴리에틸렌의 Mn이 크게 감소함으로써 MWD가 현저히 넓어졌다. 그 결과 가교 폴리에틸렌 제조에 적용시 고온 신율 특성이 저하되었다.In addition, in the case of Comparative Example 1-8, where the amount of modifier added was as small as 1.3 parts by weight, Mn of the low-density polyethylene produced was greatly reduced compared to Example 1-1 performed under the temperature and pressure conditions of the same reactor, resulting in a significant MWD. It got wider. As a result, high temperature elongation characteristics were deteriorated when applied to the production of cross-linked polyethylene.
상기한 결과로부터 본 발명에 따른 제조방법에 의해, 종래 고온 고압 반응에 의한 폴리에틸렌의 제조시의 공정 안정성 저하 등의 리스크 발생에 대한 우려 없이, 저압 공정 하에서도 동등 수준 이상의 우수한 물성을 갖는 저밀도 폴리에틸렌 및 이를 포함하는 가교 폴리에틸렌을 제조할 수 있음을 확인할 수 있다. From the above results, by the production method according to the present invention, low-density polyethylene and a low-density polyethylene having excellent physical properties at the same level or higher even under a low-pressure process without concerns about risks such as a decrease in process stability during the production of polyethylene by a conventional high-temperature and high-pressure reaction. It can be confirmed that cross-linked polyethylene containing this can be manufactured.
Claims (17)
상기 반응기는 3단 이상의 반응영역을 포함하고,
최상단으로부터 1단 이상의 제1 반응영역의 평균 온도를 T1, 최하단으로부터 1단 이상의 제2 반응영역의 평균 온도 T2, 그리고 그 사이에 있는 1단 이상의 제3 반응영역의 평균 온도를 T3이라 할 때, T2>T3>T1의 온도 조건을 충족하며,
T3과 T1의 차이(ΔT1)가 50 내지 65℃이고, T2와 T3의 차이(ΔT2)가 50 내지 70℃이며,
상기 개질제는 에틸렌 단량체 100중량부에 대하여 1.5중량부 이상의 함량으로 투입되는,
0.94 g/cm3 이하의 밀도 및 5 내지 6.05의 분자량 분포(MWD)를 갖는 폴리에틸렌의 제조방법.
Putting ethylene monomer into an autoclave reactor in the presence of an initiator, adding a modifier, and polymerizing it under a pressure of 1700 kg/cm 2 or less,
The reactor includes three or more reaction zones,
When the average temperature of the first reaction zone of one or more stages from the top is T1, the average temperature of the second reaction zone of one or more stages from the bottom is T2, and the average temperature of the third reaction zone of one or more stages in between is T3, It satisfies the temperature condition of T2>T3>T1,
The difference (ΔT1) between T3 and T1 is 50 to 65°C, and the difference (ΔT2) between T2 and T3 is 50 to 70°C,
The modifier is added in an amount of 1.5 parts by weight or more based on 100 parts by weight of ethylene monomer.
A method for producing polyethylene having a density of 0.94 g/cm 3 or less and a molecular weight distribution (MWD) of 5 to 6.05.
상기 중합이 1500 내지 1700 kg/cm2의 압력하에서 수행되는, 폴리에틸렌의 제조방법.
According to paragraph 1,
A method for producing polyethylene, wherein the polymerization is carried out under a pressure of 1500 to 1700 kg/cm 2 .
상기 반응기에서의 중합 온도가 150 내지 320℃인, 폴리에틸렌의 제조방법.
According to paragraph 1,
A method for producing polyethylene, wherein the polymerization temperature in the reactor is 150 to 320°C.
상기 제3 반응영역의 평균 온도 T3이 220 내지 250℃인, 폴리에틸렌의 제조방법.
According to paragraph 1,
A method for producing polyethylene, wherein the average temperature T3 of the third reaction zone is 220 to 250 ° C.
상기 제1 반응영역의 평균 온도 T1이 160 내지 180℃이고, 상기 제2 반응영역의 평균 온도 T2가 280 내지 300℃ 이며, 제3 반응영역의 평균 온도 T3이 T2>T3>T1의 온도 조건을 충족하는, 폴리에틸렌의 제조방법.
According to paragraph 1,
The average temperature T1 of the first reaction zone is 160 to 180°C, the average temperature T2 of the second reaction zone is 280 to 300°C, and the average temperature T3 of the third reaction zone is T2>T3>T1. A method of manufacturing polyethylene that satisfies the requirement.
상기 반응기가 7단의 반응영역을 포함하고, T1은 최상단으로부터 2개 단의 반응영역의 평균 온도이고, T2는 최하단으로부터 2개 단의 반응영역의 평균 온도이며, T3는 그 사이의 3개 단의 반응영역의 평균 온도인, 폴리에틸렌의 제조방법.
According to paragraph 1,
The reactor includes 7 reaction zones, T1 is the average temperature of the reaction zones in the two stages from the top, T2 is the average temperature of the reaction zones in the two stages from the bottom, and T3 is the average temperature of the reaction zones in the three stages in between. Method for producing polyethylene, which is the average temperature of the reaction region.
상기 개질제가 에틸렌 단량체 100중량부에 대하여 1.5 내지 3중량부로 투입되는, 폴리에틸렌의 제조방법.
According to paragraph 1,
A method for producing polyethylene, wherein the modifier is added in an amount of 1.5 to 3 parts by weight based on 100 parts by weight of ethylene monomer.
상기 개질제는 탄소수 3 내지 12의 올레핀계 탄화수소류를 포함하는, 폴리에틸렌의 제조방법.
According to paragraph 1,
A method for producing polyethylene, wherein the modifier includes olefinic hydrocarbons having 3 to 12 carbon atoms.
상기 개질제는 프로필렌을 포함하는, 폴리에틸렌의 제조방법.
According to paragraph 1,
A method for producing polyethylene, wherein the modifier includes propylene.
상기 개시제는 DIPND(1,4-di(2-neodecanoylperoxyisopropyl)benzene), CUPND(Cumylperoxy neodecanoate), SBPC(Di(sec-butyl) peroxydicarbonate), NBPC(Di(n-butyl)peroxydicarbonate), EHP(Di(2-ethylhexyl) peroxydicarbonate), TAPND(Tert-amylperoxyneodecanoate) TBPND(Tert-butyl peroxyneodecanoate), TAPPI(Tert-amylperoxy pivalate), TBPP(Tert-butylperoxy pivalate), INP(Di(3,5,5-trimethylhexanoyl) peroxide), TAPEH(Tert-amylperoxy 2-ethylhexanoate), TBPEH(Tert-butylperoxy 2-ethylhexanoate), TBPIB(Tert-butylperoxy-isobutyrate), TBPIN(Tert-butylperoxy-3,5,5-trimethylhexanoate) 및 TBPA(Tert-butylperoxyacetate)로 이루어진 군으로부터 선택된 1종 이상의 유기 과산화물을 포함하는, 폴리에틸렌의 제조방법.
According to paragraph 1,
The initiator is DIPND (1,4-di(2-neodecanoylperoxyisopropyl)benzene), CUPND (Cumylperoxy neodecanoate), SBPC (Di(sec-butyl) peroxydicarbonate), NBPC (Di(n-butyl)peroxydicarbonate), EHP(Di( 2-ethylhexyl) peroxydicarbonate), TAPND (Tert-amylperoxyneodecanoate) TBPND (Tert-butyl peroxyneodecanoate), TAPPI (Tert-amylperoxy pivalate), TBPP (Tert-butylperoxy pivalate), INP (Di(3,5,5-trimethylhexanoyl) peroxide ), Tert-amylperoxy 2-ethylhexanoate (TAPEH), Tert-butylperoxy 2-ethylhexanoate (TBPEH), Tert-butylperoxy-isobutyrate (TBPIB), Tert-butylperoxy-3,5,5-trimethylhexanoate (TBPIN), and Tert-butylperoxy-3,5,5-trimethylhexanoate (TBPIN). A method for producing polyethylene, comprising at least one organic peroxide selected from the group consisting of butylperoxyacetate.
상기 폴리에틸렌은 0.87 내지 0.94 g/cm3의 밀도를 갖는, 폴리에틸렌의 제조방법.
According to paragraph 1,
The polyethylene has a density of 0.87 to 0.94 g/cm 3 .
상기 폴리에틸렌은 하기 조건을 충족하는 것인, 폴리에틸렌의 제조방법:
수평균 분자량(Mn): 15,000 내지 30,000 g/mol
중량평균 분자량(Mw): 100,000 내지 150,000 g/mol.
According to paragraph 1,
A method for producing polyethylene, wherein the polyethylene satisfies the following conditions:
Number average molecular weight (Mn): 15,000 to 30,000 g/mol
Weight average molecular weight (Mw): 100,000 to 150,000 g/mol.
상기 폴리에틸렌을, 가교제 및 산화방지제와 혼합하고, 혼련 및 압출하여 가교시키는 단계를 포함하며,
상기 반응기는 적어도 3단 이상의 반응영역을 포함하고,
최상단으로부터 1단 이상의 제1 반응영역의 평균 온도를 T1, 최하단으로부터 1단 이상의 제2 반응영역의 평균 온도 T2, 그리고 그 사이에 있는 1단 이상의 제3 반응영역의 평균 온도를 T3이라 할 때, T2>T3>T1의 온도 조건을 충족하며,
T3과 T1의 차이(ΔT1)가 50 내지 65℃이고, T2와 T3의 차이(ΔT2)가 50 내지 70℃이며,
상기 개질제는 에틸렌 단량체 100중량부에 대하여 1.5중량부 이상의 함량으로 투입되는, 가교 폴리에틸렌의 제조방법.
Ethylene monomer is placed in an autoclave reactor in the presence of an initiator, a modifier is added, and polymerized under a pressure of 1700 kg/cm 2 or less to produce polyethylene having a density of 0.94 g/cm 3 or less and a molecular weight distribution (MWD) of 5 to 6.05. manufacturing step; and
Comprising the step of crosslinking the polyethylene by mixing it with a crosslinking agent and an antioxidant, kneading, and extruding,
The reactor includes at least three reaction zones,
When the average temperature of the first reaction zone of one or more stages from the top is T1, the average temperature of the second reaction zone of one or more stages from the bottom is T2, and the average temperature of the third reaction zone of one or more stages in between is T3, It satisfies the temperature condition of T2>T3>T1,
The difference (ΔT1) between T3 and T1 is 50 to 65°C, and the difference (ΔT2) between T2 and T3 is 50 to 70°C,
A method for producing cross-linked polyethylene, wherein the modifier is added in an amount of 1.5 parts by weight or more based on 100 parts by weight of ethylene monomer.
상기 가교제는, 디큐밀 퍼옥사이드, 벤조일 퍼옥사이드, 라우릴 퍼옥사이드, t-부틸 큐밀 퍼옥사이드, 디(t-부틸 퍼옥시이소프로필)벤젠, 2,5-디메틸-2,5-디(t-부틸 퍼옥시)헥산, 및 디-t-부틸 퍼옥사이드로 이루어진 군으로부터 선택된 어느 하나 또는 둘 이상을 포함하는, 가교 폴리에틸렌의 제조방법.
According to clause 13,
The crosslinking agent is dicumyl peroxide, benzoyl peroxide, lauryl peroxide, t-butyl cumyl peroxide, di(t-butyl peroxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t -Butyl peroxy)hexane, and di-t-butyl peroxide. A method for producing cross-linked polyethylene, comprising any one or two or more selected from the group consisting of
상기 산화 방지제는, 4,4'-티오비스(2-t-부틸-5-메틸페놀), 4,6-비스(옥틸티오메틸)-o-크레졸, 2,2'-티오 디에틸 비스-[3-(3,5-디-t-부틸-4-하이드록시페닐)-프로피오네이트], 펜타에리트리틸-테트라키스-[3-(3,5-디-t-부틸-4-하이드록시페닐)-프로피오네이트], 4,4'-티오비스(2-메틸-6-t-부틸페놀), 2,2'-티오비스(6-t-부틸-4-메틸페놀), 옥타데실-[3-(3,5-디-t-부틸-4-하이드록시페닐)-프로피오네이트], 트리에틸렌글리콜-비스-[3-(3-t-부틸-4-하이드록시-5-메틸페놀)프로피오네이트], 티오디에틸렌 비스[3-(3,5-디-t-부틸-4-하이드록시페닐)프로피오네이트], 6,6'-디-t-부틸-2,2'-티오디-p-크레졸, 1,3,5-트리스(4-t-부틸-3-하이드록시-2,6-크실릴)메틸-1,3,5-트리아진-2,4,6-(1H,3H,5H)-트리온 및 디옥타데실 3,3'-티오디프로피오네이트로 이루어진 군으로부터 선택되는 어느 하나 또는 둘 이상을 포함하는, 가교 폴리에틸렌의 제조방법.
According to clause 13,
The antioxidants include 4,4'-thiobis(2-t-butyl-5-methylphenol), 4,6-bis(octylthiomethyl)-o-cresol, 2,2'-thio diethyl bis- [3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate], pentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4- Hydroxyphenyl)-propionate], 4,4'-thiobis(2-methyl-6-t-butylphenol), 2,2'-thiobis(6-t-butyl-4-methylphenol), Octadecyl-[3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate], triethylene glycol-bis-[3-(3-t-butyl-4-hydroxy- 5-methylphenol)propionate], thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 6,6'-di-t-butyl- 2,2'-thiodi-p-cresol, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-xylyl)methyl-1,3,5-triazine-2 , 4,6-(1H,3H,5H)-trione and dioctadecyl 3,3'-thiodipropionate, comprising any one or more than one selected from the group consisting of cross-linked polyethylene.
상기 가교제 및 산화방지제는 각각 상기 폴리에틸렌 100 중량부 대비 0.1 내지 10 중량부로 투입되는, 가교 폴리에틸렌의 제조방법.
According to clause 13,
A method for producing cross-linked polyethylene, wherein the cross-linking agent and antioxidant are each added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyethylene.
상기 폴리에틸렌과 가교제 및 산화방지제와의 혼합시, 가교 촉진제 및 트리 억제제 중 1종 이상의 첨가제가 더 투입되는, 가교 폴리에틸렌의 제조방법.According to clause 13,
A method for producing cross-linked polyethylene, wherein when mixing the polyethylene with a cross-linking agent and an antioxidant, at least one additive selected from the group consisting of a cross-linking accelerator and a tri-inhibitor is further added.
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