CN1078225C - 具有特定水树生长率共聚物的制备方法 - Google Patents
具有特定水树生长率共聚物的制备方法 Download PDFInfo
- Publication number
- CN1078225C CN1078225C CN90106964.7A CN90106964A CN1078225C CN 1078225 C CN1078225 C CN 1078225C CN 90106964 A CN90106964 A CN 90106964A CN 1078225 C CN1078225 C CN 1078225C
- Authority
- CN
- China
- Prior art keywords
- multipolymer
- weight
- ethylene copolymer
- copolymer
- crosslinked
- 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.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 28
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 hydrocarbyl aluminum Chemical compound 0.000 claims abstract description 16
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 240000005572 Syzygium cordatum Species 0.000 claims abstract description 7
- 235000006650 Syzygium cordatum Nutrition 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 24
- 229910000077 silane Inorganic materials 0.000 claims description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 12
- 229920001038 ethylene copolymer Polymers 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims 1
- 210000001503 joint Anatomy 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 abstract description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000005977 Ethylene Substances 0.000 abstract description 6
- 239000012018 catalyst precursor Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000009413 insulation Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 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 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229940091250 magnesium supplement Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- ISSYTHPTTMFJKL-UHFFFAOYSA-N 1-ethenylcyclopentene Chemical class C=CC1=CCCC1 ISSYTHPTTMFJKL-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 1
- 241001589086 Bellapiscis medius Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- BQYNOZYISQGMOB-UHFFFAOYSA-N CC(C)CO[SiH3] Chemical compound CC(C)CO[SiH3] BQYNOZYISQGMOB-UHFFFAOYSA-N 0.000 description 1
- AGUIILSGLFUTKG-UHFFFAOYSA-N CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] Chemical compound CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] AGUIILSGLFUTKG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940073589 magnesium chloride anhydrous Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000005574 norbornylene group Chemical group 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000009156 water cure Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
- C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
- C08L43/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Physics & Mathematics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Sealing Devices (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Lubricants (AREA)
- Dental Preparations (AREA)
- Road Signs Or Road Markings (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Insulated Conductors (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种抗水树网络组合物，包含a)一种至少有两种共聚单体、乙烯和4-甲基-1-戊烯的共聚物，该共聚物的密度不大于约0.92g/cm；或b)一种至少包括乙烯和1-辛烯两种共聚单体的共聚物。其密度不大于约0.92g/cm ；或 c)用一种可水解的乙烯基硅烷接技的共聚物a)或b)，a)和b)的共聚物是在聚合条件下，由有关的共聚单体与下述催化剂体系接触而制备的：i)含镁、钛、卤素和电子给体的催化剂母体及烃基铝助催化剂或ii)含钒、电子给体和烃基铝卤化物的催化剂母体、烃基铝助催化剂及低级卤代烷促进剂。
Description
本发明涉及一类由于具有抗水树网络特性，因而在高低电压的绝缘中极为有用的组合物。
众所周知，用挤塑电介质而绝缘的电力电缆安装在极可能与水接触的地下时，寿命会缩短。当有机聚合材料在有液态或汽态水存在的情况下长期处于电场中时，会出现水树网络，电缆寿命的缩短被认为是由形成的水树网络造成的。因为出现水树网络的最终结果是使电缆的绝缘强度降低。
为了增加有机绝缘材料抗由于水树而降解的能力，已经提出了许多方法。这些方法包括例如：在聚乙烯中加入(i)诸如乙烯和醋酸乙烯共聚物那样的极性共聚物，(ii)诸如十二烷醇那样的电压稳定剂，和(iii)诸如粘土那样的填料。这些方法都有某些缺点，例如增加电介质的损耗，即增加功率因数损耗，增加材料的挥发性或价格。
因此，本发明的目的是提供一种适宜在高低电压绝缘中使用的、具有抗水树网络特性的组合物，它不依靠使用诸如极性共聚物，电压稳定剂或填料等改性剂未获得抗水树网络的特性，它将使“纯的”聚乙烯的令人满意的电性能，例如它的低损耗因子获得利用。
其它的目的和优点将在下文中明显看到。
按照本发明，上述目的是通过一种抗水树网络的绝缘组合物来实现的，该组合物包括：
(a)一种密度不大于0.920克/每立方厘米的乙烯共聚物，这种共聚物是通过将乙烯和4-甲基-1-戊烯的混合物，以及还可有一种或多种其它α-烯烃共聚单体，在聚合催化剂存在条件下共聚而生产的，或
(b)一种密度不大于0.920克/每立方厘米的乙烯共聚物，该共聚物是由乙烯和1-辛烯的混合物，以及还可有一种或多种其它α-烯烃共聚单体，在聚合催化剂存在条件下共聚而生产的，或
(c)一种按上述(a)或(b)与可水解的乙烯基硅烷化合物接技的乙烯共聚物，或
(d)一种将上述(a)、(b)和(c)中所述的共聚物的任意两种或多种以任何比例混合而成的混合物。
此处所述的聚合催化剂由下列物质组成：
(A)：镁、钛、卤素和一种电子给体，以及一种或多种含铝的化合物；或
(B)：钒、卤素和一种电子给体以及一种或多种含铝的化合物，还可以有一种低级卤烷烃化合物。
在本说明书中“共聚物”一词是指明两种或多种共聚单体为基础的聚合物。上面提到的两种共聚物，即乙烯/4-甲基-1-戊烯共聚物和乙烯/1-辛烯共聚物都可以包含有另外的共聚单体，例如具有3-12个碳原子的α-烯烃或二烯烃。这种二烯烃可以是包含有5-25个碳原子的共轭的或非共轭的二烯烃，例如1，4-戊二烯，1，4-己二烯，1，5-己二烯，双环戊二烯，4-乙烯基环己烯，1-乙烯基-1-环戊烯和烷基二环壬二烯，茚和降冰片烯。亚乙基降冰中烯是后者的一个例子。最好采用非共轭的二烯烃。
所述的乙烯/4-甲基-1-戊烯或1-辛烯的共聚物可以预先与下列的一种或多种物质掺合：
(i)采用常规高压技术制备的密度约为0.91-0.93的聚乙烯；
(ii)乙烯共聚物，其中至少有一种共聚单体是乙烯基酸、乙烯基酸酯、或有机酸的乙烯基酯；
(iii)乙烯三元共聚物，其中至少有二种共聚单体是在(ii)和(Viii)中提到的物质；
(iv)基于具有3-8个碳原子的α-烯烃的乙烯三元共聚物；
(v)乙丙橡胶；
(vi)乙烯/丙烯/二烯单体橡胶：
(vii)将硅烷接枝到(i)至(vi)的任一物质中形成的可水解的接枝共聚物；或
(viii)乙烯/可水解硅烷的共聚物。
第(i)项中提到的高压技术在1982年纽约出版的由史蒂勒(stille)，威廉(wiley)和桑斯(sons)著的《聚合物化学导论》(Introduction to polymer chemistry)149页至153页有描述。乙烯/可水解硅烷共聚物可按照US 3,225,018中描述的方法制备，三元共聚物可按照US 4,291,136中描述的方法制备。
与乙烯/α-烯烃基础共聚物掺合的第(i)项中的高压聚合物最好这样进行掺合，以使该掺合物的平均密度不超过约0.92g/cm3。基础共聚物与加入的共聚物的重量比通常在3∶1至1∶3的范围。若在掺合物片采用了乙烯/醋酸乙烯或乙烯/丙烯酸乙酯一类的极性共聚物，则应将极性共聚单体的浓度保持在较低的水平上，以免造成大量电介质的损耗，例如按掺合物重量计使其浓度低于约10％。
乙烯/4-甲基-1-戊烯或1-辛烯的共聚物是使用含钛或钒的催化剂体系制备的。
对于含钛的催化剂体系而言，将相应的共聚单体与催化剂体系接触，催化剂体系含有催化剂母体，该母体包含镁、钛、卤素和一种电子给体以及一种或多种含铝化合物助催化剂诸如三乙基铝和三异丁基铝。在US 4,302,565中描述了催化剂体系和共聚物的制备方法。
在含钛催化剂体系存在条件下生产的共聚物可以按下述步骤进行制备：在装有机械搅拌器的烧瓶内放入无水氯化镁和四氢呋喃(THF)。在这些混合物中再加入四氯化钛。将多孔脱水硅石加入上述溶液中并进行搅拌。将这些混合液干燥，以获得具有硅石颗粒尺度的干燥的自由流动的粉末。将适量浸渍过的母体组合物和活化剂化合物，例如三乙基铝加入装有足量无水脂族烃稀释剂例如异戊烷的混合罐混合，以获得一种淤浆体系。采用的活化剂化合物和母体化合物的用量以获得的部分活化的母体组合物具有铝/钛比达到10∶1为准。然后将淤浆体系的成份混合并干燥。得到的催化剂是渗透在硅石颗粒孔中的部分活化的母体组合物。它被注入聚合反应器，并将在其中完全活化。将活化剂化合物加入聚合反应器，以便使反应器内的铝/钛比保持在约10∶1至约400∶1的水平上。然后乙烯与4-甲基-1-戊烯进行聚合，此过程最好以气相形式在流化床中进行。在达到平衡后应在85℃，300磅/吋2，气体速度约为3-6倍Gmf，流化床反应器系统内时空产率为约4.4-6.3的条件下使反应进行1小时。
对于含钒的催化剂体系来说，相应的共聚单体最好与一个载体上的催化剂体系接触，该体系中的催化剂母体包含钒的三卤化物，电子给体，和烃基铝卤化物以及烃基铝助催化剂和卤代低级烷烃促进剂，低级烷烃促进剂具有1-7个碳原子。此催化剂体系和制备共聚物的方法已在1984年10月3日公布的欧洲专利申请0120501号中描述过。
在含钒催化剂体系存在的条件下制备的共聚物可按下述步骤制备：在装有无水四氢呋喃的烧瓶中加入三氯化钒。搅拌此混合物直到三氯化钒溶解。将脱水硅石加入此溶液并继续搅拌。将烧瓶塞子打开，并使溶液干燥到浆状。浸渍过的硅石是一种自由流动的固体，每克含有0.25毫摩尔的钒。将此固体从烧瓶中取出并贮存在氮气中。然后按下述步骤掺入改性剂。将上述浸渍过的硅石加入装有无水异戊烷的烧瓶，然后将无水己烷中的氯化二乙基铝作为改性剂加至该混合物中，边加边搅拌。改性剂的用量应足以使每摩尔四氢呋喃有1.7摩尔的改性剂。对这种混合物加热直到它成为可自由流动的粉末。然后将这种钒催化剂母体从烧瓶中取出并在氮气下贮存。乙烯共聚物是以气相形式在流化床反应器内按以下操作条件生产的：促进剂/助催化剂的摩尔比为1∶0；铝/钒的原子比为40；温度为70℃；气体速度为1.5英尺/秒；氮气压力(摩尔百分比)为50；共聚单体/乙烯的摩尔比为0.24；氢/乙烯的摩尔比为0.007；磅/小时-立方英尺为4.7(每小时每立方英尺产率为4.7磅)。在聚合反应期间加入三异丁基铝助催化剂；加入三氯甲烷作为促进剂，这种促进剂是以重量百分浓度为5％的异戊烷溶液加入的。在达到平衡后，应在300磅/2的压力下使聚合反应继续1小时以上。
虽然气相聚合反应，特别是在一个或多个流化床内进行反应是优先采用的方式，但以通常的液相方法也能生产出共聚物，例如用上面提到的《聚合物化学导论》(Introduction to Polymer Chemistry)一书中描述的方法。
在4-甲基-1-戊烯或1-辛烯是除乙烯以外的最原始共聚单体的情况下，它们在共聚物中的量以占共聚物重量的约5—50％为好，最好占共聚物重量的约15—40％。乙烯的量应以多于共聚物重量的约50％为好，最好多于60％。共聚物中使用另外的共聚单体时，这些共聚单体的量最好占共聚物重量的约1—1.5％。
乙烯/4-甲基-1-戊烯的共聚物的密度不应大于约0.92g/cm3，最好在约0.88—0.92g/cm3的范围内。熔体指数最好在约每十分钟0.5—10克的范围内。熔体指数是按照ASTM(美国标准试验手册)D-1238，条件E的要求测定的，测量是在190℃下进行的。乙烯/1-辛烃的共聚物的密度不应大于约0.92g/cm3，最好在约0.88—0.92g/cm3。熔体指数以在约每十分钟0.5—20克的范围为好，最好在约每十分钟0.5—10克。
制备硅烷接枝的聚乙烯和乙烯/硅烷共聚物的各种方法，以及制备适宜用来制备这些共聚物和承载诸如烷氧基、芳氧基、脂族氧基和卤素等可水解基团的多种不饱和硅烷的各种方法，在美国专利3,075,948,3,225,018；4,412,042；4,413,066；4,574,133；和4,593,071中已经提到。在硅烷接枝的共聚物中，掺入的硅烷单体的量以占共聚物重量的约0.5—10％为好，最好占共聚物重量的0.5—10％。其中，接枝入共聚物中的硅烷可以是乙烯基三烷氧基硅烷，例如：乙烯基三甲氧基硅烷或乙烯基三乙氧基硅烷。一般来说，任何包含有至少一个可水解基团的不饱和单体硅烷都是可以使用的。假如要求更慢的水固化或更好的贮存稳定性，则可以采用乙烯基三异丁氧基硅烷，乙烯基三-(α-乙基己氧基)硅烷或乙烯基三异丙氧基硅烷。
在制备硅烷接枝的共聚物的过程中，还要用到游离基引发剂或催化剂，其中最有用的游离基引发剂是过氧化二枯基，过氧化十二烷酰，偶氮二异丁腈，过氧化苯甲酰，过苯甲酸叔丁酯，过氧化二叔丁基，氢过氧化枯烯，2，5-二甲基-2，5-二(叔丁基过氧)-己炔，2，5-二甲基-2，5-二(叔丁基过氧)-己烷叔丁基氢过氧化物和过碳酸异丙酯。优选使用有机过氧化物。使用的游离基引发剂的重量约占共聚物重量的0.01％-5％，最好占共聚物重量的约0.01—0.1％。
有机过氧化物也用来交联或固化乙烯/4-甲基-1-戊烯和乙烯/1-辛烯的共聚物。可水解的硅烷接枝的共聚物可以使用有机过氧化物或在有常规硅醇缩合催化剂例如二月桂酸二丁基锡的条件用水汽进行交联。用于交联的有机过氧化物的量应占共聚物重量的约0.5—5％。
各种常规的添加剂可以常规用量加入该绝缘组合物中。典型的添加剂有抗氧化剂，紫外线吸收剂，抗静电剂，颜粒，填料，滑爽剂，阻燃剂，稳定剂，交联剂，卤素消除剂，烟气抑制剂，交联助促进剂，操作助剂，润滑剂，增塑剂，和粘度控制剂。
导线和电缆通常由一股或多股用聚合材料绝缘的金属导体组成。在电缆的情况下，这些元件形成芯线，并用另外的聚合材料护套或外套材料来保护。在某些场合，还在芯线和护套间夹一层缠绕物来增强保护。本发明的组合物最典型地被用作绝缘或包裹层，它是被涂覆或挤塑在电导体上的。该可水解的组合物通常在被涂覆到导线或电缆上以后才被交联。
本发明书中提到的专利、专利申请和出版物在此引入作为参考。
现通过下述实施例对本发明作进一步说明。
实施例1到7
绝缘组合物的抗水树网络的能力是按照US4,144,202描述的方法测定的。这种测量方法获得的抗水树网络的值是与标准聚乙烯绝缘材料有关的。用来说明此值的术语是“水树网络增长率”(WTGR)。根据实验室的测试和电缆加速试验的经验，已经证实，为了在电缆性能方面，即在工作中与水接触的工作电缆的寿命方面提供重要的改进，所述的WTGR值应等于标准值或小于标准值10％。
例1至3以及5和7的组合物是以乙烯/1-辛烯共聚物为基础的，并是由气相方法制备的，气相方法与上述用于钛基催化剂的典型步骤相类似。例4和例6的组合物也是以乙烯/1-辛烯共聚物为基础的，并是用与上面提到的用于钒基催化剂的典型步骤相似的气相方法制备的。共聚物中含有抗氧化剂，硬脂酸钙，及作为交联剂的过氧化二枯基。所有的样品都经过压塑和固化，即在试验前在压塑机中交联，并在80℃真空中处理7天。变量和结果列于下表： 实施例 1 2 3 4 5 6 7密度(g/cc) 0.8995 0.9018 0.9050 0.9060 0.9105 0.9110 0.9165熔体指数 0.73 0.40 1.08 0.28 0.93 0.42 1.2WTGR(％) 0.20 0.05 3.0 0.60 0.2 3.5 3.9
实施例8
除不进行交联外，重复例3的步骤。密度为0.905g/cm3；熔体指数为每十分钟1.08克；WTGR(％)为6.4。
实施例9和10
除共聚物是以熔液相制造的以外，重复例1的步骤。
实施例 9 10
密度(g/cc) 0.905 0.912
熔体指数 0.9 1.0
WTGR(％) 16.0 8.8
实施例11至14
在这些例子里，表明了密度对用催化剂制备的交联的乙烯/4-甲基-1-戊烯共聚物的WTGR的影响，这种催化剂是用与上面提到的用于钛基催化剂的典型步骤相似的方法制备的。样品如例1那样制备，密度和WTGR的关系列于下表：
实施例 11 12 13 14
密度(g/cc) 0.895 0.902 0.910 0.917
WTGR(％) 0.1 0.4 0.9 8.2
Claims (5)
1.一种制备水树生长率为0.05-0.9％的共聚物的方法，该方法包括：
a)在气相中，在流化床内，在聚合催化剂存在下，使两种共聚用单体(i)乙烯，和(ii)4-甲基-1-戊烯或1-辛烯的混合物共聚合，
b)用基于共聚物重量计，0.5-5％重量的有机过氧化物交联步骤a)得到的共聚物，从而得到交联的乙烯共聚物，该交联的乙烯共聚物的密度为0.895-0.9105g/cm3，熔体指数为每10分钟0.40至0.93g；或
c)用基于共聚物重量计，0.5-10重量％的可水解的乙烯基硅烷化合物接枝上述(a)的乙烯共聚物，并且在常规硅醇缩合催化剂的存在下，用水汽对接枝的共聚物进行交联，从而得到交联的乙烯共聚物，该交联的乙烯共聚物的密度为0.895-0.9105g/cm3，熔体指数为每10分钟0.40至0.93g，
其中所述的聚合催化剂由镁、钛、卤素和一种电子给体以及一种或多种含铝的化合物组成；
其中所述乙烯的用量基于共聚物重量计多于50％重量，4-甲基-1-戊烯或1-辛烯的用量基于共聚物重量计为5-50％重量。
2.根据权利要求1的方法，其中的共聚用单体(ii)是4-甲基-1-戊烯。
3.根据权利要求1的方法，其中的共聚用单体(ii)是1-辛烯。
4.根据权利要求1的方法，其中的乙烯共聚物用可水解的乙烯基硅烷化合物接枝。
5.根据权利要求1的方法，其中步骤(a)得到的共聚物中还可含有一种单体不饱和硅烷和一种游离基引发剂，其中所述的硅烷含有至少一种可水解基团。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US38570289A | 1989-07-26 | 1989-07-26 | |
| US385,702 | 1989-07-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1050728A CN1050728A (zh) | 1991-04-17 |
| CN1078225C true CN1078225C (zh) | 2002-01-23 |
Family
ID=23522507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90106964.7A Expired - Fee Related CN1078225C (zh) | 1989-07-26 | 1990-07-25 | 具有特定水树生长率共聚物的制备方法 |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0410431B1 (zh) |
| JP (1) | JPH0819291B2 (zh) |
| CN (1) | CN1078225C (zh) |
| AT (1) | ATE122815T1 (zh) |
| AU (1) | AU636900B2 (zh) |
| CZ (1) | CZ285069B6 (zh) |
| DE (1) | DE69019429T2 (zh) |
| ES (1) | ES2071709T3 (zh) |
| HU (1) | HUT56125A (zh) |
| NO (1) | NO903298L (zh) |
| SK (1) | SK370790A3 (zh) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5246783A (en) * | 1991-08-15 | 1993-09-21 | Exxon Chemical Patents Inc. | Electrical devices comprising polymeric insulating or semiconducting members |
| US6270856B1 (en) | 1991-08-15 | 2001-08-07 | Exxon Mobil Chemical Patents Inc. | Electrical cables having polymeric components |
| US5492760A (en) * | 1994-12-05 | 1996-02-20 | At Plastics Inc. | Water tree resistant, moisture curable insulation composition for power cables |
| US5731082A (en) * | 1996-06-24 | 1998-03-24 | Union Carbide Chemicals & Plastics Technology Corporation | Tree resistant cable |
| ATE393016T1 (de) * | 2001-03-08 | 2008-05-15 | Biolog Insel Lothar Moll Gmbh | Verwendung von ionomeren zur abdichtung von dämmstoffen |
| CN100347792C (zh) * | 2005-02-24 | 2007-11-07 | 无锡江南电缆有限公司 | 轨道交通用阻燃电力电缆及制备方法 |
| CN100370556C (zh) * | 2005-12-01 | 2008-02-20 | 上海交通大学 | 不饱和羧酸盐改性的抗水树绝缘材料及制备方法 |
| CN101104713B (zh) * | 2006-07-12 | 2010-09-08 | 上海电缆研究所 | 抗水树的聚烯烃电绝缘组合物 |
| WO2014052200A1 (en) * | 2012-09-27 | 2014-04-03 | Exxonmobil Chemical Patents Inc. | Vinyl terminated polymers and methods to produce thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4302565A (en) * | 1978-03-31 | 1981-11-24 | Union Carbide Corporation | Impregnated polymerization catalyst, process for preparing, and use for ethylene copolymerization |
| JPS5558210A (en) * | 1978-10-26 | 1980-04-30 | Nippon Oil Co Ltd | Production of copolymer |
| US4379759A (en) * | 1979-02-16 | 1983-04-12 | Union Carbide Corporation | Impregnated polymerization catalyst, process for preparing, and use for ethylene copolymerization |
| JPS5999613A (ja) * | 1982-11-30 | 1984-06-08 | 住友電気工業株式会社 | 架橋ポリエチレンケ−ブル |
| IL71356A (en) * | 1983-03-29 | 1987-07-31 | Union Carbide Corp | Process for producing polyethylene,a supported vanadium catalyst precursor therefor and a catalyst composition containing said supported precursor |
| US4508842A (en) * | 1983-03-29 | 1985-04-02 | Union Carbide Corporation | Ethylene polymerization using supported vanadium catalyst |
| JP2571562B2 (ja) * | 1986-10-02 | 1997-01-16 | 日立電線株式会社 | 耐水トリ−性絶縁電線 |
| DE3816397A1 (de) * | 1988-05-13 | 1989-11-23 | Basf Ag | Elektrische kabel, die isolierungen auf basis von ehtylenpolymerisaten mit hoher widerstandsfaehigkeit gegenueber der bildung von wasserbaeumchen enthalten |
-
1990
- 1990-07-25 CN CN90106964.7A patent/CN1078225C/zh not_active Expired - Fee Related
- 1990-07-25 AU AU59772/90A patent/AU636900B2/en not_active Ceased
- 1990-07-25 NO NO90903298A patent/NO903298L/no unknown
- 1990-07-25 CZ CS903707A patent/CZ285069B6/cs not_active IP Right Cessation
- 1990-07-25 HU HU904614A patent/HUT56125A/hu unknown
- 1990-07-25 EP EP90114288A patent/EP0410431B1/en not_active Expired - Lifetime
- 1990-07-25 AT AT90114288T patent/ATE122815T1/de not_active IP Right Cessation
- 1990-07-25 SK SK3707-90A patent/SK370790A3/sk unknown
- 1990-07-25 DE DE69019429T patent/DE69019429T2/de not_active Expired - Fee Related
- 1990-07-25 ES ES90114288T patent/ES2071709T3/es not_active Expired - Lifetime
- 1990-07-25 JP JP2195112A patent/JPH0819291B2/ja not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE69019429T2 (de) | 1995-09-14 |
| AU636900B2 (en) | 1993-05-13 |
| ATE122815T1 (de) | 1995-06-15 |
| JPH0366736A (ja) | 1991-03-22 |
| HUT56125A (en) | 1991-07-29 |
| JPH0819291B2 (ja) | 1996-02-28 |
| ES2071709T3 (es) | 1995-07-01 |
| CZ370790A3 (cs) | 1999-02-17 |
| SK280811B6 (sk) | 2000-08-14 |
| CN1050728A (zh) | 1991-04-17 |
| NO903298D0 (no) | 1990-07-25 |
| EP0410431B1 (en) | 1995-05-17 |
| CZ285069B6 (cs) | 1999-05-12 |
| SK370790A3 (en) | 2000-08-14 |
| HU904614D0 (en) | 1991-01-28 |
| NO903298L (no) | 1991-01-28 |
| DE69019429D1 (de) | 1995-06-22 |
| EP0410431A1 (en) | 1991-01-30 |
| AU5977290A (en) | 1991-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR910000200B1 (ko) | 저분자량 에틸렌/알파올레핀 공중합체 중간물 | |
| JP5334981B2 (ja) | シラン官能性樹脂の架橋のための現場での水分発生及び多官能性アルコールの使用 | |
| US8247696B2 (en) | Cross-linking agent | |
| CN1078225C (zh) | 具有特定水树生长率共聚物的制备方法 | |
| FI80056C (fi) | Polymerisation av etylen med anvaendande av en vanadinkatalysator pao en baerare. | |
| CA2859011C (en) | Interpolymer compositions and methods for making same | |
| EP0206644B1 (en) | Block copolymer | |
| EP3140327A1 (en) | Process for making ethylene-based polymers using hydrocarbon initiators | |
| CN113563524A (zh) | 一种硅烷改性的聚丙烯接枝物作为绝缘材料的应用和绝缘材料 | |
| CA1335217C (en) | Tree resistant compositions | |
| US5128086A (en) | Epoxy-modified encapsulation composition | |
| US4787703A (en) | Cable containing epoxy-modified encapsulation composition | |
| US4033939A (en) | Stress-crack resistant ethylene-perhaloethylene terpolymers | |
| EP0989139A1 (en) | Unbridged monocyclopentadienyl metal complex catalyst for olefin polymerization by reacting with particulate solids with functional groups | |
| CA2022312C (en) | Tree resistant compositions | |
| KR20010030950A (ko) | 아크릴 중합체의 열 산화 안정성의 개선방법 | |
| JPH038647B2 (zh) | ||
| KR100386379B1 (ko) | 정온도 특성이 우수한 전도성 고분자 수지 및 그 제조방법 | |
| CN120757687A (zh) | 一种乙烯-丙烯-α-烯烃-二烯烃四元共聚橡胶及其制备方法 | |
| CN110938157B (zh) | 用于烯烃聚合的催化剂体系和预聚合催化剂组合物及它们的应用 | |
| EP0206645B1 (en) | Block copolymer | |
| CN1224025A (zh) | 无桥联单环戊二烯基金属络合催化剂及聚烯烃的生产方法 | |
| KR20100138655A (ko) | 프로필렌 중합 및 공중합 방법 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |