JPS648010B2 - - Google Patents
Info
- Publication number
- JPS648010B2 JPS648010B2 JP12855478A JP12855478A JPS648010B2 JP S648010 B2 JPS648010 B2 JP S648010B2 JP 12855478 A JP12855478 A JP 12855478A JP 12855478 A JP12855478 A JP 12855478A JP S648010 B2 JPS648010 B2 JP S648010B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- copolymer
- compound
- density
- titanium
- 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
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 38
- 239000003054 catalyst Substances 0.000 claims description 29
- 229920001577 copolymer Polymers 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 150000003609 titanium compounds Chemical class 0.000 claims description 14
- 150000003682 vanadium compounds Chemical class 0.000 claims description 12
- 239000011343 solid material Substances 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000002484 inorganic compounds Chemical class 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 39
- 229920000642 polymer Polymers 0.000 description 27
- 238000000034 method Methods 0.000 description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 22
- 239000005977 Ethylene Substances 0.000 description 22
- 239000010936 titanium Substances 0.000 description 18
- 239000004711 α-olefin Substances 0.000 description 15
- 239000002002 slurry Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- 229910052719 titanium Inorganic materials 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000012685 gas phase polymerization Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 230000037048 polymerization activity Effects 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 7
- -1 Polyethylene Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001038 ethylene copolymer Polymers 0.000 description 4
- 150000002902 organometallic compounds Chemical class 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 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
- 238000009826 distribution Methods 0.000 description 2
- 230000006353 environmental stress Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910003902 SiCl 4 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
- 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
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 229920001887 crystalline plastic Polymers 0.000 description 1
- 229920006038 crystalline resin Polymers 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
- 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000000843 powder Substances 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-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
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明は高活性なチーグラー型触媒を用いた気
相重合法による低密度エチレン共重合体の製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a low density ethylene copolymer by a gas phase polymerization method using a highly active Ziegler type catalyst.
遷移金属化合物および有機金属化合物よりなる
触媒を用いた重合により得られるポリエチレンは
一般にスラリー重合法によつて製造され、その密
度は重合時に反応器内部で内壁や撹拌機に析出、
フアウリングなどを起こすことのない限界である
とされている0.945以上のものしか通常製造され
ていない。 Polyethylene obtained by polymerization using a catalyst consisting of a transition metal compound and an organometallic compound is generally produced by a slurry polymerization method.
Only those with a value of 0.945 or higher are normally manufactured, which is considered to be the limit that will not cause fouling.
密度が0.945g/cm3以下の中密度あるいは低密
度ポリエチレンは通常ラジカル触媒による、いわ
ゆる高圧法により専ら製造されているがごく最近
になつて、チーグラー系触媒を用いた高温溶液法
も試みられるようになつた。またバナジウム化合
物を用いてエチレンと他のα−オレフインとの共
重合を行ないエラストマーを製造することも行な
われている。 Medium-density or low-density polyethylene with a density of 0.945 g/cm 3 or less is normally produced exclusively by the so-called high-pressure method using radical catalysts, but very recently, high-temperature solution methods using Ziegler catalysts have also been attempted. It became. Furthermore, elastomers have also been produced by copolymerizing ethylene and other α-olefins using vanadium compounds.
しかしながら、上記の方法によつて合成された
ポリマーは結晶性樹脂であるか、あるいは非晶性
のエラストマーであるかのいずれかであつて、そ
の性格ははつきりしている。これらポリオレフイ
ン系のプラスチツクスやエラストマー類は各々す
ぐれた性能を示し様々な用途に用いられている
が、使用目的によつては、例えばプラスチツクス
に幾分かのエラストマー的性格を与えることによ
り耐環境応力亀裂性を向上することが求められた
り、あるいは逆にエラストマーに結晶性に基づく
強度が求められたりすることは日常よく経験する
ことである。しかしながらそのような目的のため
に両成分を混合すると多くの場合、引張強度や剛
性などの諸物性が低下してしまうことはよく知ら
れていることである。 However, the polymer synthesized by the above method is either a crystalline resin or an amorphous elastomer, and its characteristics are distinct. Each of these polyolefin-based plastics and elastomers exhibits excellent performance and is used for a variety of purposes. It is a common experience that an elastomer is required to have improved stress cracking resistance, or conversely, that an elastomer is required to have strength based on its crystallinity. However, it is well known that when the two components are mixed for such purposes, physical properties such as tensile strength and rigidity often deteriorate.
しかし、樹脂そのものが結晶性のプラスチツク
スでもなければエラストマーでもない中間の構造
をもつたもので高度の伸長性を示す軟質もしくは
半硬質樹脂を合成できればその樹脂そのものが上
記の目的にかなつたものとなり得ようし、あるい
は他のプラスチツクスに混合することによりエラ
ストマー的性格を付与することができプラスチツ
クスの性質を改良することが可能となる。しかし
ながらこのような軟質あるいは半硬質の樹脂につ
いてはあまり知られていない。最近、このような
中間の物性を示す樹脂の製造方法に関していくつ
かの報告がなされているが、それらは種々の欠点
を有しており、工業的に実施するには多くの解決
すべき問題点がある。 However, if it is possible to synthesize a soft or semi-rigid resin that has an intermediate structure between neither crystalline plastics nor elastomers and exhibits a high degree of elongation, that resin itself will meet the above objectives. By mixing it with other plastics, it is possible to impart elastomeric properties and improve the properties of plastics. However, little is known about such soft or semi-hard resins. Recently, several reports have been made on methods for producing resins that exhibit intermediate physical properties, but they have various drawbacks and many problems need to be solved before they can be implemented industrially. There is.
たとえば、特公昭46−11028号にはエチレン・
α−オレフイン共重合体の製造方法において芳香
族炭化水素溶剤を用い溶液重合を行なうことを示
しているが、この方法では触媒効率が悪く、また
溶液重合であるため溶剤の分離、回収が煩雑であ
るという欠点を有している。 For example, in Special Publication No. 46-11028, ethylene
The method for producing α-olefin copolymers involves solution polymerization using aromatic hydrocarbon solvents, but this method has poor catalyst efficiency and is complicated to separate and recover the solvent because it is solution polymerization. It has some drawbacks.
また特公昭47−26185号においては、ハロゲン
化脂肪族炭化水素を溶剤としてエチレンとα−オ
レフインとの共重合を行なう方法を提示している
が、ハロゲン化炭化水素溶剤が分子量調節剤とし
て作用するためか低分子量共重合体が多量に生成
するのでその成形物は表面がべたつくという欠点
がある。また同特許公報には炭素数3〜5の低級
炭化水素を溶剤とする方法も併せ開示されている
が、これらの溶剤を用いて重合を行なうと溶剤に
よる蒸気圧により反応圧を高くすることが必要で
あり、また溶剤回収工程においては回収溶剤を液
化するために圧縮、冷却することが必要であるな
どの欠点を有している。 Furthermore, Japanese Patent Publication No. 47-26185 proposes a method of copolymerizing ethylene and α-olefin using a halogenated aliphatic hydrocarbon as a solvent, but the halogenated hydrocarbon solvent acts as a molecular weight regulator. Because of this, a large amount of low molecular weight copolymer is produced, and the resulting molded product has the disadvantage of a sticky surface. The same patent publication also discloses a method using a lower hydrocarbon having 3 to 5 carbon atoms as a solvent, but when polymerization is carried out using these solvents, the reaction pressure cannot be increased due to the vapor pressure of the solvent. Moreover, in the solvent recovery process, it is necessary to compress and cool the recovered solvent in order to liquefy it.
さらに特開昭51−41784号にはエチレンとブテ
ン−1とをスラリー共重合させる方法が開示され
ているが、この場合においても重合温度および原
料組成が細かく規定されており、この範囲を越え
るとスラリーがミルク状ないしはカユ状となり反
応器の運転およびスラリーの輸送が困難となるな
どの欠点が示されている。 Furthermore, JP-A-51-41784 discloses a method of slurry copolymerization of ethylene and butene-1, but even in this case, the polymerization temperature and raw material composition are specified in detail, and if the temperature exceeds this range, Disadvantages include that the slurry becomes milky or oyster-like, making it difficult to operate the reactor and transport the slurry.
以上の例にみられる各々の欠点は、結局触媒活
性が低く、溶液重合であるため溶剤の分離、回収
が煩雑であり、また溶剤との連鎖移動により低分
子量共重合体が多く生成すること、またスラリー
重合の場合はポリマースラリーを維持するために
は重合温度、原料組成を規定しなければならない
事に基づくものである。さらにこれらの例におい
ては共重合させるコモノマーがきわめて多量に必
要であるという欠点もある。 The disadvantages of each of the above examples are that the catalyst activity is low, that separation and recovery of the solvent is complicated due to solution polymerization, and that a large amount of low molecular weight copolymer is produced due to chain transfer with the solvent. In the case of slurry polymerization, the polymerization temperature and raw material composition must be regulated in order to maintain the polymer slurry. A further disadvantage in these examples is that very large amounts of comonomer are required to be copolymerized.
近年、触媒活性の向上については多くの研究が
なされMgO、Mg(OH)2、MgCl2、MgCO3、Mg
(OH)Clなど種々のMg含有固体担体に遷移金属
を担持せしめ、しかるのち有機金属化合物と組み
合わせた触媒系は著しく高活性なオレフイン重合
用の触媒となりうることが知られている。また、
RMgX、R2Mg、RMg(OR)などの各種有機マ
グネシウム化合物と遷移金属化合物との反応物が
すぐれたオレフインの高重合触媒となりうること
も知られている(特公昭39−12105号、ベルギー
特許第742112号、特公昭43−13050号、特公昭45
−9548号その他)。 In recent years, much research has been conducted on improving catalytic activity.
It is known that a catalyst system in which a transition metal is supported on various Mg-containing solid supports such as (OH)Cl, and then combined with an organometallic compound can be a highly active catalyst for olefin polymerization. Also,
It is also known that reactants of various organomagnesium compounds such as RMgX, R 2 Mg, and RMg (OR) with transition metal compounds can serve as excellent catalysts for the high polymerization of olefins (Japanese Patent Publication No. 39-12105, Belgian patent). No. 742112, Special Publication No. 13050, Special Publication No. 13050, Special Publication No. 13050
−9548 and others).
しかしながら、このような担体付高活性触媒を
用いてスラリー重合あるいは溶液重合による低密
度化を行なう場合にも前述の各々の欠点は何ら解
決されるものではなかつた。 However, even when the density is reduced by slurry polymerization or solution polymerization using such a highly active catalyst with a carrier, the above-mentioned drawbacks have not been solved at all.
本発明はこれらの問題点を一挙に解決した新規
な方法を提供するものである。 The present invention provides a novel method that solves these problems all at once.
すなわち、本発明者らは、上記の技術課題につ
き鋭意研究の結果溶液あるいはスラリー重合に際
して問題であつた、活性、かさ密度、付着あるい
は粗大化などの種々の問題点を解決することがで
き、本発明を完成させることができたもので、本
発明の方法により、きわめて安定に気相重合反応
を実施でき、かつ触媒除去工程も省略できるた
め、全体としてきわめて簡略なエチレンとブテン
−1の気相重合方法を完成させることができた。
さらに本発明の方法を実施することによつて得ら
れるエチレンとブテン−1との共重合体は優れた
物性を有していることが明らかとなつた。 That is, as a result of intensive research into the above-mentioned technical problems, the present inventors were able to solve various problems such as activity, bulk density, adhesion, and coarsening that were problems in solution or slurry polymerization, and the present invention The invention has been completed, and the method of the present invention makes it possible to carry out a gas phase polymerization reaction in an extremely stable manner, and also to omit the catalyst removal step. We were able to complete the polymerization method.
Furthermore, it has become clear that the copolymer of ethylene and butene-1 obtained by carrying out the method of the present invention has excellent physical properties.
すなわち本発明は(a)ケイ素、アルミニウムおよ
び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
または水酸化物、(b)水酸化マグネシウム、(c)炭酸
マグネシウム、(d)酸化マグネシウムおよび(e)塩化
マグネシウムからなる群より選ばれる少なくとも
一種の固体の無機化合物を含酸素化合物、含硫黄
化合物、炭化水素およびハロゲン含有物質から選
ばれる少なくとも一種の物質で処理または反応さ
せたものとチタン化合物またはチタン化合物とバ
ナジウム化合物と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、実質
上溶媒のない気相状態でエチレンとエチレンに対
して10ないし45mol%のブテン−1を共重合させ
ることによりメルトインデツクス0.01ないし10、
かつ密度0.850g/cm3以上0.910g/cm3未満を有す
る軟質または半硬質のエチレン・ブテン−1共重
合体を得ることを特徴とする共重合体の製造方法
に関するものであり、本発明に規定する固体物質
および有機アルミニウム化合物からなる触媒を用
い本発明において規定した範囲内の量比のエチレ
ンとブテン−1を用いて気相重合を行なうことに
よりきわめて高活性で、かつ生成ポリマーが粘着
性の高い低密度であるにもかかわらず、粗大粒子
や超微粒子の生成割合が減少し、粒子性状が良好
となり、かさ密度が高く、更には反応器への付
着、重合体粒子の塊化もきわめて少なく、非常に
安定的に気相重合反応を実施できることが明らか
となつた。本発明の方法により、きわめて円滑に
気相重合反応を実施できるようになつたばかり
か、容易に低密度エチレン共重合体が容易に得ら
れることは全く予期されない事実であり、驚くべ
きことと言わねばならない。 That is, the present invention provides (a) a double salt, double oxide, carbonate, chloride or hydroxide containing a metal selected from silicon, aluminum and calcium and a magnesium atom, (b) magnesium hydroxide, (c) At least one solid inorganic compound selected from the group consisting of magnesium carbonate, (d) magnesium oxide, and (e) magnesium chloride with at least one substance selected from oxygen-containing compounds, sulfur-containing compounds, hydrocarbons, and halogen-containing substances. 10 to 45 mol of ethylene and ethylene in a substantially solvent-free gas phase in the presence of a solid substance containing a treated or reacted substance and a titanium compound or a titanium compound and a vanadium compound and a catalyst consisting of an organoaluminum compound. melt index 0.01 to 10 by copolymerizing % butene-1,
The present invention relates to a method for producing a copolymer, characterized by obtaining a soft or semi-rigid ethylene-butene-1 copolymer having a density of 0.850 g/cm 3 or more and less than 0.910 g/cm 3 . By carrying out gas phase polymerization using a catalyst consisting of a specified solid substance and an organoaluminium compound and using ethylene and butene-1 in the quantitative ratio within the range specified in the present invention, the resulting polymer has extremely high activity and is sticky. Despite its high low density, the proportion of coarse particles and ultrafine particles produced is reduced, the particle properties are good, the bulk density is high, and it is extremely resistant to adhesion to the reactor and agglomeration of polymer particles. It has become clear that the gas phase polymerization reaction can be carried out very stably with a small amount of gas. The fact that the method of the present invention not only makes it possible to carry out the gas phase polymerization reaction extremely smoothly, but also that low-density ethylene copolymers can be easily obtained is a totally unexpected and surprising fact. No.
また本発明においては50〜80℃の如き比較的低
温でも共重合反応が実施可能であり容易に低密度
エチレン共重合体が得られるもので生成物の反応
器への付着、塊化の点できわめて有利でありこの
点も本発明の他の利点である。また本発明の方法
においては高メルトインデツクスの低密度エチレ
ン共重合体が容易に得られることが特徴であり、
この点もまた本発明の他の利点である。すなわ
ち、かかる利点により前述したように本発明に記
載の如き軟質ないし半硬質の共重合体が気相重合
により効率よく得られるものである。 In addition, in the present invention, the copolymerization reaction can be carried out even at a relatively low temperature such as 50 to 80°C, and a low-density ethylene copolymer can be easily obtained. This is very advantageous and is another advantage of the present invention. Furthermore, the method of the present invention is characterized in that a low density ethylene copolymer with a high melt index can be easily obtained.
This point is also another advantage of the present invention. That is, due to these advantages, as described above, the soft to semi-hard copolymers described in the present invention can be efficiently obtained by gas phase polymerization.
本発明の方法においてエチレンと共に重合させ
るブテン−1は共重合体の密度および分子量を調
節し、さらに得られる共重合体は透明性が高く、
外観および光沢が良好であり、柔軟性、ゴム弾性
が常温はもち論のこと、低温においても優れてい
る。一方、このような柔軟性を有しているにもか
かわらず本発明により得られる共重合体の強度は
通常のポリオレフイン樹脂と同等もしくはそれ以
上の値を示す。さらに不飽和結合および触媒残渣
などの不純物をほとんど含まないため耐候性、耐
薬品性および誘電損失、破壊電圧あるいは固有抵
抗などの電気特性が非常に優れている。また耐衝
撃性、耐環境応力亀裂性に対してもきわめて優れ
た性能を示している。したがつて本発明の方法に
よつて得られる共重合物は押出、中空、射出、プ
レスおよび真空成形などの既存の成形法によりフ
イルムシート、中空容器、電線その他各種製品に
成形でき各用途に供することができる。 Butene-1, which is copolymerized with ethylene in the method of the present invention, controls the density and molecular weight of the copolymer, and the resulting copolymer has high transparency;
It has good appearance and gloss, and has excellent flexibility and rubber elasticity not only at room temperature but also at low temperature. On the other hand, despite having such flexibility, the strength of the copolymer obtained by the present invention is equal to or higher than that of ordinary polyolefin resins. Furthermore, since it contains almost no impurities such as unsaturated bonds and catalyst residues, it has excellent weather resistance, chemical resistance, and electrical properties such as dielectric loss, breakdown voltage, and specific resistance. It also shows extremely excellent performance in terms of impact resistance and environmental stress cracking resistance. Therefore, the copolymer obtained by the method of the present invention can be molded into film sheets, hollow containers, electric wires, and various other products by existing molding methods such as extrusion, hollow molding, injection, press, and vacuum molding, and can be used for various purposes. be able to.
また本発明の方法によつて得られる共重合物は
オレフインを成分としているためポリオレフイン
樹脂と組成が非常によく似ており、かつ低結晶性
であるために、他のポリオレフイン樹脂、たとえ
ば高密度および低密度のポリエチレン、ポリプロ
ピレン、エチレン−酢酸ビニル共重合体などとは
特に相溶性が良く、これらの樹脂へブレンドする
ことにより耐衝撃性、耐寒性、耐環境応力亀裂性
などの性質を向上させることができる。 In addition, since the copolymer obtained by the method of the present invention contains olefin as a component, it has a composition very similar to that of polyolefin resin, and has low crystallinity, so it cannot be used with other polyolefin resins, such as high density and It is particularly compatible with low-density polyethylene, polypropylene, and ethylene-vinyl acetate copolymers, and by blending it with these resins, properties such as impact resistance, cold resistance, and environmental stress cracking resistance can be improved. I can do it.
本発明において使用する触媒系における該固体
物質としては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、塩化マグネシウムおよ
びケイ素、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、塩化物もしくは水酸化物並びに
所望によりを含酸素化合物、含硫黄化合物、炭化
水素もしくはハロゲン含有物質で処理または反応
させたものにチタン化合物またはチタンとバナジ
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。 The solid substances in the catalyst system used in the present invention include magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium chloride, and double salts, double oxides, and carbonates containing magnesium atoms and metals selected from silicon, aluminum, and calcium. Titanium compounds or titanium and vanadium compounds supported by a known method on salts, chlorides, or hydroxides, and optionally treated or reacted with oxygen-containing compounds, sulfur-containing compounds, hydrocarbons, or halogen-containing substances. can be mentioned.
ここでいう、チタン化合物またはチタンとバナ
ジウム化合物としては、これら金属のハロゲン化
物、アルコキシハロゲン化物、酸化物、ハロゲン
化酸化物を挙げることができる。これらの具体例
として四塩化チタン、四臭化チタン、四ヨウ化チ
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、テトライソプロポキシチタン等の4価のチ
タン化合物、四ハロゲン化チタンを水素、アルミ
ニウム、チタンまたは有機金属化合物により還元
して得られる各種の三ハロゲン化チタンがあげら
れ、また各種の4価のハロゲン化アルコキシチタ
ンを有機金属化合物により還元して得られる化合
物等の3価のチタン化合物、四塩化バナジウムの
ような四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ような五
価のバナジウム化合物、三塩化バナジウム、バナ
ジウムトリエトキシドのような三価のバナジウム
化合物等があげられる。 The titanium compound or titanium and vanadium compound mentioned here includes halides, alkoxy halides, oxides, and halogenated oxides of these metals. Specific examples of these include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, Examples include tetravalent titanium compounds such as tetraisopropoxytitanium, various titanium trihalides obtained by reducing titanium tetrahalides with hydrogen, aluminum, titanium, or organometallic compounds; Trivalent titanium compounds such as compounds obtained by reducing alkoxytitanium with organometallic compounds, tetravalent vanadium compounds such as vanadium tetrachloride, pentavalent vanadium compounds such as vanadium oxytrichloride and orthoalkylvanadate. , trivalent vanadium compounds such as vanadium trichloride and vanadium triethoxide.
これらのチタン化合物およびバナジウム化合物
のうち、四価のチタン化合物が特に好ましい。 Among these titanium compounds and vanadium compounds, tetravalent titanium compounds are particularly preferred.
本発明の触媒としては、前記した固体担体にチ
タン化合物またはチタンとバナジウム化合物を担
持させて得た固体物質に有機アルミニウム化合物
を組合せたものが使用される。 As the catalyst of the present invention, a combination of a solid material obtained by supporting a titanium compound or a titanium and vanadium compound on the solid carrier described above and an organoaluminum compound is used.
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51−3514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52−11710号)、Mg
−POCl3−TiCl4系(特公昭51−153号)、MgCl2
−AlOCl−TiCl4系(特開昭51−133386号)など
の固体物質(前記式中において、Rは有機残基を
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。 Specific examples of these catalysts include, for example, MgO-RX-TiCl 4 system (Japanese Patent Publication No. 51-3514),
MgCl 2 −Al(OR) 3 −TiCl 4 system (Special Publication No. 1987-152,
Special Publication No. 52-15111), MgCl 2 −SiCl 4 −ROH−
TiCl 4 series (JP-A-49-106581), Mg (OOCR) 2 −
Al (OR) 3 −TiCl 4 system (Special Publication No. 11710, Showa 52-11710), Mg
−POCl 3 −TiCl 4 system (Special Publication No. 51-153), MgCl 2
An example of a preferable catalyst system is one in which an organoaluminum compound is combined with a solid substance (in the above formula, R represents an organic residue) such as -AlOCl-TiCl 4 system (Japanese Patent Application Laid-Open No. 133386/1986). .
これらの触媒系において、チタン化合物または
チタンと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担体
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
て使用して何ら支障がない。さらには、本発明に
おける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。 In these catalyst systems, a titanium compound or a titanium and vanadium compound can also be used as an adduct with an organic carboxylic acid ester, or after contacting the above-mentioned magnesium-containing inorganic compound solid support with an organic carboxylic acid ester. You can also use Further, there is no problem in using the organoaluminum compound as an adduct with the organic carboxylic acid ester. Furthermore, in all cases of the present invention, catalyst systems prepared in the presence of organic carboxylic acid esters can be used without any problem.
ここで有機カルボン酸エステルとしては各種の
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。 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.
本発明に用いる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(ただしRは炭素数1〜20のア
ルキル基またはアリール基、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
れるもので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。 Specific examples of organoaluminum compounds used in the present invention include general formulas R 3 Al, R 2 AlX, RAlX 2 ,
Organoaluminum compounds of R 2 AlOR, RAl ( OR )X and R 3 Al 2 triethylaluminum, triisobutylaluminum, trihexylaluminum,
Examples include trioctylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, and mixtures thereof.
本発明において、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。 In the present invention, the amount of the organoaluminum compound to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 times the amount of the transition metal compound.
重合反応はエチレンとブテン−1との混合物を
気相で重合させる。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。 In the polymerization reaction, a mixture of ethylene and butene-1 is polymerized in the gas phase. As the reactor used, known reactors such as a fluidized bed and a stirring tank can be used.
重合反応温度は、通常20〜110℃、好ましくは
50〜100℃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、
本発明の方法を用いて、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も何ら支障なく実
施できる。 The polymerization reaction temperature is usually 20 to 110°C, preferably
The temperature is 50 to 100℃, the pressure is normal pressure to 70Kg/ cm2・G,
Preferably it is 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,
Using the method of the present invention, two-stage or more multi-stage polymerization reactions with different polymerization conditions such as hydrogen concentration, comonomer concentration, and polymerization temperature can be carried out without any problem.
また本発明においては、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等およびこれらの混合物などをあげ
ることができる。本発明の触媒と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。 In addition, in the present invention, by bringing the catalyst system into contact with an α-olefin and then using it in a gas phase polymerization reaction, the polymerization activity is greatly improved,
It is also possible to operate more stably than in the untreated case. Various α-olefins can be used at this time, but α-olefins having 3 to 12 carbon atoms are preferred, and α-olefins having 3 to 8 carbon atoms are more preferred.
Examples of these α-olefins include propylene, butene-1, pentene-1, 4-methylpentene-1, heptene-1, hexene-1,
Examples include octene-1 and mixtures thereof. The temperature and time during contact between the catalyst of the present invention and α-olefin can be selected within a wide range, for example, 0 to 200°C, preferably 0 to 110°C.
The contact treatment can be carried out in 1 minute to 24 hours.
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、−1〜100Kg/cm2・Gの圧力下に
接触させることが望ましい。 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 contact under a pressure of -1 to 100 kg/cm 2 ·G.
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
化合物をエチレンの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、前記触媒と
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。 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 the gas phase polymerization of ethylene. Further, when the catalyst 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.
本発明の方法において用いられるブテン−1の
使用量はエチレンに対して10ないし45mol%の範
囲で用いることが必要である。この範囲をはずれ
ると本発明の目的とするメルトインデツクス0.01
ないし10、かつ密度0.850ないし0.910g/cm3未満
を有するエチレン・ブテン−1共重合体を得るこ
とができない。また、ブテン−1の使用量は重合
器中の気相の組成比によつて容易に調節すること
ができる。 The amount of butene-1 used in the method of the present invention needs to be in the range of 10 to 45 mol% based on ethylene. Outside this range, the melt index targeted by the present invention is 0.01.
10 to 10 and a density of less than 0.850 to 0.910 g/cm 3 cannot be obtained. Further, the amount of butene-1 used can be easily adjusted by changing the composition ratio of the gas phase in the polymerization vessel.
さらに本発明の方法においてはターモノマーと
してブタジエン、1,4−ヘキサジエン、1,5
−ヘキサジエン、ビニルノルボルネン、エチリデ
ンノルボルネンおよびジシクロペンタジエンなど
の各種のジエン類を加えて共重合することもでき
る。 Furthermore, in the method of the present invention, butadiene, 1,4-hexadiene, 1,5
- Various dienes such as hexadiene, vinylnorbornene, ethylidenenorbornene and dicyclopentadiene can also be added for copolymerization.
以下に実施例をのべるが、これらは本発明を実
施するための説明用のものであつて、本発明はこ
れらに制限されるものではない。 Examples will be described below, but these are for illustrative purposes in carrying out the present invention, and the present invention is not limited thereto.
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35mgのチタンを含有していた。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 35mg of titanium per serving.
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。 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.
重合温度は80℃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、ブテン−1および水素の組成(モル比)をそ
れぞれ74%、16%および10%となるように調整し
ながら重合を行なつた。 The polymerization temperature was set at 80°C, and the above solid substances were fed into the autoclave at a rate of 250 mg/hr and triethylaluminum at a rate of 50 m-mol/hr, and ethylene, butene-1 and hydrogen in the gas fed to the autoclave were controlled by a blower. Polymerization was carried out while adjusting the composition (molar ratio) to be 74%, 16%, and 10%, respectively.
生成ポリマーはメルトインデツクス(MI)
1.3、かさ密度0.391、密度0.897であり、密度がき
わめて低いにもかかわらず粘着性がなくその大部
分が300〜600μの粉末であつた。また重合活性は
201500gポリマー/g−Tiと非常に高活性であ
つた。 The produced polymer is melt index (MI)
1.3, bulk density 0.391, and density 0.897, and although the density was extremely low, there was no stickiness and most of the powder was 300 to 600μ in size. Also, the polymerization activity is
It had a very high activity of 201,500g polymer/g-Ti.
10時間の連続運転後、重合を停止し、オートク
レーブ内を点検したところ、内壁、撹拌機および
ポリマー抜出管にはポリマーの付着は全くみとめ
られなかつた。すなわち、比較例1で示したスラ
リー重合では安定に長時間の連続運転を行なうこ
とが不可能であつたのに対して本発明の方法に従
えばきわめて安定に長時間の連続運転ができるこ
とが明らかである。 After 10 hours of continuous operation, the polymerization was stopped and the inside of the autoclave was inspected, and no polymer was found to be attached to the inner wall, stirrer, or polymer extraction tube. In other words, it is clear that in the slurry polymerization shown in Comparative Example 1, it was impossible to carry out stable continuous operation for a long time, whereas by following the method of the present invention, it is possible to carry out very stable continuous operation for a long time. It is.
この共重合物をプレス成形したものは透明で表
面のべたつきもなく、破断点強度210Kg/cm2、伸
び750%であつた。 A press molded product of this copolymer was transparent, had no stickiness on the surface, had a strength at break of 210 kg/cm 2 and an elongation of 750%.
また、この共重合体は容易に押出機によつて造
粒でき、さらに容易にインフレーシヨンフイルム
に成形できた。 Further, this copolymer could be easily granulated using an extruder, and furthermore, it could be easily formed into a blown film.
比較例 1
実施例1と同じ触媒を用い85℃でヘキサンを溶
媒とする連続スラリー重合を行なつた。Comparative Example 1 Using the same catalyst as in Example 1, continuous slurry polymerization was carried out at 85°C using hexane as a solvent.
固体物質を5mg/、トリエチルアルミニウム
を1m−mol/とし、ヘキサンを40/hr、エ
チレン8Kg/hr、ブテン−1を8Kg/hr(エチレ
ンに対して50mol%)および水素を3Nm3/hrの
割合で供給し連続重合を行なつた。 The ratio of solid substance is 5 mg/hr, triethylaluminum is 1 m-mol/hr, hexane is 40/hr, ethylene is 8 Kg/hr, butene-1 is 8 Kg/hr (50 mol% relative to ethylene), and hydrogen is 3 Nm 3 /hr. Continuous polymerization was carried out by supplying
生成ポリマーをスラリーとして連続的に抜出し
たが、抜出されたスラリーは重合初期よりポリマ
ー粒子が著しく膨潤しており、またヘキサン層は
ミルク状であつた。2時間後にはスラリー抜出し
管が閉塞し、重合を停止せざるを得なかつた。反
応器内部の点検を行なつたところ内壁、撹拌機に
多量のポリマーが付着していた。 The produced polymer was continuously extracted as a slurry, but the polymer particles in the slurry extracted were significantly swollen from the initial stage of polymerization, and the hexane layer was milky. After 2 hours, the slurry extraction pipe became clogged, and the polymerization had to be stopped. When the inside of the reactor was inspected, a large amount of polymer was found adhering to the inner wall and the stirrer.
生成ポリマーはMI1.8、かさ密度0.246、密度
0.913の値をもつものであつた。このようにコモ
ノマーのブテン−1を非常に多量に加えているに
もかかわらず、生成ポリマーの密度は十分に低下
しておらず、非常に効率の悪い重合の例であるこ
とが明らかである。 The resulting polymer has an MI of 1.8, a bulk density of 0.246, and a density of
It had a value of 0.913. Despite this very large addition of the comonomer butene-1, the density of the resulting polymer was not sufficiently reduced, clearly indicating an example of very inefficient polymerization.
またこの共重合体のプレス成形物は表面がべた
つき、破断点強度は145Kg/cm2、伸び680%であつ
た。 The press-molded product of this copolymer had a sticky surface, a strength at break of 145 kg/cm 2 and an elongation of 680%.
実施例 2
無水塩化マグネシウム830g、オキシ塩化アル
ミニウム50gおよび四塩化チタン170gを実施例
1と同様にしてボールミリングした。得られた固
体物質は1gあたりチタンを41mg含有していた。Example 2 830 g of anhydrous magnesium chloride, 50 g of aluminum oxychloride and 170 g of titanium tetrachloride were ball milled in the same manner as in Example 1. The solid material obtained contained 41 mg titanium per gram.
この固体物質を200mg/hr、トリエチルアルミ
ニウムを50m−mol/hrの速度で供給して80℃で
実施例1と同様の重合を行なつた。ただし気相中
の組成はエチレン、ブテン−1および水素を65:
25:10(モル比)の割合とした。 Polymerization was carried out in the same manner as in Example 1 at 80° C. by feeding this solid substance at a rate of 200 mg/hr and triethylaluminum at a rate of 50 mmol/hr. However, the composition in the gas phase is ethylene, butene-1, and hydrogen at 65:
The ratio was 25:10 (molar ratio).
10時間連続運転の後重合を停止し、反応器の内
部を点検したがポリマーの付着は全くなかつた。 After 10 hours of continuous operation, polymerization was stopped and the inside of the reactor was inspected, but no polymer was observed at all.
得られたポリマーはMI2.9、かさ密度0.403、密
度0.863であり、また重合活性は302000gポリマ
ー/g−Tiであつた。またこの共重合体のプレ
ス成形物は透明であり表面にべたつきはなく、そ
の破断点強度は185Kg/cm2、伸びは750%であつ
た。 The obtained polymer had an MI of 2.9, a bulk density of 0.403, a density of 0.863, and a polymerization activity of 302,000 g polymer/g-Ti. The press-molded product of this copolymer was transparent and had no stickiness on the surface, and had a strength at break of 185 Kg/cm 2 and an elongation of 750%.
押出機により造粒したものを10%高密度ポリエ
チレンにペレツトブレンドし、インフレーシヨン
フイルムに成膜したところ、高密度ポリエチレン
単独の場合に比べ、透明性が著しく改善された。 When the pellets granulated using an extruder were blended with 10% high-density polyethylene and formed into a blown film, the transparency was significantly improved compared to when high-density polyethylene was used alone.
比較例 2
実施例2と同じ触媒を用いてn−パラフインを
溶媒として溶液重合による連続重合を行なつた。Comparative Example 2 Continuous solution polymerization was carried out using the same catalyst as in Example 2 and n-paraffin as a solvent.
すなわち実施例2で合成した固体物質を1当
り25mg、トリエチルアルミニウムを5m−mol含
むn−パラフインを40/hrの速度で供給し、エ
チレン8Kg/hr、ブテン−1を19Kg/hr(エチレ
ンに対して120mol%)、水素0.1Nm3/hrの割合で
供給し、160℃で連続重合を行なつた。 That is, 25 mg/hr of the solid material synthesized in Example 2 and n-paraffin containing 5 mmol of triethylaluminum were supplied at a rate of 40/hr, and 8 kg/hr of ethylene and 19 kg/hr of butene-1 (relative to ethylene) were supplied at a rate of 40/hr. (120 mol%) and hydrogen at a rate of 0.1 Nm 3 /hr, and continuous polymerization was carried out at 160°C.
得られた共重合体はMI1.8、密度0.931であり、
重合活性は82000gポリマー/g−Tiであつた。
またこの共重合体のプレス成形物は破断点強度
150Kg/cm2、伸び570%であつた。 The obtained copolymer had an MI of 1.8 and a density of 0.931.
The polymerization activity was 82000 g polymer/g-Ti.
In addition, press-molded products of this copolymer have a strength at breakage of
The weight was 150Kg/cm 2 and the elongation was 570%.
このように溶液重合による場合にはエチレンに
対して大過剰のブテン−1を使用しているにもか
かわらず、密度はあまり低下せず、また重合活性
も低く、効率の悪い重合の例であることが明らか
である。 In this way, in the case of solution polymerization, although a large excess of butene-1 is used relative to ethylene, the density does not decrease much and the polymerization activity is also low, which is an example of inefficient polymerization. That is clear.
実施例 3
無水塩化マグネシウム830g、アントラセン120
gおよび四塩化チタン180gを実施例1と同様に
ボールミリングして固体物質を得た。該固体物質
は1gあたりチタンを40mg含有していた。Example 3 Anhydrous magnesium chloride 830g, anthracene 120g
g and 180 g of titanium tetrachloride were ball milled in the same manner as in Example 1 to obtain a solid material. The solid material contained 40 mg titanium per gram.
実施例1と同じ装置を用い80℃で固体物質を
500mg/hr、トリイソブチルアルミニウム150m−
mol/hrの速度で供給し、気相中のエチレン、ブ
テン−1および水素の割合(モル比)を68:21:
11となるように調整しながら連続重合を行なつ
た。 Using the same equipment as in Example 1, a solid substance was prepared at 80°C.
500mg/hr, triisobutylaluminum 150m-
The ratio (mole ratio) of ethylene, butene-1 and hydrogen in the gas phase was 68:21:
Continuous polymerization was carried out while adjusting the molecular weight to 11.
10時間安定に連続運転を行なつたのちリアクタ
ーを開放したところ付着は全くなかつた。 When the reactor was opened after 10 hours of stable continuous operation, there was no adhesion at all.
生成ポリマーはMI2.6、かさ密度0.374、密度
0.878であり、重合活性は137000gポリマー/g
−Tiであつた。またこの共重合体をプレス成形
したものは透明で表面にべたつきがなく、破断点
強度200Kg/cm2、伸び800%であつた。 The resulting polymer has an MI of 2.6, a bulk density of 0.374, and a density of
0.878, and the polymerization activity is 137000g polymer/g
-It was Ti. Press-molded products of this copolymer were transparent, had no stickiness on the surface, had a strength at break of 200 kg/cm 2 and an elongation of 800%.
実施例 4
酸化マグネシウム400gと塩化アルミニウム1.3
Kgとを300℃で4時間反応させて得られた反応物
を950gと四塩化チタン180gとを実施例1と同様
にして処理して固体物質を得た。該固体物質は1
gあたりチタンを40mg含有していた。Example 4 Magnesium oxide 400g and aluminum chloride 1.3
950 g of the reaction product obtained by reacting Kg at 300° C. for 4 hours and 180 g of titanium tetrachloride were treated in the same manner as in Example 1 to obtain a solid material. The solid substance is 1
Contains 40mg of titanium per gram.
実施例1と同じ装置を用い、この固体物質500
mg/hrおよびトリイソブチルアルミニウム250m
−mol/hrの割合で触媒を供給し、また気相中の
エチレン、ブテン−1および水素の割合(モル
比)を75:15:10となるようにして80℃で連続重
合を行なつた。 Using the same apparatus as in Example 1, 500
mg/hr and triisobutyl aluminum 250m
Continuous polymerization was carried out at 80°C by supplying the catalyst at a rate of -mol/hr and by adjusting the ratio (molar ratio) of ethylene, butene-1 and hydrogen in the gas phase to 75:15:10. .
16時間連続運転後重合を停止し、リアクター内
部の点検を行なつたがポリマーの付着はみられな
かつた。 After 16 hours of continuous operation, polymerization was stopped and the inside of the reactor was inspected, but no polymer was observed.
生成ポリマーは平均粒径600μの粒度分布の狭
いほぼ真球の粒子で、かさ密度0.391、MI0.71、
密度0.902であり、また重合活性は231000gポリ
マー/g−Tiであつた。またこの共重合体のプ
レス成形物は透明で表面にべたつきがなく、破断
点強度260Kg/cm2、伸び600%であつた。 The resulting polymer has an average particle size of 600μ, a narrow particle size distribution, almost perfectly spherical particles, a bulk density of 0.391, an MI of 0.71,
The density was 0.902, and the polymerization activity was 231,000 g polymer/g-Ti. Further, a press-molded product of this copolymer was transparent, had no stickiness on the surface, had a strength at break of 260 kg/cm 2 and an elongation of 600%.
実施例 5
酸化マグネシウム400gと塩化アルミニウム1.3
Kgとを300℃で4時間反応させて得られた反応物
950g、四塩化チタン180gならびにVO
(OC2H5)345gとを窒素雰囲気下、室温で14時間
ボールミリングして、チタン化合物およびバナジ
ウム化合物を担体に担持させた。この固体物質は
1gあたり40mgのチタンおよび9.8mgのバナジウ
ムを含有していた。Example 5 Magnesium oxide 400g and aluminum chloride 1.3
Reactant obtained by reacting with Kg at 300℃ for 4 hours
950g, titanium tetrachloride 180g and VO
(OC 2 H 5 ) 3 was ball milled for 14 hours at room temperature under a nitrogen atmosphere to support the titanium compound and vanadium compound on the carrier. This solid material contained 40 mg titanium and 9.8 mg vanadium per gram.
気相重合装置としてはステンレス製オートクレ
ーブを用い、ブロワー、流量調節器および乾式サ
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を調節し
た。 A stainless steel autoclave was used as the gas phase polymerization apparatus, a loop was created with a blower, a flow rate controller, and a dry cyclone, and the temperature of the autoclave was adjusted by flowing hot water through the jacket.
重合温度は80℃とし、オートクレーブに上記固
体物質を600mg/hrおよびトリイソブチルアルミ
ニウム250m−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、ブテン−1および水素の組成(モル比)
をそれぞれ75%、15%および10%となるように調
整しながら5重合を行つた。 The polymerization temperature was 80°C, the above solid material was fed into the autoclave at a rate of 600 mg/hr and triisobutylaluminum 250 m-mol/hr, and
Composition (mole ratio) of ethylene, butene-1 and hydrogen in the gas supplied to the autoclave by the blower
Five polymerizations were carried out while adjusting the amounts to 75%, 15%, and 10%, respectively.
生成ポリマーはメルトインデツクス(MI)
0.65、かさ密度0.401、密度0.905であり、密度が
きわめて低いにもかかわらず粘着性がなく、平均
粒径600μの粒度分布の狭いほぼ真球の粒子であ
つた。また重合活性は216000gポリマー/g−
Tiと非常に高活性であつた。 The produced polymer is melt index (MI)
0.65, bulk density 0.401, and density 0.905, and although the density was extremely low, there was no stickiness, and the particles were almost perfectly spherical with an average particle size of 600 μm and a narrow particle size distribution. In addition, the polymerization activity is 216,000g polymer/g-
It was highly active with Ti.
16時間の連続運転後、重合を停止し、オートク
レーブ内を点検したところ、内壁、撹拌機および
ポリマー抜出管にはポリマーの付着は全く認めら
れなかつた。 After 16 hours of continuous operation, polymerization was stopped and the inside of the autoclave was inspected, and no polymer was observed on the inner wall, stirrer, or polymer outlet tube.
この共重合物をプレス成形したものは透明で表
面のべたつきもなく、破断点強度280Kg/cm2、伸
び630%であつた。 A press molded product of this copolymer was transparent, had no stickiness on the surface, had a strength at break of 280 kg/cm 2 and an elongation of 630%.
また、この共重合体は容易に押出機によつて造
粒でき、さらに容易にインフレーシヨンフイルム
に成形できた。 Further, this copolymer could be easily granulated using an extruder, and furthermore, it could be easily formed into a blown film.
第1図は本発明方法で用いる触媒の調製工程を
示すフローチヤート図である。
FIG. 1 is a flowchart showing the steps for preparing a catalyst used in the method of the present invention.
Claims (1)
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、塩化物または水酸化
物、(b)水酸化マグネシウム、(c)炭酸マグネシウ
ム、(d)酸化マグネシウムおよび(e)塩化マグネシウ
ムからなる群より選ばれる少なくとも一種の固体
の無機化合物を含酸素化合物、含硫黄化合物、炭
化水素、ハロゲン含有物質から選ばれる少なくと
も一種の物質で処理または反応させたものとチタ
ン化合物またはチタン化合物とバナジウム化合物
と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、実質上溶媒のない気
相状態でエチレンとエチレンに対して10ないし
45mol%のブテン−1を共重合させることにより
メルトインデツクス0.01ないし10、かつ密度
0.850g/cm3以上0.910g/cm3未満を有する軟質ま
たは半硬質のエチレン・ブテン−1共重合体を得
ることを特徴とする共重合体の製造方法。1 (a) a double salt, double oxide, carbonate, chloride or hydroxide containing a metal selected from silicon, aluminum and calcium and a magnesium atom, (b) magnesium hydroxide, (c) magnesium carbonate, (d) Treat or react at least one solid inorganic compound selected from the group consisting of magnesium oxide and (e) magnesium chloride with at least one substance selected from oxygen-containing compounds, sulfur-containing compounds, hydrocarbons, and halogen-containing substances. In the presence of a catalyst consisting of a solid material containing a titanium compound or a titanium compound and a vanadium compound and an organoaluminum compound, 10 to 10% of
By copolymerizing 45 mol% butene-1, the melt index is 0.01 to 10 and the density is
A method for producing a copolymer, characterized in that a soft or semi-rigid ethylene-butene-1 copolymer having a weight of 0.850 g/cm 3 or more and less than 0.910 g/cm 3 is obtained.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12855478A JPS5556110A (en) | 1978-10-20 | 1978-10-20 | Preparation of copolymer |
FR7926083A FR2439211B1 (en) | 1978-10-20 | 1979-10-19 | PROCESS FOR PREPARING A COPOLYMER OF ETHYLENE AND BUTENE-1 |
DE19792942367 DE2942367A1 (en) | 1978-10-20 | 1979-10-19 | SOFT OR SEMI-HARD AETHYLENE-BUTEN-1-COPOLYMERS AND METHOD FOR THE PRODUCTION THEREOF |
GB7936295A GB2034336B (en) | 1978-10-20 | 1979-10-19 | Preparation of ethylene-butene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12855478A JPS5556110A (en) | 1978-10-20 | 1978-10-20 | Preparation of copolymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5556110A JPS5556110A (en) | 1980-04-24 |
JPS648010B2 true JPS648010B2 (en) | 1989-02-10 |
Family
ID=14987623
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12855478A Granted JPS5556110A (en) | 1978-10-20 | 1978-10-20 | Preparation of copolymer |
Country Status (4)
Country | Link |
---|---|
JP (1) | JPS5556110A (en) |
DE (1) | DE2942367A1 (en) |
FR (1) | FR2439211B1 (en) |
GB (1) | GB2034336B (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6042806B2 (en) * | 1979-12-26 | 1985-09-25 | 日石三菱株式会社 | Copolymer manufacturing method |
JPS5738837A (en) * | 1980-08-19 | 1982-03-03 | Mitsubishi Chem Ind Ltd | Production of polyolefin film |
JPS57102909A (en) * | 1980-12-17 | 1982-06-26 | Nippon Petrochem Co Ltd | Polyolefin lid |
CA1174800A (en) * | 1981-08-24 | 1984-09-18 | Charles Cozewith | Gas phase method for producing copolymers of ethylene and higher alpha-olefins |
JPS58157839A (en) * | 1982-03-16 | 1983-09-20 | Nippon Oil Co Ltd | Impact-resistant polyolefin resin composition |
IL71357A (en) * | 1983-03-29 | 1987-03-31 | Union Carbide Corp | Process for producing low density ethylene copolymers |
ZA845448B (en) * | 1983-07-15 | 1985-03-27 | Union Carbide Corp | Preparation of elastomeric chlorinated ethylene polymers |
US5256351A (en) * | 1985-06-17 | 1993-10-26 | Viskase Corporation | Process for making biaxially stretched, heat shrinkable VLDPE films |
CA1340037C (en) * | 1985-06-17 | 1998-09-08 | Stanley Lustig | Puncture resistant, heat-shrinkable films containing very low density polyethylene copolymer |
US4976898A (en) * | 1985-06-17 | 1990-12-11 | Viskase Corporation | Process for making puncture resistant, heat-shrinkable films containing very low density polyethylene |
US5059481A (en) * | 1985-06-17 | 1991-10-22 | Viskase Corporation | Biaxially stretched, heat shrinkable VLDPE film |
FR2654108B1 (en) * | 1989-11-08 | 1993-08-20 | Norsolor Sa | NOVEL POLYOLEFIN RUBBERS AND THEIR PREPARATION METHOD. |
JP2539114B2 (en) * | 1991-06-26 | 1996-10-02 | 出光石油化学株式会社 | Method for producing polyolefin |
US5208309A (en) * | 1992-01-31 | 1993-05-04 | Phillips Petroleum Company | Linear, very low density polyethylene polymerization process and products thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AR206852A1 (en) * | 1975-03-10 | 1976-08-23 | Union Carbide Corp | PROCEDURE FOR PREPARING LOW AND MEDIUM DENSITY ETHYLENE POLYMERS IN A FLUID BED REACTOR |
JPS51133386A (en) * | 1975-05-15 | 1976-11-19 | Nippon Oil Co Ltd | A process for manufacturing a polyolefin |
FR2405961A1 (en) * | 1977-10-12 | 1979-05-11 | Naphtachimie Sa | PROCESS FOR THE COPOLYMERIZATION OF OLEFINS IN A GAS PHASE IN THE PRESENCE OF A FLUIDIZED COPOLYMER BED AND A CATALYST CONTAINING TITANIUM AND MAGNESIUM |
-
1978
- 1978-10-20 JP JP12855478A patent/JPS5556110A/en active Granted
-
1979
- 1979-10-19 FR FR7926083A patent/FR2439211B1/en not_active Expired
- 1979-10-19 GB GB7936295A patent/GB2034336B/en not_active Expired
- 1979-10-19 DE DE19792942367 patent/DE2942367A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
DE2942367A1 (en) | 1980-05-08 |
FR2439211B1 (en) | 1986-03-21 |
GB2034336B (en) | 1983-03-30 |
GB2034336A (en) | 1980-06-04 |
JPS5556110A (en) | 1980-04-24 |
FR2439211A1 (en) | 1980-05-16 |
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