JPS6342363B2 - - Google Patents
Info
- Publication number
- JPS6342363B2 JPS6342363B2 JP55047768A JP4776880A JPS6342363B2 JP S6342363 B2 JPS6342363 B2 JP S6342363B2 JP 55047768 A JP55047768 A JP 55047768A JP 4776880 A JP4776880 A JP 4776880A JP S6342363 B2 JPS6342363 B2 JP S6342363B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- titanium
- olefin
- vanadium
- compounds
- 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
Links
- 239000004711 α-olefin Substances 0.000 claims description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 19
- 239000005977 Ethylene Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011253 protective coating Substances 0.000 claims description 4
- 125000002370 organoaluminium group Chemical group 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 19
- -1 polyethylene Polymers 0.000 description 14
- 150000003609 titanium compounds Chemical class 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 229920000098 polyolefin Polymers 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 150000003682 vanadium compounds Chemical class 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000006353 environmental stress Effects 0.000 description 4
- 150000002901 organomagnesium compounds Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000012685 gas phase polymerization Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BDBNCVOMHKVOST-UHFFFAOYSA-K CCCCCO[Ti](Cl)(Cl)Cl Chemical compound CCCCCO[Ti](Cl)(Cl)Cl BDBNCVOMHKVOST-UHFFFAOYSA-K 0.000 description 1
- NTWOIGOPFDMZAE-UHFFFAOYSA-M CCO[Ti](Cl)(OCC)OCC Chemical compound CCO[Ti](Cl)(OCC)OCC NTWOIGOPFDMZAE-UHFFFAOYSA-M 0.000 description 1
- ZALOHOLPKHYYAX-UHFFFAOYSA-L CO[Ti](Cl)(Cl)OC Chemical compound CO[Ti](Cl)(Cl)OC ZALOHOLPKHYYAX-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- MGSCVPSSIVOYMY-UHFFFAOYSA-N [V+3].CC[O-].CC[O-].CC[O-] Chemical compound [V+3].CC[O-].CC[O-].CC[O-] MGSCVPSSIVOYMY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical compound [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 description 1
- RMTCVMQBBYEAPC-UHFFFAOYSA-K ethanolate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CCO[Ti+3] RMTCVMQBBYEAPC-UHFFFAOYSA-K 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- QZCOACXZLDQHLQ-UHFFFAOYSA-M methanolate titanium(4+) chloride Chemical compound [Cl-].[Ti+4].[O-]C.[O-]C.[O-]C QZCOACXZLDQHLQ-UHFFFAOYSA-M 0.000 description 1
- OKENUZUGNVCOMC-UHFFFAOYSA-K methanolate titanium(4+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].CO[Ti+3] OKENUZUGNVCOMC-UHFFFAOYSA-K 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- LTEDQKPGOZDGRZ-UHFFFAOYSA-L propan-2-olate;titanium(4+);dichloride Chemical compound Cl[Ti+2]Cl.CC(C)[O-].CC(C)[O-] LTEDQKPGOZDGRZ-UHFFFAOYSA-L 0.000 description 1
- FLALGSYYVIWTFQ-UHFFFAOYSA-K propan-2-olate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CC(C)O[Ti+3] FLALGSYYVIWTFQ-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- BIEFSHWAGDHEIT-UHFFFAOYSA-J tetrabromovanadium Chemical compound [V+4].[Br-].[Br-].[Br-].[Br-] BIEFSHWAGDHEIT-UHFFFAOYSA-J 0.000 description 1
- JYHZWKLCYKMFOD-UHFFFAOYSA-J tetraiodovanadium Chemical compound [V+4].[I-].[I-].[I-].[I-] JYHZWKLCYKMFOD-UHFFFAOYSA-J 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- ZLMGMVJGEULFPP-UHFFFAOYSA-J titanium(4+) trichloride phenoxide Chemical compound Cl[Ti](Cl)(Cl)OC1=CC=CC=C1 ZLMGMVJGEULFPP-UHFFFAOYSA-J 0.000 description 1
- DPNUIZVZBWBCPB-UHFFFAOYSA-J titanium(4+);tetraphenoxide Chemical compound [Ti+4].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 DPNUIZVZBWBCPB-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
Landscapes
- Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Description
【発明の詳細な説明】
本発明は電線、ケーブルの保護被覆層の製造方
法に関する。
一般に、電線、ケーブルは導体上にプラスチツ
クあるいはゴム等の絶縁層を有し、更に外部環境
から保護するための保護被覆層（シース層）を有
する構造となつている。このシース層は、耐環境
応力亀裂性、耐候性、耐寒性、耐摩耗性、耐油
性、耐薬品性等の諸特性が要求されている。従
来、シース層形成材料として高圧法ポリエチレン
やエチレン・酢酸ビニル共重合体が用いられてい
るが、高圧法ポリエチレンは耐環境応力亀裂性が
未だ不十分であり、エチレン・酢酸ビニル共重合
体は耐寒性、耐摩耗性が悪いという欠点があつ
た。
本発明者らは、上記欠点を解決するために鋭意
研究の結果、特定の方法で製造された特殊ポリオ
レフインを用いることにより、上記問題点が一挙
に解決し得ることを見出し、本発明を完成させる
に至つたものである。すなわち、本発明はマグネ
シウムとチタンおよび／またはバナジウムとを含
有する固体物質と有機アルミニウムとからなる触
媒の存在下、実質上溶媒の存在しない気相状態で
エチレンと炭素数３〜12のα−オレフインとを共
重合させて得られる密度が0.890〜0.945で、かつ
メルトインデツクスが0.01〜５のエチレン・α−
オレフイン共重合体を主体として、電線、ケーブ
ルの保護被覆層の製造方法に関する。
本発明の特殊ポリオレフインを用いて得られた
本発明のシース層は、耐環境応力亀裂性が著しく
すぐれているばかりか、耐候性、耐寒性、耐摩耗
性、耐油性、耐薬品性が極めて良好である。更
に、本発明の特殊ポリオレフインは加工性のうえ
でも極めてすぐれている。
本発明のシース層形成材料に用いるポリオレフ
インは、マグネシウムとチタンおよび／またはバ
ナジウムとを含有する固体物質と有機アルミニウ
ム化合物とからなる触媒の存在下で、実質上溶媒
のない気相状態でエチレンと炭素数３〜12のα−
オレフインとを共重合させて得られるもので、密
度が0.890〜0.945、好ましくは0.910〜0.940、メ
ルトインデツクスが0.01〜５、好ましくは0.2〜
１のエチレン・α−オレフイン共重合体である。
以下に、本発明において用いるエチレンとα−
オレフインの共重合体の製造法について説明す
る。
まず使用する触媒系は、マグネシウムとチタン
および／またはバナジウムとを含有する固体物質
と有機アルミニウム化合物を組み合わせたもの
で、該固体物質としてはたとえば金属マグネシウ
ム、水酸化マグネシウム、炭酸マグネシウム、酸
化マグネシウム、塩化マグネシウムなど、またケ
イ素、アルミニウム、カルシウムから選ばれる金
属とマグネシウム原子とを含有する複塩、複酸化
物、炭酸塩、塩化物、水酸化物などさらにはこれ
らの無機質固体坦体を含酸素化合物、含硫黄化合
物、芳香族炭化水素、ハロゲン含有物質で処理又
は反応させたもの等の無機質固体坦体にチタン化
合物および／またはバナジウム化合物を公知の方
法により担持させたものが挙げられる。
上記の含酸素化合物としては、例えば水、アル
コール、フエノール、ケトン、アルデヒド、カル
ボン酸、エステル、酸アミド等の有機含酸素化合
物、金属アルコキシド、金属のオキシ塩化物等の
無機含酸素化合物を例示することができる。含硫
黄化合物としては、チオール、チオエーテルの如
き有機含硫黄化合物、二酸化硫黄、三酸化硫黄、
硫酸の如き無機硫黄化合物を例示することができ
る。芳香族炭化水素としては、ベンゼン、トルエ
ン、キシレン、アントラセン、フエナンスレンの
如き各種単環および多環の芳香族炭化水素化合物
を例示することができる。ハロゲン含有物質とし
ては、塩素、塩化水素、金属塩化物、有機ハロゲ
ン化物の如き化合物等を例示することができる。
チタン化合物および／またはバナジウム化合物
としては、チタンおよび／またはバナジウムのハ
ロゲン化物、アルコキシハロゲン化物、アルコキ
シド、ハロゲン化酸化物等を挙げることができ
る。チタン化合物としては４価のチタン化合物と
３価のチタン化合物が好適であり、４価のチタン
化合物としては具体的には一般式Ti（OR）nX4−
ｎ（ここでＲは炭素数１〜20のアルキル基、アリ
ール基またはアラルキル基を示し、Ｘはハロゲン
原子を示す。ｎは０≦ｎ≦４である。）で示され
るものが好ましく、四塩化チタン、四臭化チタ
ン、四ヨウ化チタン、モノメトキシトリクロロチ
タン、ジメトキシジクロロチタン、トリメトキシ
モノクロロチタン、テトラメトキシチタン、モノ
エトキシトリクロロチタン、ジエトキシジクロロ
チタン、トリエトキシモノクロロチタン、テトラ
エトキシチタン、モノイソプロポキシトリクロロ
チタン、ジイソプロポキシジクロロチタン、トリ
イソプロポキシモノクロロチタン、テトライソプ
ロポキシチタン、モノブトキシトリクロロチタ
ン、ジブトキシジクロロチタン、モノペントキシ
トリクロロチタン、モノフエノキシトリクロロチ
タン、ジフエノキシジクロロチタン、トリフエノ
キシモノクロロチタン、テトラフエノキシチタン
等を挙げることができる。３価のチタン化合物と
しては、四塩化チタン、四臭化チタン等の四ハロ
ゲン化チタンを水素、アルミニウム、チタンある
いは周期律−族金属の有機金属化合物により
還元して得られる三ハロゲン化チタンが挙げられ
る。また一般式Ti（OR）mX4−ｍ（ここでＲは炭
素数１〜20のアルキル基、アリール基またはアラ
ルキル基を示し、Ｘはハロゲン原子を示す。ｍは
０＜ｍ＜４である。）で示される４価のハロゲン
化アルコキシチタンを周期律表−族金属の有
機金属化合物により還元して得られる３価のチタ
ン化合物が挙げられる。バナジウム化合物として
は、四塩化バナジウム、四臭化バナジウム、四ヨ
ウ化バナジウムの如き４価のバナジウム化合物、
オキシ三塩化バナジウム、オルソアルキルバナデ
ートの如き５価のバナジム化合物、三塩化バナジ
ウム、バナジウムトリエトキシドの如き３価のバ
ナジウム化合物が挙げられる。
これらのチタン化合物およびバナジウム化合物
のうち、４価のチタン化合物が特に好ましい。
これらの触媒の具体的なものとしては、たとえ
ばMgO−RX−TiCl4系（特公昭５−3514号）、
Mg−SiCl4−ROH−TiCl4系（特公昭50−23864
号）、MgCl2−Al（OR）3−TiCl4系（特公昭51−
152号、特公昭52−15111号）、MgCl2−SiCl4−
ROH−TiCl4系（特開昭49−106581号）、Mg
（OOCR）2−Al（OR）3−TiCl4系（特公昭52−1710
号）、Mg−POCl3−TiCl4系（特公昭51−153号）、
MgCl2−AlOCl−TiCl4系（特公昭54−15316号）
などの固体物質（前記式中において、Ｒは有機残
基、Ｘはハロゲン原子を示す）に有機アルミニウ
ム化合物を組み合わせたものが好ましい触媒系の
例としてあげられる。
他の触媒系の例としては固体物質として、いわ
ゆるグリニヤ化合物などの有機マグネシウム化合
物とチタン化合物および／またはバナジウム化合
物との反応生成物を用い、これに有機アルミニウ
ム化合物を組み合わせた触媒系を例示することが
できる。有機マグネシウム化合物としては、たと
えば、一般式RMgX、R2Mg、RMg（OR）など
の有機マグネシウム化合物（ここで、Ｒは炭素数
１〜20の有機残基、Ｘはハロゲンを示す）および
これらのエーテル錯合体、またこれらの有機マグ
ネシウム化合物をさらに、他の有機金属化合物た
とえば有機ナトリウム、有機リチウム、有機カリ
ウム、有機ホウ素、有機カルシウム、有機亜鉛な
どの各種化合物を加えて変性したものを用いるこ
とができる。
これらの触媒系の具体的な例としては、例えば
RMgX−TiCl4系（特公昭50−39470号）、RMgX
−フエノール−TiCl4系（特公昭54−12953号）、
RMgX−ハロゲン化フエノール−TiCl4系（特公
昭54−12954号）等の固体物質に有機アルミニウ
ム化合物を組み合わせたものを挙げることができ
る。
これらの触媒系において、チタン化合物およ
び／またはバナジウム化合物を有機カルボン酸エ
ステルとの付加物として使用することもでき、ま
た前記したマグネシウムを含む無機化合物固体坦
体を有機カルボン酸エステルと接触処理させたの
ち使用することもできる。また、有機アルミニウ
ム化合物を有機カルボン酸エステルとの付加物と
して使用しても何ら支障がない。さらには、あら
ゆる場合において、有機カルボン酸エステルの存
在下に調製された触媒系を使用することも何ら支
障なく実施できる。
ここで有機カルボン酸エステルとしては各種脂
肪族、脂環族、芳香族カルボン酸エステルが用い
られ、好ましくは炭素数７〜12の芳香族カルボン
酸が用いられる。具体的な例としては安息香酸、
アニス酸、トルイル酸のメチル、エチルなどのア
ルキルエステルをあげることができる。
上記した固体物質と組合わせるべき有機アルミ
ニウム化合物の具体的な例としては一般式R3Al、
R2AlX、RAlX2、R2AlOR、RAl（OR）Ｘおよび
R3Al2X3の有機アルミニウム化合物（ここでＲは
炭素数１〜20のアルキル基、アリール基またはア
ラルキル基、Ｘはハロゲン原子を示し、Ｒは同一
でもまた異なつてもよい）で示される化合物が好
ましく、トリエチルアルミニウム、トリイソブチ
ルアルミニウム、トリヘキシルアルミニウム、ト
リオクチルアルミニウム、ジエチルアルミニウム
クロリド、エチルアルミニウムセスキクロリド、
およびこれらの混合物等があげられる。
有機アルミニウム化合物の使用量はとくに制限
されないが通常遷移金属化合物に対して0.1〜
1000モル倍使用することができる。
また、前記の触媒系をα−オレフインと接触さ
せたのち気相重合反応に用いることによつて、そ
の重合活性を大巾に向上させ、未処理の場合より
も一層安定に運転することもできる。このとき使
用するα−オレフインとしては種々のものが使用
可能であるが、好ましくは炭素数３〜12のα−オ
レフインであり、さらに好ましくは炭素数３〜８
のα−オレフインが望ましい。これらのα−オレ
フインの例としてはたとえばプロピレン、ブテン
−１、ペンテン−１、４−メチルペンテン−１、
ヘプテン−１、ヘキセン−１、オクテン−１、デ
セン−１、ドデセン−１等およびこれらの混合物
などをあげることができる。触媒系とα−オレフ
インとの接触時の温度、時間は広い範囲で選ぶこ
とができ、たとえば０〜200℃、好ましくは０〜
110℃で１分〜24時間で接触処理させることがで
きる。接触させるα−オレフインの量も広い範囲
で選べるが、通常、前記固体物質１ｇ当り１ｇ〜
50000ｇ、好ましくは５ｇ〜30000ｇ程度のα−オ
レフインで処理し、前記固体物質１ｇ当り１ｇ〜
500ｇのα−オレフインを反応させることが望ま
しい。このとき、接触時の圧力は任意に選ぶこと
ができるが通常、−１Kg／cm2・Ｇ（１気圧減圧下を
意味する）〜100Kg／cm2・Ｇの圧力下に接触させ
ることが望ましい。
α−オレフイン処理の際、使用する有機アルミ
ニウム化合物を全量、前記固体物質と組み合わせ
たのちα−オレフインと接触させてもよいし、ま
た、使用する有機アルミニウム化合物のうち一部
を前記固体物質と組み合わせたのちガス状のα−
オレフインと接触させ、残りの有機アルミニウム
化合物を気相重合のさいに別途添加して重合反応
を行なつてもよい。また、触媒系とα−オレフイ
ンとの接触時に、水素ガスが共存しても支障な
く、また、窒素、アルゴン、ヘリウムなどその他
の不活性ガスが共存しても何ら支障ない。
本発明における特殊ポリオレフインは前記した
マグネシウムとチタン化合物および／またはバナ
ジウム化合物を含有する固体物質および有機アル
ミニウム化合物からなる触媒の存在下に、気相で
エチレンとα−オレフインの共重合を行なうこと
によつて得られた所定のメルトインデツクスと密
度を有する共重合体を用いることを本質とし、共
重合反応に用いられるα−オレフインとしては、
炭素数３〜12のものが用いられる。具体的にはプ
ロピレン、ブテン−１、ペンテン−１、４−メチ
ルペンテン−１、ヘプテン−１、ヘキセン−１、
オクテン−１、デセン−１、ドデセン−１などを
挙げることができる。
重合反応は、実質的に溶媒の存在しない気相状
態で行なわれる。使用する反応器としては、流動
床、撹拌槽など公知のものが使用できる。
重合反応温度は、通常０〜110℃、好ましくは
20〜80℃であり、圧力は常圧〜70Kg／cm2・Ｇ、好
ましくは２〜60Kg／cm2・Ｇである。分子量の調節
は重合温度、触媒のモル比、コモノマー量などに
よつても調節できるが、重合系中に水素を添加す
ることにより効果的に行なわれる。もちろん、水
素濃度、コモノマー濃度、重合温度など重合条件
の異なつた２段階ないしそれ以上の多段階の重合
反応を行つてもよい。
本発明は、以上の如くマグネシウムとチタンお
よび／またはバナジウムとを含有する固体物質と
有機アルミニウムとからなる触媒の存在下、実質
上溶媒の存在しない気相状態でエチレンと炭数数
３〜12のα−オレフインを共重合させて得られる
密度が0.890〜0.945で、かつメルトインデツクス
が0.01〜５のエチレン・α−オレフイン共重合体
をシース層形成材料として用いることにより、シ
ース層の特性を著しく改善できたことは全く予期
できないことであつた。
本発明においては、本発明の特殊ポリオレフイ
ンに必要により顔料、充填剤、分散剤、酸化防止
剤、紫外線吸収剤などの公知の助剤を適宜配合す
ることができる。
また、本発明においては本発明の特定の方法に
より得られた特殊ポリオレフインに、他の方法で
得られたポリオレフインを適宜配合することは、
本発明の特殊ポリオレフインの特性を損わない限
りにおいて何ら問題はない。これら他のポリオレ
フインの例としては高圧法ポリエチレン、エチレ
ン・酢酸ビニル共重合体、中・低圧法による溶液
重合あるいはスラリー重合により得られるポリオ
レフインが挙げられる。これらの配合割合は本発
明の特殊ポリオレフイン100重量部に対して100重
量部以下が望ましい。
以下に、本発明を実施例により具体的に説明す
るが、本発明はこれらに制限されるものではな
い。
実施例 １
無水塩化マグネシウム1000ｇ、１，２−ジクロ
ルエタン50ｇおよび四塩化チタン170ｇを窒素雰
囲気下、室温で16時間ボールミリングし、チタン
化合物を担体に担持させた。この固体物質は１ｇ
当り40mgのチタンを含有していた。
気相重合用の装置としてはステンレス製のオー
トクレーブを用い、ブロワー、流量調節弁、およ
び生成ポリマー分離用の乾式サイクロンでループ
をつくりオートクレーブはジヤケツトに温水を流
すことにより温度コントロールを行なつた。
重合温度は70℃とし、オートクレーブに上記固
体物質を250mg／hr、およびトリエチルアルミニ
ウムを50ｍ−mol／hrの速度で供給し、またブロ
ワーでオートクレーブに供給するガス中のエチレ
ンおよびプロピレンの組成（モル比）をそれぞれ
75％および25％となるように調整し、水素を全圧
の10％となるように調整しながらエチレンとプロ
ピレンの共重合を行なつた。
生成したエチレン・プロピレン共重合体は、メ
ルトインデツクス0.2、密度0.925であつた。
上記のエチレン・プロピレン共重合体100重量
部にカーボンブラツク2.5重量部および４，4′−
チオビス（６−ｔ−ブチル−４−ハイドロキシベ
ンジル）0.2重量部を添加し、160℃に設定したロ
ール上で混合した。混合物のメルトインデツクス
は0.2、密度は0.935であつた。次に該混合物を厚
さ3.0±0.2ｍ／ｍのシートとしASTM Ｄ−1693
により耐環境応力亀裂性（ESCR）を測定したと
ころ、6000時間以上経過しても全く割れなかつ
た。また該混合物を厚さ2.0±0.2ｍ／ｍのシート
としてJIS K6760に準じて−75℃の温度で低温脆
性を調べたところ全く割れなかつた。また該混合
物を厚さ3.0±0.1ｍ／ｍのシートとして、テーパ
式摩耗試験機により摩耗性を調べたところ摩耗は
非常に少なかつた。
実施例 ２
実施例１において、オートクレーブに供給する
ガスの組成をエチレン96モル％およびヘキセン−
１ ４モル％とし、また水素を全圧の18％とし
て、85℃で重合を行つた以外は実施例１と同様の
方法にてエチレンとヘキセン−１の共重合を行つ
た。生成したエチレン・ヘキセン−１共重合体の
メルトインデツクスは1.0で、密度は0.925であつ
た。このエチレン・ヘキセン−１共重合体100重
量部に、カーボンブラツク2.5重量部および４，
4′−チオビス（６−ｔ−ブチル−４−ハイドロキ
シベンジル）0.2重量部を添加し、混合して得ら
れるメルトインデツクス1.0、密度0.935の混合物
を実施例１と同様の方法にてESCR、低温脆性お
よび耐摩耗性を調べたところ全ての点で良好であ
つた。
実施例 ３
実施例１において、オートクレーブに供給する
ガスの組成をエチレン88モル％およびブテン−１
12モル％とし、また水素を全圧の14％として、
80℃で重合を行つた以外は実施例１と同様の方法
にてエチレンとブテン−１の共重合を行つた。生
成したエチレン・ブテン−１共重合体のメルトイ
ンデツクンは1.0で、密度は0.920であつた。この
エチレン・ブテン−１共重合体100重量部に、カ
ーボンブラツク2.5重量部および４，4′−チオビ
ス（６−ｔ−ブチル−４−ハイドロキシベンジ
ル）0.2重量部を添加し、混合して得られるメル
トインデツクス1.0、密度0.930の混合物を実施例
１と同様の方法にてESCR、低温脆性および耐摩
耗性を調べたところ全ての点で良好であつた。
比較例 １
実施例１において使用したエチレン・プロピレ
ン共重合体の代わりに、高圧法により製造された
メルトインデツクス0.15、密度0.920の低密度ポ
リエチレンを用いたことを除いては実施例１と同
様な方法でESCR、低温脆性および耐摩耗性を調
べたところ、ESCRは非常に悪く、また耐摩耗性
も満足できないものであつた。
比較例 ２
実施例１において使用したエチレン・プロピレ
ン共重合体の代わりに、高圧法により製造された
メルトインデツクス0.15、密度0.922のエチレ
ン・酢酸ビニル共重合体（酢酸ビニル含量３モル
％）を用いたことを除いては実施例１と同様な方
法でESCR、低温脆性および耐摩耗性を調べたと
ころ全ての点において満足できないものであつ
た。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a protective coating layer for electric wires and cables. Generally, electric wires and cables have an insulating layer of plastic or rubber on the conductor, and a protective coating layer (sheath layer) for protection from the external environment. This sheath layer is required to have various properties such as environmental stress cracking resistance, weather resistance, cold resistance, abrasion resistance, oil resistance, and chemical resistance. Conventionally, high-pressure polyethylene and ethylene/vinyl acetate copolymer have been used as materials for forming the sheath layer, but high-pressure polyethylene still has insufficient environmental stress cracking resistance, and ethylene/vinyl acetate copolymer has poor cold resistance. The drawbacks were poor wear resistance and wear resistance. As a result of intensive research to solve the above drawbacks, the present inventors discovered that the above problems could be solved all at once by using a special polyolefin manufactured by a specific method, and completed the present invention. This is what led to this. That is, the present invention provides ethylene and an α-olefin having 3 to 12 carbon atoms in a gas phase substantially free from a solvent in the presence of a catalyst consisting of a solid substance containing magnesium, titanium, and/or vanadium, and an organic aluminum. Ethylene α- having a density of 0.890 to 0.945 and a melt index of 0.01 to 5 obtained by copolymerizing with
This invention relates to a method for producing a protective coating layer for electric wires and cables, mainly using an olefin copolymer. The sheath layer of the present invention obtained using the special polyolefin of the present invention not only has excellent environmental stress cracking resistance, but also extremely good weather resistance, cold resistance, abrasion resistance, oil resistance, and chemical resistance. It is. Furthermore, the special polyolefin of the present invention has extremely excellent processability. The polyolefin used in the sheath layer forming material of the present invention is produced by combining ethylene and carbon in a gas phase substantially without a solvent in the presence of a catalyst consisting of a solid substance containing magnesium, titanium and/or vanadium, and an organoaluminum compound. α− of numbers 3 to 12
It is obtained by copolymerizing with olefin, and has a density of 0.890 to 0.945, preferably 0.910 to 0.940, and a melt index of 0.01 to 5, preferably 0.2 to
It is an ethylene/α-olefin copolymer of No. 1. Below, ethylene used in the present invention and α-
A method for producing an olefin copolymer will be explained. The catalyst system used is a combination of a solid substance containing magnesium, titanium and/or vanadium, and an organoaluminium compound, such as magnesium metal, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium chloride, etc. Magnesium, etc., and double salts, double oxides, carbonates, chlorides, hydroxides, etc. containing magnesium atoms and metals selected from silicon, aluminum, and calcium. Examples include those in which a titanium compound and/or vanadium compound is supported by a known method on an inorganic solid carrier, such as one treated or reacted with a sulfur-containing compound, an aromatic hydrocarbon, or a halogen-containing substance. Examples of the above oxygen-containing compounds include organic oxygen-containing compounds such as water, alcohol, phenol, ketone, aldehyde, carboxylic acid, ester, and acid amide, and inorganic oxygen-containing compounds such as metal alkoxides and metal oxychlorides. be able to. Examples of sulfur-containing compounds include organic sulfur-containing compounds such as thiols and thioethers, sulfur dioxide, sulfur trioxide,
Examples include inorganic sulfur compounds such as sulfuric acid. Examples of aromatic hydrocarbons include various monocyclic and polycyclic aromatic hydrocarbon compounds such as benzene, toluene, xylene, anthracene, and phenanthrene. Examples of the halogen-containing substance include compounds such as chlorine, hydrogen chloride, metal chlorides, and organic halides. Examples of the titanium compound and/or vanadium compound include halides, alkoxy halides, alkoxides, and halogenated oxides of titanium and/or vanadium. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are suitable, and the tetravalent titanium compound specifically has the general formula Ti(OR)nX 4 −
Preferred are those represented by n (where R represents an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, and X represents a halogen atom. n is 0≦n≦4), and tetrachloride Titanium, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, mono Isopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, Examples include triphenoxymonochlorotitanium and tetraphenoxytitanium. Examples of trivalent titanium compounds include titanium trihalides obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium, or organometallic compounds of periodic group metals. It will be done. Further, it has the general formula Ti(OR)mX 4 -m (where R represents an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, and X represents a halogen atom. m satisfies 0<m<4). Examples include trivalent titanium compounds obtained by reducing a tetravalent alkoxy titanium halide represented by ) with an organometallic compound of a group metal of the periodic table. Examples of vanadium compounds include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, and vanadium tetraiodide;
Examples include pentavalent vanadium compounds such as vanadium oxytrichloride and orthoalkylvanadate, and trivalent vanadium compounds such as vanadium trichloride and vanadium triethoxide. Among these titanium compounds and vanadium compounds, tetravalent titanium compounds are particularly preferred. Specific examples of these catalysts include, for example, MgO-RX-TiCl 4 system (Japanese Patent Publication No. 5-3514),
Mg- SiCl4 -ROH- TiCl4 system
), MgCl 2 −Al(OR) 3 −TiCl 4 system (Special Publication No. 51-
152, Special Publication No. 52-15111), MgCl 2 −SiCl 4 −
ROH-TiCl 4 system (JP-A-49-106581), Mg
(OOCR) 2 −Al(OR) 3 −TiCl 4 system (Special Publication No. 52-1710
), Mg-POCl 3 -TiCl 4 system (Special Publication No. 51-153),
MgCl 2 −AlOCl−TiCl 4 system (Special Publication No. 54-15316)
An example of a preferred catalyst system is a combination of a solid substance such as (in the above formula, R is an organic residue and X is a halogen atom) and an organic aluminum compound. As an example of another catalyst system, a reaction product of an organomagnesium compound such as a so-called Grignard compound and a titanium compound and/or a vanadium compound is used as a solid substance, and an organoaluminum compound is combined with this. Can be done. Examples of organomagnesium compounds include organomagnesium compounds with the general formula RMgX, R 2 Mg, RMg (OR) (where R is an organic residue having 1 to 20 carbon atoms, and X represents a halogen); Ether complexes and these organomagnesium compounds further modified by adding various other organometallic compounds such as organosodium, organolithium, organopotassium, organoboron, organic calcium, and organozinc can be used. can. Specific examples of these catalyst systems include, for example:
RMgX-TiCl 4 series (Special Publication No. 50-39470), RMgX
-Phenol-TiCl 4 system (Special Publication No. 12953/1983),
Examples include combinations of organic aluminum compounds with solid substances such as RMgX-halogenated phenol-TiCl 4 system (Japanese Patent Publication No. 12954/1983). In these catalyst systems, titanium compounds and/or vanadium compounds can also be used as adducts with organic carboxylic acid esters, and the above-mentioned magnesium-containing inorganic compound solid carrier can be contacted with organic carboxylic acid esters. It can also be used later. Moreover, there is no problem in using an organoaluminum compound as an adduct with an organic carboxylic acid ester. Furthermore, in all cases it is also possible to use catalyst systems prepared in the presence of organic carboxylic esters without any problems. As the organic carboxylic acid ester, various aliphatic, alicyclic, and aromatic carboxylic acid esters are used, and aromatic carboxylic acids having 7 to 12 carbon atoms are preferably used. Specific examples include benzoic acid,
Examples include alkyl esters of anisic acid and toluic acid, such as methyl and ethyl. Specific examples of organoaluminum compounds to be combined with the above-mentioned solid substances include general formula R 3 Al;
R 2 AlX, RAlX 2 , R 2 AlOR, RAl(OR)X and
Organoaluminum compound of R 3 Al 2 Preferred compounds include triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminium chloride, ethylaluminum sesquichloride,
and mixtures thereof. The amount of organoaluminum compound used is not particularly limited, but is usually 0.1 to 0.1 to the amount of transition metal compound.
1000 mole times can be used. In addition, by bringing the above catalyst system into contact with α-olefin and then using it in a gas phase polymerization reaction, the polymerization activity can be greatly improved and operation can be made more stable than when untreated. . Various α-olefins can be used as the α-olefin used at this time, but α-olefins having 3 to 12 carbon atoms are preferable, and α-olefins having 3 to 8 carbon atoms are more preferable.
α-olefin is preferred. Examples of these α-olefins include propylene, butene-1, pentene-1, 4-methylpentene-1,
Examples include heptene-1, hexene-1, octene-1, decene-1, dodecene-1, and mixtures thereof. The temperature and time during contact between the catalyst system and the α-olefin can be selected within a wide range, for example 0 to 200°C, preferably 0 to 200°C.
Contact treatment can be carried out at 110°C for 1 minute to 24 hours. The amount of α-olefin to be brought into contact can be selected within a wide range, but it is usually 1 g to 1 g per 1 g of the solid substance.
50000g, preferably about 5g to 30000g of α-olefin, and 1g to 1g per 1g of the solid material.
It is desirable to react 500 g of alpha-olefin. At this time, the pressure at the time of contact can be arbitrarily selected, but it is usually desirable to bring them into contact under a pressure of -1 Kg/cm 2 ·G (meaning under reduced pressure of 1 atmosphere) to 100 Kg/cm 2 ·G. During the α-olefin treatment, the entire amount of the organoaluminum compound used may be combined with the solid substance and then brought into contact with the α-olefin, or a part of the organoaluminum compound used may be combined with the solid substance. Afterwards gaseous α-
The polymerization reaction may be carried out by contacting with olefin and adding the remaining organoaluminum compound separately during gas phase polymerization. Further, when the catalyst system and the α-olefin are brought into contact, there is no problem even if hydrogen gas coexists, and there is no problem even if other inert gases such as nitrogen, argon, helium, etc. coexist. The special polyolefin in the present invention is produced by copolymerizing ethylene and α-olefin in the gas phase in the presence of a solid material containing magnesium and a titanium compound and/or a vanadium compound and a catalyst consisting of an organoaluminum compound. The essence is to use a copolymer having a predetermined melt index and density obtained by the above method, and the α-olefin used in the copolymerization reaction is
Those having 3 to 12 carbon atoms are used. Specifically, propylene, butene-1, pentene-1, 4-methylpentene-1, heptene-1, hexene-1,
Octene-1, decene-1, dodecene-1, etc. can be mentioned. The polymerization reaction is carried out in a gas phase substantially free of solvent. As the reactor used, known reactors such as a fluidized bed and a stirring tank can be used. The polymerization reaction temperature is usually 0 to 110°C, preferably
The temperature is 20 to 80°C, and the pressure is normal pressure to 70 kg/cm 2 ·G, preferably 2 to 60 kg/cm 2 ·G. Although the molecular weight can be controlled by adjusting the polymerization temperature, the molar ratio of the catalyst, the amount of comonomer, etc., it is effectively carried out by adding hydrogen to the polymerization system. Of course, a two-stage or more multi-stage polymerization reaction may be carried out using different polymerization conditions such as hydrogen concentration, comonomer concentration, and polymerization temperature. As described above, in the presence of a catalyst consisting of a solid material containing magnesium, titanium and/or vanadium, and an organoaluminium, the present invention is capable of combining ethylene and carbon atoms having a carbon number of 3 to 12 in a gas phase substantially free of a solvent. By using an ethylene/α-olefin copolymer obtained by copolymerizing α-olefin with a density of 0.890 to 0.945 and a melt index of 0.01 to 5 as the sheath layer forming material, the properties of the sheath layer can be significantly improved. The improvement was completely unexpected. In the present invention, known auxiliary agents such as pigments, fillers, dispersants, antioxidants, and ultraviolet absorbers may be appropriately blended with the special polyolefin of the present invention, if necessary. In addition, in the present invention, it is possible to appropriately blend polyolefins obtained by other methods with the special polyolefins obtained by the specific method of the present invention.
There is no problem as long as the properties of the special polyolefin of the present invention are not impaired. Examples of these other polyolefins include high-pressure polyethylene, ethylene/vinyl acetate copolymers, and polyolefins obtained by medium- or low-pressure solution polymerization or slurry polymerization. The blending ratio of these is preferably 100 parts by weight or less based on 100 parts by weight of the special polyolefin of the present invention. EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited thereto. Example 1 1000 g of anhydrous magnesium chloride, 50 g of 1,2-dichloroethane and 170 g of titanium tetrachloride were ball milled at room temperature in a nitrogen atmosphere for 16 hours to support the titanium compound on the carrier. 1g of this solid substance
Contains 40mg of titanium per serving. A stainless steel autoclave was used as the apparatus for gas phase polymerization, and a loop was formed with a blower, a flow control valve, and a dry cyclone for separating the produced polymer, and the temperature of the autoclave was controlled by flowing hot water through the jacket. The polymerization temperature was set at 70°C, and the above solid substances were supplied to the autoclave at a rate of 250 mg/hr and triethylaluminum at a rate of 50 m-mol/hr. ) respectively
Copolymerization of ethylene and propylene was carried out while adjusting the hydrogen pressure to be 10% of the total pressure. The produced ethylene-propylene copolymer had a melt index of 0.2 and a density of 0.925. 100 parts by weight of the above ethylene-propylene copolymer, 2.5 parts by weight of carbon black and 4,4'-
0.2 parts by weight of thiobis(6-t-butyl-4-hydroxybenzyl) was added and mixed on a roll set at 160°C. The melt index of the mixture was 0.2 and the density was 0.935. Next, the mixture was made into a sheet with a thickness of 3.0±0.2m/m and tested according to ASTM D-1693.
When the environmental stress cracking resistance (ESCR) was measured using a method, there was no cracking at all even after more than 6,000 hours. Furthermore, when the mixture was tested for low temperature brittleness at a temperature of -75°C in accordance with JIS K6760 using a sheet having a thickness of 2.0±0.2 m/m, no cracks were found. Further, when the mixture was made into a sheet with a thickness of 3.0±0.1 m/m and its abrasion properties were examined using a taper type abrasion tester, the abrasion was extremely small. Example 2 In Example 1, the composition of the gas supplied to the autoclave was changed to 96 mol% ethylene and hexene.
Copolymerization of ethylene and hexene-1 was carried out in the same manner as in Example 1, except that the polymerization concentration was 14 mol %, hydrogen was 18% of the total pressure, and the polymerization was carried out at 85°C. The produced ethylene/hexene-1 copolymer had a melt index of 1.0 and a density of 0.925. To 100 parts by weight of this ethylene-hexene-1 copolymer, 2.5 parts by weight of carbon black and 4,
0.2 parts by weight of 4'-thiobis(6-t-butyl-4-hydroxybenzyl) was added and mixed, resulting in a mixture with a melt index of 1.0 and a density of 0.935, which was subjected to ESCR and low temperature in the same manner as Example 1. When brittleness and abrasion resistance were examined, all points were good. Example 3 In Example 1, the composition of the gas supplied to the autoclave was changed to 88 mol% ethylene and 1 butene-1.
Assuming 12 mol% and hydrogen as 14% of the total pressure,
Copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 except that the polymerization was carried out at 80°C. The resulting ethylene-butene-1 copolymer had a melt index of 1.0 and a density of 0.920. To 100 parts by weight of this ethylene-butene-1 copolymer, 2.5 parts by weight of carbon black and 0.2 parts by weight of 4,4'-thiobis(6-t-butyl-4-hydroxybenzyl) are added and mixed. A mixture having a melt index of 1.0 and a density of 0.930 was examined for ESCR, low temperature brittleness and wear resistance in the same manner as in Example 1, and was found to be good in all respects. Comparative Example 1 Same as Example 1 except that low-density polyethylene with a melt index of 0.15 and a density of 0.920 manufactured by a high-pressure method was used instead of the ethylene-propylene copolymer used in Example 1. When the ESCR, low-temperature brittleness and wear resistance were examined by the method, the ESCR was very poor and the wear resistance was also unsatisfactory. Comparative Example 2 Instead of the ethylene/propylene copolymer used in Example 1, an ethylene/vinyl acetate copolymer (vinyl acetate content: 3 mol%) with a melt index of 0.15 and a density of 0.922 produced by a high-pressure method was used. The ESCR, low-temperature brittleness and wear resistance were examined in the same manner as in Example 1, except that the results were unsatisfactory in all respects. 【table】
Claims (1)
ウムとを含有する固体物質と有機アルミニウムと
からなる触媒の存在下、実質上溶媒の存在しない
気相状態でエチレンと炭素数３〜12のα−オレフ
インとを共重合させて得られる密度が0.890〜
0.945で、かつメルトインデツクスが0.01〜５の
エチレン・α−オレフイン共重合体を主体とし
て、電線、ケーブルの保護被覆層を製造する方
法。1. Copolymerization of ethylene and α-olefin having 3 to 12 carbon atoms in a gas phase substantially free of solvent in the presence of a catalyst consisting of a solid substance containing magnesium, titanium, and/or vanadium, and organoaluminium. The resulting density is 0.890 ~
0.945 and a melt index of 0.01 to 5. A method for producing a protective coating layer for electric wires and cables, mainly consisting of an ethylene/α-olefin copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4776880A JPS56145607A (en) | 1980-04-11 | 1980-04-11 | Wire or cable protection coating layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4776880A JPS56145607A (en) | 1980-04-11 | 1980-04-11 | Wire or cable protection coating layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56145607A JPS56145607A (en) | 1981-11-12 |
| JPS6342363B2 true JPS6342363B2 (en) | 1988-08-23 |
Family
ID=12784546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4776880A Granted JPS56145607A (en) | 1980-04-11 | 1980-04-11 | Wire or cable protection coating layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56145607A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6010311U (en) * | 1983-06-28 | 1985-01-24 | 神鋼電機株式会社 | Electromagnetic induction guide wire for unmanned vehicles |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4076698A (en) * | 1956-03-01 | 1978-02-28 | E. I. Du Pont De Nemours And Company | Hydrocarbon interpolymer compositions |
| JPS54148093A (en) * | 1978-03-31 | 1979-11-19 | Union Carbide Corp | Impregnation polymerization catalyst * manufacture thereof * and use to polymerization |
| JPS5554308A (en) * | 1978-10-17 | 1980-04-21 | Nippon Oil Co Ltd | Preparation of copolymer |
| JPS5556111A (en) * | 1978-10-20 | 1980-04-24 | Nippon Oil Co Ltd | Preparation of copolymer |
| JPS5573712A (en) * | 1978-11-29 | 1980-06-03 | Nippon Oil Co Ltd | Preparation of copolymer |
| JPS6320845A (en) * | 1986-07-14 | 1988-01-28 | Nec Ic Microcomput Syst Ltd | Semiconductor integrated circuit |
-
1980
- 1980-04-11 JP JP4776880A patent/JPS56145607A/en active Granted
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4076698A (en) * | 1956-03-01 | 1978-02-28 | E. I. Du Pont De Nemours And Company | Hydrocarbon interpolymer compositions |
| US4076698B1 (en) * | 1956-03-01 | 1993-04-27 | Du Pont | |
| JPS54148093A (en) * | 1978-03-31 | 1979-11-19 | Union Carbide Corp | Impregnation polymerization catalyst * manufacture thereof * and use to polymerization |
| JPS5554308A (en) * | 1978-10-17 | 1980-04-21 | Nippon Oil Co Ltd | Preparation of copolymer |
| JPS5556111A (en) * | 1978-10-20 | 1980-04-24 | Nippon Oil Co Ltd | Preparation of copolymer |
| JPS5573712A (en) * | 1978-11-29 | 1980-06-03 | Nippon Oil Co Ltd | Preparation of copolymer |
| JPS6320845A (en) * | 1986-07-14 | 1988-01-28 | Nec Ic Microcomput Syst Ltd | Semiconductor integrated circuit |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56145607A (en) | 1981-11-12 |
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