JPS63230752A - Butene-1-polymer composition - Google Patents
Butene-1-polymer compositionInfo
- Publication number
- JPS63230752A JPS63230752A JP6355087A JP6355087A JPS63230752A JP S63230752 A JPS63230752 A JP S63230752A JP 6355087 A JP6355087 A JP 6355087A JP 6355087 A JP6355087 A JP 6355087A JP S63230752 A JPS63230752 A JP S63230752A
- Authority
- JP
- Japan
- Prior art keywords
- butene
- polymer
- weight
- polymer composition
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims description 37
- 239000000203 mixture Substances 0.000 title claims description 28
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 96
- 239000011256 inorganic filler Substances 0.000 claims description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 description 19
- -1 ethylene, propylene Chemical group 0.000 description 14
- 239000010936 titanium Substances 0.000 description 14
- 239000011949 solid catalyst Substances 0.000 description 13
- 229910052719 titanium Inorganic materials 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 5
- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 4
- 150000002391 heterocyclic compounds Chemical class 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- HBEDSQVIWPRPAY-UHFFFAOYSA-N 2,3-dihydrobenzofuran Chemical compound C1=CC=C2OCCC2=C1 HBEDSQVIWPRPAY-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229960005233 cineole Drugs 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- SHSGDXCJYVZFTP-UHFFFAOYSA-N 4-ethoxybenzoic acid Chemical compound CCOC1=CC=C(C(O)=O)C=C1 SHSGDXCJYVZFTP-UHFFFAOYSA-N 0.000 description 2
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KXDANLFHGCWFRQ-UHFFFAOYSA-N magnesium;butane;octane Chemical compound [Mg+2].CCC[CH2-].CCCCCCC[CH2-] KXDANLFHGCWFRQ-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- SKBXVAOMEVOTGJ-UHFFFAOYSA-N xi-Pinol Chemical compound CC1=CCC2C(C)(C)OC1C2 SKBXVAOMEVOTGJ-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- JCIDEANDDNSHQC-UHFFFAOYSA-N 4H-chromene Chemical compound C1=CC=C2CC=COC2=C1 JCIDEANDDNSHQC-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- FDIQRCXSVQETOX-UHFFFAOYSA-N C(CCC)OCCO.C(C1=CC=CC=C1)(=O)OC(C1=CC=CC=C1)=O Chemical compound C(CCC)OCCO.C(C1=CC=CC=C1)(=O)OC(C1=CC=CC=C1)=O FDIQRCXSVQETOX-UHFFFAOYSA-N 0.000 description 1
- NYEVYCIEQJOVQY-UHFFFAOYSA-N C1CCCCC1[Mg]C1CCCCC1 Chemical compound C1CCCCC1[Mg]C1CCCCC1 NYEVYCIEQJOVQY-UHFFFAOYSA-N 0.000 description 1
- HENIWZDYNSCJGQ-UHFFFAOYSA-N CCCCCCCC[Mg]CC Chemical compound CCCCCCCC[Mg]CC HENIWZDYNSCJGQ-UHFFFAOYSA-N 0.000 description 1
- HYLHFOVZFADXNK-UHFFFAOYSA-N CCCCCC[Mg]CC Chemical compound CCCCCC[Mg]CC HYLHFOVZFADXNK-UHFFFAOYSA-N 0.000 description 1
- YELRSUYYIQXYLP-UHFFFAOYSA-N CCCCCC[Mg]CCCC Chemical compound CCCCCC[Mg]CCCC YELRSUYYIQXYLP-UHFFFAOYSA-N 0.000 description 1
- MVECFARLYQAUNR-UHFFFAOYSA-N CCCC[Mg]CC Chemical compound CCCC[Mg]CC MVECFARLYQAUNR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 239000004677 Nylon Chemical group 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010066 TiC14 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical compound C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910000830 fernico Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000011494 foam glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZDTVRDLORWIEDJ-UHFFFAOYSA-M magnesium butan-1-olate titanium(4+) chloride Chemical compound [O-]CCCC.[O-]CCCC.[O-]CCCC.[O-]CCCC.[Ti+4].[Cl-].[Mg+2] ZDTVRDLORWIEDJ-UHFFFAOYSA-M 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001778 nylon Chemical group 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229910000889 permalloy Inorganic materials 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000008039 phosphoramides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001294 propane Substances 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
- 239000008262 pumice Substances 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000005335 volcanic glass Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229940075420 xanthine Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明はブテン−１重合体組成物に関し、さらに詳し
く言うと、無機質充填材の均一分散性が高く、優れた成
形品外観を実現するとともに耐衝撃性などの機械的特性
にも優れ、各種射出成形品および押出成形品に好適に利
用することができるブテン−１重合体組成物に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a butene-1 polymer composition, and more specifically, the present invention relates to a butene-1 polymer composition, which has high uniform dispersibility of an inorganic filler, realizes an excellent appearance of a molded product, and The present invention relates to a butene-1 polymer composition that has excellent mechanical properties such as impact resistance and can be suitably used for various injection molded products and extrusion molded products.
［従来の技術およびその問題点］
ブテン−１重合体に無機質充填材を配合してなる組成物
としては、たとえばカーボンブラックを配合してなる導
電性樹脂組成物（特開昭４８−３２４２２号公報参照）
、金属酸化物粉末を配合してなる導電性樹脂組成物（特
開昭５０−８５５１号、特開昭８０−３１５５０号公報
参照）などが知られており、また実用に供されている。[Prior art and its problems] As a composition made by blending an inorganic filler with a butene-1 polymer, for example, a conductive resin composition containing carbon black (Japanese Patent Application Laid-open No. 32422/1983) reference)
, conductive resin compositions containing metal oxide powder (see JP-A-50-8551 and JP-A-80-31,550) are known and are in practical use.
これらの従来の樹脂組成物を製造するにあたっては、通
常の場合、無機質充填材を高濃度で含有するマスターバ
ッチを調製し、これを残余の樹脂に混合する方法が用い
られている。In producing these conventional resin compositions, a method is usually used in which a masterbatch containing a high concentration of inorganic filler is prepared and mixed with the remaining resin.
しかしながら、従来の樹脂組成物においては。However, in conventional resin compositions.
使用するブテン−１重合体の分子量分布が狭いため、マ
スターバッチにおける樹脂への分散が悪く、その結果、
得られる成形品の外観が良好とは言い難く、また、導電
性繊維などの無機質充填材を配合する場合、その配合・
量に相当する導電性の向上を図ることができないという
問題を有している。Due to the narrow molecular weight distribution of the butene-1 polymer used, dispersion into the resin in the masterbatch is poor, and as a result,
It is difficult to say that the appearance of the resulting molded product is good, and when adding inorganic fillers such as conductive fibers, the mixing and
There is a problem in that it is not possible to improve the conductivity corresponding to the amount.
［発明の目的］
この発明の目的は、前記問題を解消し、無機質充填材の
分散性が高く、成形品外観および機械的特性が優れたブ
テン−１重合体組成物を提供することである。[Object of the Invention] An object of the present invention is to solve the above-mentioned problems and provide a butene-1 polymer composition in which the inorganic filler is highly dispersible and the molded product has excellent appearance and mechanical properties.
［前記目的を達成するための手段］
前記目的を達成するために、この発明者が鋭意検討を重
ねた結果、特定のブテン−１重合体を用いた場合には、
無機質充填材の均一分散性を高めて成形品外観および機
械的特性に優れたブテン−１重合体組成物が得られるこ
とを見い出してこの発明に到達した。[Means for achieving the above object] In order to achieve the above object, as a result of extensive studies by this inventor, when a specific butene-1 polymer is used,
The present invention was accomplished by discovering that a butene-1 polymer composition with improved uniform dispersibility of an inorganic filler and excellent molded product appearance and mechanical properties can be obtained.
すなわち、この発明の概要は、ブテン−１重合体１００
重量部と、無機質充填材２〜４００重量部とを配合して
なる組成物であって、ブテン−１ｆｆｉ合体のメルトイ
ンデックスが３〜８０ ｇ／１０分であり、かつ重量平
均分子量／ａ平均分子量が４〜１５の範囲内のものであ
ることを特徴とするブテン−１重合体組成物である。That is, the outline of this invention is that butene-1 polymer 100
parts by weight and 2 to 400 parts by weight of an inorganic filler, the melt index of the butene-1ffi combination is 3 to 80 g/10 minutes, and the weight average molecular weight/a average molecular weight is in the range of 4 to 15.
この発明において、前記ブテン−１重合体は、ブテン−
単独重合体またはブテン−１共重合体である。In this invention, the butene-1 polymer is
It is a homopolymer or a butene-1 copolymer.
ブテン−１共重合体は、モノマ一単位としてブテン−１
以外のオレフィンを２５モル％以下の割合で含有するの
が好ましい。Butene-1 copolymer has butene-1 as one monomer unit.
It is preferable to contain olefins other than 25 mol % or less.
七ツマ一単位としての前記オレフィンの含有量が２５モ
ル％を超えると、成形品の表面がべとつき易くなること
がある。If the content of the olefin as one unit exceeds 25 mol%, the surface of the molded product may become sticky.
モノマ一単位としてブテン−１共重合体中に組み込まれ
る前記オレフィンとしては、たとえばエチレン、プロピ
レン、ペンテン−１、オクテン−１１ヘキセン−１，デ
セン−１，Ｆデセン−１等の直鎖モノオレフィン：４−
メチル−ペンテン−１等の分岐モノオレフィン：ブタジ
ェン等のジエン類などが挙げられる。Examples of the olefin incorporated into the butene-1 copolymer as a monomer unit include linear monoolefins such as ethylene, propylene, pentene-1, octene-11hexene-1, decene-1, and F-decene-1: 4-
Branched monoolefins such as methyl-pentene-1; and dienes such as butadiene.
ブテン−１共重合体中のモノマ一単位としてのこれらオ
レフィンは、一種単独であっても良いし、また二種以上
であっても良い。These olefins as one monomer unit in the butene-1 copolymer may be used alone or in combination of two or more.
本発明におけるブテン−１共重合体は、たとえば、触媒
として一般式
％式％
（ただし、式中 ｌｉｔ 、 Ｒ２はアルキル基、ｍは
０≦ｍ≦２、ｎは０≦ｎ≦２を満足する。）で示される
マグネシウムを含む特定の固体酸触媒成分、有機アルミ
ニウム化合物および特定の電子供与性化合物を使用して
、エチレンとブテン−１とを気相にて反応させることに
より容易に製造することができる。The butene-1 copolymer in the present invention can be used as a catalyst, for example, by the following formula: Easily produced by reacting ethylene and butene-1 in the gas phase using a specific solid acid catalyst component containing magnesium, an organoaluminum compound, and a specific electron-donating compound shown in Can be done.
具体的には、特願昭８１−１４４０９３号、特願昭８１
−１９８２８５号、特願昭８１−１９８２８８号、特願
昭８１−１９８７２２号明細書に記載された製造技術に
おいて、本発明の共重合体の前記特性を目安として、製
造条件を実験的に設定することにより、製造することが
できる。Specifically, Japanese Patent Application No. 81-144093, Japanese Patent Application No. 1981
-198285, Japanese Patent Application No. 81-198288, and Japanese Patent Application No. 81-198722, the manufacturing conditions are experimentally set using the above characteristics of the copolymer of the present invention as a guide. It can be manufactured by
以下、本発明のブテン−１共重合体を製造する方法につ
いて、特願昭８１−１９８２８５号明細書に記載された
方法に沿って説明するが、本発明のブテン−１共重合体
がこの製造方法により拘束を受けるものではない。The method for producing the butene-1 copolymer of the present invention will be explained below in accordance with the method described in Japanese Patent Application No. 198285/1985. There are no restrictions on the method.
本発明におけるブテン−１共重合体は、特定の固体触媒
成分（Ａ）、有機アルミニウム化合物ＣＢ）および特定
の電子供与性化合物（Ｃ）から得られる触媒の存在下に
、気相重合条件下で、ブテン−１またはブテン−１とブ
テン−１以外のオレフィンとを反応させることにより得
ることができる固体触媒成分（Ａ）は。The butene-1 copolymer in the present invention is produced under gas phase polymerization conditions in the presence of a catalyst obtained from a specific solid catalyst component (A), an organoaluminum compound CB) and a specific electron donating compound (C). , the solid catalyst component (A) can be obtained by reacting butene-1 or butene-1 with an olefin other than butene-1.
式＝ＭｇＲ’ Ｒ２
（式中 Ｒ１及びＲ２は、炭素数１〜２０のアルキル基
を表し、同一であっても異なっていてもよい、）
で示される有機マグネシウム化合物の少なくとも一種を
、少なくとも一種の塩素化剤で塩素化して担体を得、こ
の担体を、電子供与体の存在下に、かつ−２５〜＋１８
０℃の範囲内の温度下に、４価チタンのハロゲン化物と
接触させることにより調製することができる。At least one organomagnesium compound represented by the formula = MgR' R2 (wherein R1 and R2 represent an alkyl group having 1 to 20 carbon atoms and may be the same or different), A carrier is obtained by chlorination with a chlorinating agent, and this carrier is treated in the presence of an electron donor and between −25 and +18
It can be prepared by contacting a tetravalent titanium halide at a temperature within the range of 0°C.
前記有機マグネシウム化合物としては、ジエチルマグネ
シウム、エチルブチルマグネシウム、エチルヘキシルマ
グネシウム、エチルオクチルマグネシウム、ジブチルマ
グネシウム、ブチルヘキシルマグネシウム、ブチルオク
チルマグネシウム、ジシクロヘキシルマグネシウムなど
のアルキルマグネシウムが挙げられる。Examples of the organic magnesium compound include alkylmagnesiums such as diethylmagnesium, ethylbutylmagnesium, ethylhexylmagnesium, ethyloctylmagnesium, dibutylmagnesium, butylhexylmagnesium, butyloctylmagnesium, and dicyclohexylmagnesium.
前記塩素化剤としては、塩素ガスおよび塩化アルキルを
挙げることができ、特に塩素ガスと塩化ブチルとを併用
するのが好ましい。Examples of the chlorinating agent include chlorine gas and alkyl chloride, and it is particularly preferable to use chlorine gas and butyl chloride in combination.
前記塩素化は、通常、０〜１００℃、好ましくは２０〜
８０℃、特に好ましくは２０〜４０℃の温度下に行なう
。The chlorination is usually carried out at a temperature of 0 to 100°C, preferably 20 to 100°C.
It is carried out at a temperature of 80°C, particularly preferably from 20 to 40°C.
この塩素化によって、マグネシウム原子に結合している
アルキル基の一部が塩素原子で置換される。しかも、ア
ルキル基の少なくとも一部は残存しているので、この残
存するアルキル基の作用によって正常な結晶格子の生成
が妨げられ、適当な表面積及び孔容積を有する非常に小
さい結晶サイズの非層状物が生成する。By this chlorination, a part of the alkyl group bonded to the magnesium atom is replaced with a chlorine atom. Moreover, since at least some of the alkyl groups remain, the action of the remaining alkyl groups prevents the formation of a normal crystal lattice, resulting in a very small crystal size non-layered product with appropriate surface area and pore volume. is generated.
このようにして得られた非層状物は、要すればアルコー
ル処理を行った後、非層状物を電子供与体の存在下に４
価チタンのハロゲン化物で処理する。４価チタンのハロ
ゲン化物による処理は２通常の場合、−２５〜＋１８０
℃の範囲内の温度下に行なう。The non-layered material obtained in this way is treated with alcohol if necessary, and then the non-layered material is 4
treatment with titanium halides. Treatment of tetravalent titanium with halides is usually -25 to +180
Perform the test at a temperature within the range of °C.
前記４価チタンのハロゲン化物としては、テトラハロゲ
ン化チタン、トリハロゲン化アルコキシチタン、ジハロ
ゲン化アルコキシチタン、モノハロゲン化トリアルコキ
シチタンなどを挙げることができ、特に四塩化チタンを
用いるのが好ましい。Examples of the tetravalent titanium halide include titanium tetrahalide, alkoxytitanium trihalide, alkoxytitanium dihalide, trialkoxytitanium monohalide, and titanium tetrachloride is particularly preferred.
前記電子供与体としては、酸素、窒素、リンあるいは硫
黄を含有する有機化合物を使用することができ、この電
子供与体の具体例としては、たとえばアミン類、アミド
類、ケトン類、ニトリル類、ホスフィン類、ホスホルア
ミド類、エステル類、エーテル類、チオエーテル類、チ
オエステル類、酸無水物類、酸ハライド類、アルデヒド
類、有機酸類およびエステル類などが挙げられる。As the electron donor, an organic compound containing oxygen, nitrogen, phosphorus, or sulfur can be used, and specific examples of the electron donor include amines, amides, ketones, nitriles, and phosphines. Examples include phosphoramides, esters, ethers, thioethers, thioesters, acid anhydrides, acid halides, aldehydes, organic acids, and esters.
これらの中でも、好ましいのは、エステル類。Among these, esters are preferred.
エーテル類、ケトン類、酸無水物類であり、さらに具体
的には、安息香酸、ｐ−メトキシ安息香酸、ｐ−エトキ
シ安息香酸、トルイル酸、ジインブチルフタレート、ベ
ンゾキノン、無水安息香酸エチレングリコールブチルエ
ーテルなどを好適に使用することができる。Ethers, ketones, acid anhydrides, and more specifically, benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, toluic acid, diynebutyl phthalate, benzoquinone, benzoic anhydride ethylene glycol butyl ether, etc. can be suitably used.
このようにして調製した固体触媒成分（轟）は。The solid catalyst component (Todoroki) prepared in this way is:
ハロゲン／チタン（モル比）が、通常、３〜２００゜好
ましくは４〜１００であり、マグネシウム／チタン（モ
ル比）が、通常、ｌ〜３０、好ましくは５〜７０である
。The halogen/titanium (molar ratio) is usually 3 to 200°, preferably 4 to 100, and the magnesium/titanium (molar ratio) is usually 1 to 30, preferably 5 to 70.
前記有機アルミニウム化合物（Ｂ）としては、特に制限
はないが、特１′、、−リアルキルアルミニウムが好適
である。The organoaluminum compound (B) is not particularly limited, but 1'--realkylaluminum is particularly preferred.
前記電子供与性化合物（Ｃ）は、次の一般式で表わされ
る複素環式化合物である。The electron donating compound (C) is a heterocyclic compound represented by the following general formula.
（ただし、式中、Ｒ３およびＲ６は炭化水素基を、好ま
しくは炭′１ｇ数２〜５の置換または非置換の飽和また
は不飽和の炭化水素を、また、Ｒ４、Ｒ５およびＲ７は
水素または炭化水素基を、好ましくは水素または炭素数
２〜５の置換または非置換の飽和または不飽和の炭化水
素基をそれぞれ表わす、）
前記複素環式化合物としては、たとえば、 １．４−シ
ネオール、１．８−シネオール、膳−シネオール、ピノ
ール、ベンゾフラン、２，３−ジヒドロベンゾフラン（
クマラン） 、 ２Ｈ−クロメン、 ４Ｈ−クロメン、
クロマン、インクロマン、ジベンゾフラン、キサンチン
などが挙げられる。(However, in the formula, R3 and R6 represent a hydrocarbon group, preferably a substituted or unsubstituted saturated or unsaturated hydrocarbon having 2 to 5 carbon atoms, and R4, R5 and R7 represent hydrogen or a hydrocarbon group. The heterocyclic compound preferably represents hydrogen or a substituted or unsubstituted saturated or unsaturated hydrocarbon group having 2 to 5 carbon atoms, respectively. 8-cineole, Zen-cineole, pinol, benzofuran, 2,3-dihydrobenzofuran (
Kumaran), 2H-chromene, 4H-chromene,
Examples include chroman, inchroman, dibenzofuran, and xanthine.
これら各種の複素環式化合物は、一種単独で使用しても
良いし、また二種以上を併用しても良い。These various heterocyclic compounds may be used alone or in combination of two or more.
前記各種の複素環式化合物の中でも、ｌ、８−シネオー
ルが好ましい。Among the various heterocyclic compounds, l,8-cineole is preferred.
なお、このブテン−１ｆｉ合体の製造における触媒の組
成として、前記有機アルミニウム化合物（Ｂ）の使用量
は、前記固体触媒成分（Ａ）中の４価チタンのハロゲン
化合物に対して１通常、０．１〜１０００倍モル、好ま
しくは１〜５００倍モルである。As for the composition of the catalyst in the production of this butene-1fi combination, the amount of the organoaluminum compound (B) used is usually 1. The amount is 1 to 1000 times by mole, preferably 1 to 500 times by mole.
また、前記電子供与性化合物（Ｇ）の使用量は、前記固
体触媒成分（Ａ）中の４価チタンのハロゲン化合物にお
けるチタン原子に対して、通常、０゜１〜５００倍モル
、好ましくは０．５〜２００倍モルである。The amount of the electron donating compound (G) to be used is usually 0.1 to 500 times the mole of titanium in the halogen compound of tetravalent titanium in the solid catalyst component (A), preferably 0. .5 to 200 times the mole.
気相重合温度は、通常、４５〜８０℃、好ましくは５０
〜７０℃である。The gas phase polymerization temperature is usually 45 to 80°C, preferably 50°C.
~70°C.
重合圧力は、原料成分の液化が実質的に起こらない範囲
内で適宜に設定することができ１通常の場合は、１〜ｔ
５Ｋｇ／ｃゴ程度である。The polymerization pressure can be appropriately set within a range in which liquefaction of the raw material components does not substantially occur.
It is about 5Kg/c.
また、分子量をｒＡ節する目的で、水素のような分子１
ｋｇ４Ｗｉ剤を共存させても良い、さらにまた。In addition, for the purpose of reducing the molecular weight to rA, a molecule such as hydrogen 1
Furthermore, kg4Wi agent may also be present.
共重合体の凝集防止を目的として、ブテン−１より沸点
の低い不活性ガス（例、窒素、メタン、エタン、プロパ
ン）を共存させることもできる。For the purpose of preventing agglomeration of the copolymer, an inert gas having a boiling point lower than that of butene-1 (eg, nitrogen, methane, ethane, propane) may also be present.
この発明においては、上記製造方法により、得られるブ
テン−１重合体のメルトインデックスを３〜６０ ｇ／
ｌｏ分の範囲内とするとともに１重量平均分子量／数平
均分子量（Ｍ ｗ ／ Ｍ ｎ ）を４〜１５の範囲内
とする。In this invention, the melt index of the butene-1 polymer obtained by the above production method is 3 to 60 g/
The weight average molecular weight/number average molecular weight (Mw/Mn) is within the range of 4 to 15.
このような特性を有するブテン−１ｆｉ合体を得るため
の製造条件は、実験により容易に設定することができる
。Manufacturing conditions for obtaining a butene-1fi combination having such characteristics can be easily set through experiments.
この発明で重要なこととして、このブテン−１のメルト
インデックスが、通常、３〜８０ ｇ／１０分、好まし
くは４〜４０ ｇ／ｌｏ分である。It is important for this invention that the melt index of this butene-1 is usually between 3 and 80 g/10 min, preferably between 4 and 40 g/lo min.
前記メルトインデックスが３ ｇ／１０分未満の場合に
は、無機質充填材の均一分散性が低下して得られる組成
物の成形品外観が悪化する。一方、６０ｇ／１０分を超
える場合には、得られる組成物の機械的強度が低下する
。When the melt index is less than 3 g/10 minutes, the uniform dispersibility of the inorganic filler decreases and the appearance of the molded product obtained from the composition deteriorates. On the other hand, if it exceeds 60 g/10 minutes, the mechanical strength of the resulting composition will decrease.
この発明において用いる重合体における分子量分布、す
なわち重合体の重量平均分子量（Ｍｗ）と数平均分子量
（Ｍｏ）との比（Ｍ、／Ｍｎ ）は、通常、４〜１５、
好ましくは４〜ｔｏである。The molecular weight distribution of the polymer used in this invention, that is, the ratio (M, /Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mo) of the polymer is usually 4 to 15,
Preferably it is 4 to to.
前記重量平均分子量／数平均分子量（Ｍｌｌ ／Ｍｌ＋
）が４未満の場合には、成形時の剪断力が増加し、後
述する金属繊維等を配合すると、この金属繊維等が切断
されて導電性の向上が不十分になることがある。一方、
１５を超える場合には、成形品の光沢が低下して得られ
る組成物の成形品外観が悪化することがある。The weight average molecular weight/number average molecular weight (Mll/Ml+
) is less than 4, the shearing force during molding increases, and when metal fibers, etc., which will be described later, are added, the metal fibers, etc. may be cut, resulting in insufficient improvement in conductivity. on the other hand,
If it exceeds 15, the gloss of the molded product may decrease and the appearance of the molded product obtained from the composition may deteriorate.
この発明に用いるブテン−１重合体につき、示差走査熱
量分析装置を用いて示差熱分析を行なうと、最低融点お
よび最高融点を示す二種類の吸熱カーブが得られる。こ
のうち、最高融点は、通常、７０〜１３０℃の範囲内に
ある。When the butene-1 polymer used in this invention is subjected to differential thermal analysis using a differential scanning calorimeter, two types of endothermic curves showing the lowest melting point and the highest melting point are obtained. Among these, the highest melting point is usually within the range of 70 to 130°C.
そして、この発明に用いるブテン−１重合体においては
、最高融点と最低融点の温度差（融点の最高値と最低値
との差）が、通常、４０℃以下、特に０〜３５℃のａ！
囲内にあることが望ましい。In the butene-1 polymer used in this invention, the temperature difference between the highest and lowest melting points (difference between the highest and lowest melting points) is usually 40°C or less, especially a! of 0 to 35°C.
It is desirable that it be within this range.
前記温度差が４０℃を超える場合には、成形品の表面が
べたつき易くなる。If the temperature difference exceeds 40°C, the surface of the molded product tends to become sticky.
前記ブテン−１の示差熱分析に基づく融解熱量は、通常
、４〜２５ ｃａｌ／ｇである。この融解熱量が４ ｃ
ａｌ／ｇ未満の場合には、成形品の表面がべたつき易く
なる。一方、２５ ｃａｌ／ｇを超える場合には、成形
品の透明度が低下することがある。The heat of fusion of butene-1 based on differential thermal analysis is usually 4 to 25 cal/g. This heat of fusion is 4 c
If it is less than al/g, the surface of the molded product tends to become sticky. On the other hand, if it exceeds 25 cal/g, the transparency of the molded product may decrease.
前記無機質充填材としては、たとえば炭酸マグネシウム
、炭酸カルシウム、クレー、カオリン、ベントナイト、
タルク、シリカ、マイカ、けい藻土、けい砂、軽石粒、
スレート粉、アスベスト、アルミナホワイト、硫酸バリ
ウム、リトポン、硫酸カルシウム、二硫化モリブデン、
グラファイト、ガラス繊維、ガラス球、発泡ガラス球、
フライアッシュ、火山ガラス中空体、合成無機中空体、
単結晶チタン酸カリ、カーボンブラック、カーボンファ
イバー、炭素中空体、無煙炭粉末、人造水晶石、マグネ
シウムやカルシウム等の硫酸塩、雲母ひる石、石墨、鉄
、アルコール、亜鉛等の金属または金Ｅ酸化物、フェラ
イトなど各種の天然産および人工の繊維状、もしくはフ
レーク状のものを挙げることができる。Examples of the inorganic filler include magnesium carbonate, calcium carbonate, clay, kaolin, bentonite,
Talc, silica, mica, diatomaceous earth, silica sand, pumice grains,
Slate powder, asbestos, alumina white, barium sulfate, lithopone, calcium sulfate, molybdenum disulfide,
graphite, glass fiber, glass bulb, foam glass bulb,
fly ash, volcanic glass hollow body, synthetic inorganic hollow body,
Single crystal potassium titanate, carbon black, carbon fiber, hollow carbon, anthracite powder, artificial quartzite, sulfates such as magnesium and calcium, mica vermiculite, graphite, iron, alcohol, metals such as zinc, or gold E oxide , ferrite, and various other natural and artificial fibers or flakes.
特に、この発明の組成物を導電性樹脂組成物とする場合
には、金属繊維を配合するのが好ましい。In particular, when the composition of the present invention is used as a conductive resin composition, it is preferable to incorporate metal fibers into the composition.
前記金属繊維としては、長さが３〜１０ｍｍ、好ましく
は４〜８ｍｍであり、アスペクト比が２００〜５０００
、好ましくは３００〜１０００のものが用いられる。The metal fiber has a length of 3 to 10 mm, preferably 4 to 8 mm, and an aspect ratio of 200 to 5000.
, preferably 300 to 1000.
前記長さが３ｍｍ未満の場合には導電効果が十分でない
ことがある。一方、１０ｍｍを超える場合には、混線が
困難になって混線スクリュウ−の摩耗原因になることが
ある。＠記アスペクト比が２００未満の場合には、配合
量を増加させないと十分な導電性を得ることができない
ことがある。一方、アスペクト比が５０００を超える場
合には混練時に金属繊維が破断し易くなり、また混練が
困難になることがある。If the length is less than 3 mm, the conductive effect may not be sufficient. On the other hand, if it exceeds 10 mm, crosstalk becomes difficult and may cause wear of the crosswire screw. If the aspect ratio is less than 200, sufficient conductivity may not be obtained unless the blending amount is increased. On the other hand, if the aspect ratio exceeds 5000, the metal fibers are likely to break during kneading, and kneading may become difficult.
前記金属繊維をａ成する金属としては、たとえばステン
レス、黄銅、アルミニウム、銅、ニッケル、ケイ素鋼、
スズ青銅、リン青銅、フェルニコ、パーマロイ等が挙げ
られる。Examples of the metal forming the metal fiber include stainless steel, brass, aluminum, copper, nickel, silicon steel,
Examples include tin bronze, phosphor bronze, Fernico, and permalloy.
これらの中でも、ステンレス繊維が特に好ましい。Among these, stainless steel fibers are particularly preferred.
前記無機質充填材の配合割合は、前記ブテン−１重合体
１００重量部に対して、通常、２〜４００重量部、好ま
しくは３〜３００重量部である。この配合割合が２重量
部未満の場合には１．たとえば導電性の向上などの充填
効果が十分に得られないことがある。一方、４００重量
部を超える場合には、均一分散性が低下して成形品外観
が悪化することがある。The blending ratio of the inorganic filler is usually 2 to 400 parts by weight, preferably 3 to 300 parts by weight, based on 100 parts by weight of the butene-1 polymer. If this blending ratio is less than 2 parts by weight, 1. For example, a sufficient filling effect such as improved conductivity may not be obtained. On the other hand, if it exceeds 400 parts by weight, the uniform dispersibility may decrease and the appearance of the molded product may deteriorate.
この発明におけるブテン−１２合体組成物は、前記ブテ
ン−１重合体および無機質充填材の他に、さらに第３成
分として熱可塑性樹脂を含んでいても良い。In addition to the butene-1 polymer and the inorganic filler, the butene-12 composite composition of the present invention may further contain a thermoplastic resin as a third component.
前記熱可塑性樹脂としては、たとえばポリエチレン、ポ
リプロピレン、結晶性および非品性エチレンープロピレ
ン共ｍ合体、プロピレン−α−オレフィン共重合体、ポ
リメチルペンテン−１など。Examples of the thermoplastic resin include polyethylene, polypropylene, crystalline and non-crystalline ethylene-propylene copolymers, propylene-α-olefin copolymers, and polymethylpentene-1.
のポリオレフィンおよびこれらの混合物；ポリオレフィ
ンの無水マレイン酸変性物：無水マレイン酸−アクリル
酸グリシジルメタアクリレートなどの共重合性ビニルポ
リマーあるいはビニルシラン：γ−メタクリロキシプロ
ピルトリメトキシシランなどの不飽和基を有する有機シ
ラン化合物で変性したポリオレフィン；ナイロン：ポリ
エチレンテレフタレート；ホリブチレンテレフタレート
：塩化ビニル；ポリアセタール：ポリカーボネート；ポ
リスチレン、ＡＢＳ 、ポリフェニレンサルファイドな
どが挙げられる。これらの中でも、好ましいのはポリオ
レフィン、ポリオレフィンの無水マレイン酸変性物：ポ
リスチレン、ポリエチレンテレフタレート、ポリブチレ
ンテレフタレート。polyolefins and mixtures thereof; polyolefins modified with maleic anhydride: copolymerizable vinyl polymers such as maleic anhydride-glycidyl acrylate methacrylate, or vinyl silanes: organic compounds having unsaturated groups such as γ-methacryloxypropyltrimethoxysilane Polyolefins modified with silane compounds; nylon: polyethylene terephthalate; polybutylene terephthalate: vinyl chloride; polyacetal: polycarbonate; polystyrene, ABS, polyphenylene sulfide, and the like. Among these, preferred are polyolefins and polyolefins modified with maleic anhydride: polystyrene, polyethylene terephthalate, and polybutylene terephthalate.
ポリカーボネートである。It is polycarbonate.
これらの熱可塑性樹脂は、そのメルトインデックスが、
通常、０．５〜３０ ｇ７１０分のものを用いるのが好
ましい。These thermoplastic resins have a melt index of
Usually, it is preferable to use 0.5 to 30 g for 710 minutes.
前記熱可塑性樹脂を用いる場合、その配合割合は前記ブ
テン−１重合体１００重量部に対して、通常、１００重
量部以下である。この配合割合が１００重量部を超える
場合には、得られる成形品の外観が悪化して、この発明
の目的を阻害することがある。When the thermoplastic resin is used, its blending ratio is usually 100 parts by weight or less per 100 parts by weight of the butene-1 polymer. If this blending ratio exceeds 100 parts by weight, the appearance of the resulting molded product may deteriorate, which may impede the object of the present invention.
この発明のブテン−１重合体組成物は、たとえば前記ブ
テン−１重合体の一部と前記無機質充填材とを用いて予
めマスターバッチを形成し、このマスターバッチを残余
のブテン−１重合体と混練する方法や、各成分の全量を
ヘンシェルミキサー等を用いてトライブレンドした後、
バンバリーミキサ−、ニーグー、ロールミル、ｌ軸また
は２軸押出機等を用いて混練する方法などにより得るこ
とができる。The butene-1 polymer composition of the present invention can be obtained by forming a masterbatch in advance using, for example, a portion of the butene-1 polymer and the inorganic filler, and combining this masterbatch with the remaining butene-1 polymer. After the kneading method and the total amount of each ingredient are tri-blended using a Henschel mixer etc.
It can be obtained by kneading using a Banbury mixer, Nigu, roll mill, l-shaft or twin-screw extruder, or the like.
この際、この発明の効果を阻害しない限り、必要に応じ
て帯電防止剤、紫外線吸収剤、熱安定剤、可塑剤、酸化
防止剤、アンチブロッキング剤、滑剤、染顔料等の公知
の添加剤を配合することもで覆る。At this time, known additives such as antistatic agents, ultraviolet absorbers, heat stabilizers, plasticizers, antioxidants, anti-blocking agents, lubricants, dyes and pigments may be added as necessary, as long as they do not impede the effects of the present invention. It can also be mixed and covered.
このようにして得られるこの発明のブテン−１重合体組
成物は、押出成形法、射出成形法、プレス成形法等の成
形手段により所望形状に成形して各種成形品とすること
ができる。また、金属繊維を配合した場合には、少量の
配合量で導電性を高めることができ、電子機器、家電機
器等の軽量電磁波シールド材などに好適に利用すること
ができる。The butene-1 polymer composition of the present invention thus obtained can be molded into a desired shape by a molding method such as an extrusion molding method, an injection molding method, a press molding method, or the like to form various molded products. Furthermore, when metal fibers are blended, the conductivity can be improved with a small amount of blending, and it can be suitably used for lightweight electromagnetic shielding materials for electronic devices, home appliances, and the like.
［発明の効果］
この発明によると、
（１）貨来のブテン−１重合体に比較して分子１分布幅
が広いブテン−１ｆｉ合体を用いているので、金属繊維
などの無機質充填材の均一分散性を高めることができ、
（２） その結果、得られる成形品の外観が良好であ
り、
（３）シかも、機械的特性、特に耐衝撃性に優れる、
等の種々の効果を有するブテン−１重合体組成物を提供
することができる。[Effects of the Invention] According to the present invention, (1) Since a butene-1fi polymer having a wider molecule 1 distribution width than the conventional butene-1 polymer is used, inorganic fillers such as metal fibers can be uniformly distributed. Butene has various effects such as: (2) good appearance of the molded product obtained as a result; and (3) excellent mechanical properties, particularly impact resistance. -1 polymer composition can be provided.
［実施例］ 次に、この発明の実施例および比較例を示し。[Example] Next, examples and comparative examples of the present invention will be shown.
この発明についてさらに詳しく説明する。This invention will be explained in more detail.
（実施例１）
■ 固体触媒 分Ａ）の調
ブチルオクチルマグネシウム（２０％へブタン溶液）
３００ ｇを、機械式攪拌機、還流冷却器１滴下ロート
、ガス供給弁および温度計を備えた５ツロフラスコに仕
込み、フラスコ内に窒素を導入して、フラスコ内憂不活
性雰囲気に保ち、これに、ブチルクロライド５ ｍ ｌ
を滴下ロートを用いて室温で加えた。その後、塩ぶガス
を５ｍｍ交会の速度で加えて塩素化した。(Example 1) ■ Preparation of solid catalyst component A) Butyloctylmagnesium (20% hebutane solution)
300 g was placed in a 5-hour flask equipped with a mechanical stirrer, a reflux condenser, one dropping funnel, a gas supply valve and a thermometer, nitrogen was introduced into the flask to maintain an inert atmosphere within the flask, and the butyl Chloride 5ml
was added at room temperature using an addition funnel. Thereafter, chlorine gas was added at a rate of 5 mm for chlorination.
次に、２５〜３５℃で、 ２．５ ｍｌのシリコンオイ
ルを加え、さらにこの混合物中に１１３ｍＪＬのエタノ
ールを滴下した。エタノールの添加によって生成した塩
素化物が沈殿した。この沈殿物を含む混合液を４０℃で
１時間攪拌した後、温度を７５〜８０℃に上げ、溶液を
この温度で一夜放置した。Next, 2.5 ml of silicone oil was added at 25 to 35°C, and 113 mJL of ethanol was added dropwise into the mixture. The chlorides produced by the addition of ethanol were precipitated. After stirring the mixture containing the precipitate at 40°C for 1 hour, the temperature was raised to 75-80°C and the solution was left at this temperature overnight.
この高温溶液をジインブチルフタレート（電子供与体）
と過剰量の↑ｒｃｌａ とを含む一２５℃に冷却した溶
液中にサイフオンで静かに加え、この低温ＴｒＣ１４中
に反応中間体を沈澱させた０次に。This hot solution is diimbutyl phthalate (electron donor)
The reaction intermediate was precipitated into this cold TrC14 by gently adding it with a siphon into a solution cooled to -25°C containing ↑rcla and an excess of ↑rcla.
この沈殿物を含む混合溶液を室温にまで昇温した。The mixed solution containing this precipitate was heated to room temperature.
次いで、この沈殿物を含む混合溶液に、電子供与体とし
てジイソブチルフタレートをさらに加え、温度を１００
〜１１０℃に上げ、混合溶液をこの温度で１時間保った
８反応生成物を沈降させ、８５℃のへブタンで５〜６回
洗浄し、溶液をサイフオンで他の容器に移した。Next, diisobutyl phthalate was further added as an electron donor to the mixed solution containing the precipitate, and the temperature was raised to 100°C.
The temperature was raised to ~110°C and the mixed solution was kept at this temperature for 1 hour.8 The reaction product was precipitated, washed 5-6 times with hebutane at 85°C, and the solution was transferred to another container with a siphon.
さらに、この溶液に過剰量のＴｉＣ１４を加え、混合物
を１１０℃で１時間攪拌した。生成した沈降物と溶液と
をサイフオンで分離した後、生成した触媒成分（沈殿物
）を数回、ヘプタンで洗浄した（８０℃で５〜６回）。Furthermore, an excess amount of TiC14 was added to this solution, and the mixture was stirred at 110° C. for 1 hour. After separating the generated precipitate and solution using a siphon, the generated catalyst component (precipitate) was washed several times with heptane (5 to 6 times at 80° C.).
得られた沈殿を集めて弱い減圧下に乾燥することにより
チタン含有量が３．０重量％である固体触媒成分（Ａ）
を得た。The obtained precipitate was collected and dried under weak vacuum to obtain a solid catalyst component (A) having a titanium content of 3.0% by weight.
I got it.
■ 度立薩腹皮１１
前記■で得られた固体触媒成分（Ａ）を１文中のチタン
濃度が２ミリモルになるように、触媒５１ｍｌ槽に投入
した。この触媒調製槽に、トリイソブチルアルミニウム
３０ミリモル／ｌ、および１．８−シネオール１２ミリ
モル／見を投入した。その後、チタン原子ｌ騰■ｏｌ当
り５０ｇとなる割合でプロピレンを投入し、触媒調製槽
内を４０℃に昇温し、触媒調製のための反応を行なった
。(2) Hidetachi Satsuma Belly Skin 11 The solid catalyst component (A) obtained in (1) above was placed in a 51 ml catalyst tank so that the titanium concentration per portion was 2 mmol. 30 mmol/l of triisobutylaluminum and 12 mmol/l of 1,8-cineole were charged into this catalyst preparation tank. Thereafter, propylene was added at a rate of 50 g per 1 ol of titanium atom, the temperature inside the catalyst preparation tank was raised to 40° C., and a reaction for catalyst preparation was carried out.
■ ブテン−１７の
直径３００−ｍ、容ａｌ１００ Ｈの流動層重合器を使
用し、前記■で得た触媒をＴｉ原子換算で３．６ミリモ
ル／！Ｌに再調製したＴｉ触媒スラリーを、触媒調製槽
から重犯重合器に０．１５交／時間の流量で、またトリ
インブチルアルミニウム３０ミリモル／時間の流量で、
また１、８−シネオール２４ミリモル／時間の流量でそ
れぞれ前記重合器に供給した。(2) Using a butene-17 fluidized bed polymerization vessel with a diameter of 300 m and a volume of 100 H, the catalyst obtained in (2) above was used at a rate of 3.6 mmol/! in terms of Ti atoms! The Ti catalyst slurry re-prepared to L was transferred from the catalyst preparation tank to the heavy polymerization vessel at a flow rate of 0.15 cycles/hour and at a flow rate of 30 mmol/hour of tri-butylaluminum.
Further, 1,8-cineole was supplied to the polymerization vessel at a flow rate of 24 mmol/hour.
ブテン−１の分圧を３ Ｋｇ／ ｃｒｒｒ’に、窒素の
分圧を４ Ｋｇ／ ｃゴにそれぞれ調整し、ガス空塔速
度が３４ｃ腸１秒の速度となるようにブテン−１、水素
ガスおよび窒素ガスを供給し、反応温度６０℃で重合を
行なってブテン−１重合体を得た。The partial pressure of butene-1 was adjusted to 3 Kg/crrr' and the partial pressure of nitrogen was adjusted to 4 Kg/crr', respectively, and the butene-1 and hydrogen gas were adjusted so that the superficial gas velocity was 34 cm per second. and nitrogen gas were supplied, and polymerization was carried out at a reaction temperature of 60°C to obtain a butene-1 polymer.
■ 紅處糎亘１】
前記■で得られた重合体１００重量部に対して、ステン
レス繊、４９６重量部をトライブレンドした後、１８０
℃の温度下に射出成形して試験片を作成し、得られた試
験片につき、体積固有抵抗、外観およびアイゾツト＃撃
強さの評価を行なった。■ Benifu Wataru 1] After tri-blending 496 parts by weight of stainless steel fibers to 100 parts by weight of the polymer obtained in step (1) above, 180 parts by weight of
A test piece was prepared by injection molding at a temperature of .degree. C., and the resulting test piece was evaluated for volume resistivity, appearance, and Izot impact strength.
（実施例２〜ｌＯ１比較例１および３〜６）前記実施例
１の■において、水素量およびオレフィンモノマー屋を
変えるとともに各成分の配合割合を第１表に示したよう
に変えた以外は、前記実施例１と同様にしてブテン−１
重合体組成物を製造した。(Examples 2 to 1O1 Comparative Examples 1 and 3 to 6) In Example 1, except that the amount of hydrogen and the olefin monomer were changed, and the proportions of each component were changed as shown in Table 1, Butene-1 was prepared in the same manner as in Example 1 above.
A polymer composition was produced.
結果を第１表に示す。The results are shown in Table 1.
（実施例Ｕ）
前記実施例１の■において、トリイソブチルアルミニウ
ム３０ミリモル／時間に代えて、トリイソブチルアルミ
エム２フミリ
ルアルミニウムモノクロライド３ミリモル／時間とした
こと以外は、前記実施例１と同様にしてブテン−１重合
体組成物を製造した。(Example U) Same as Example 1, except that in (1) of Example 1, 30 mmol/hour of triisobutylaluminum was replaced with 3 mmol/hour of triisobutylaluminum 2 fumylylaluminum monochloride. A butene-1 polymer composition was prepared.
結果を第１表に示す。The results are shown in Table 1.
（比較例２）
■ 固体 の調
加熱乾燥した５００ｍｊＬ容量のガラス製三ツロフラス
コ（温度計、攪拌機付き）に、チタンテトラブトキシド
？５ｒｎｌおよび無水塩化マグネシウム１０ｇを完全に
溶解させた。(Comparative Example 2) ■ Preparation of solid Titanium tetrabutoxide was placed in a heat-dried 500 mjL glass Mitsuro flask (with thermometer and stirrer). 5 rnl and 10 g of anhydrous magnesium chloride were completely dissolved.
次いで、この溶液を４０℃にまで冷却し、メチルハイド
ロジエンポリシロキサン１５ｍ Ｊｌを加えることによ
り、塩化マグネシウム拳チタンテトラブトキシド錯体を
析出させた．これを精製へブタンで洗浄した後、四塩化
ケイ素８．７ｍｌとフタル酸ジヘプチル１．８ｍｉとを
加えて５０℃の温度下に２時間保持した。Next, this solution was cooled to 40° C. and 15 m Jl of methylhydrodiene polysiloxane was added to precipitate a magnesium chloride titanium tetrabutoxide complex. After washing this with purified butane, 8.7 ml of silicon tetrachloride and 1.8 ml of diheptyl phthalate were added, and the mixture was kept at a temperature of 50° C. for 2 hours.
その後，さらに精製へブタンによる洗浄を行なって固体
触媒成分を得た。Thereafter, the product was further purified and washed with butane to obtain a solid catalyst component.
得られた固体触媒成分中のチタン含有率は３．０重量％
であり，また、フタル酸ジヘプチル含有率は２５．０％
であった。The titanium content in the obtained solid catalyst component was 3.0% by weight.
, and the diheptyl phthalate content is 25.0%
Met.
■ 火力ｍ装置１
前記実施例１の■において、固体触媒（Ａ）に代えて上
記■で得られた固体触媒を用いたほかは、前記実施例１
の■と同様にして重合触媒を調製した。■ Thermal power m device 1 The same procedure as described in Example 1 was performed except that in (■) of Example 1, the solid catalyst obtained in () above was used instead of the solid catalyst (A).
A polymerization catalyst was prepared in the same manner as in (2).
■ ブテン−１１合体の調製
２０１の重合器へ１時間当り５ｋｇのブテン−１、トリ
エチルアルミニウム１０ミリモルのトリエチルアルミニ
ウム、ビニルトリエトキシシラン１ミリモルおよび上記
■で得た固体触媒Ｏ．ＯＳ ミリモル（Ｔｉｊｉ子換算
）を連続的に導入した。(2) Preparation of butene-11 polymerization 5 kg of butene-1 per hour, 10 mmol of triethylaluminum, 1 mmol of vinyltriethoxysilane, and the solid catalyst O obtained in step (2) above were added to the polymerization vessel of 201. Millimoles of OS (in terms of Tiji particles) was continuously introduced.
なお、反応温度は７０℃に保った。Note that the reaction temperature was maintained at 70°C.
次いで、反応容器の液量が１０見になるように重合液を
連続的に抜き取り、抜き取った反応生成物に少量のエタ
ノールを添加して重合反応を停止させると共に、未反応
成分を除去して、ブテン−１重合体を得た。Next, the polymerization liquid is continuously withdrawn so that the liquid volume in the reaction container becomes 10 mm, and a small amount of ethanol is added to the withdrawn reaction product to stop the polymerization reaction, and unreacted components are removed. A butene-1 polymer was obtained.
■ 紋處隻五１１
前記■で得られた重合体１００重量部に対して、ステン
レス繊！１６重量部をトライブレンドした後、１８０℃
の温度下に射出成形して試験片を作成し、得られた試験
片につき１体積固有抵抗、外観およびアイゾツト衝撃強
さの評価を行なった。■ Mongosengo 11 Stainless steel fiber is added to 100 parts by weight of the polymer obtained in step (■) above! After tri-blending 16 parts by weight, 180°C
A test piece was prepared by injection molding at a temperature of 100.degree. C., and the resulting test piece was evaluated for 1 volume resistivity, appearance, and Izot impact strength.
結果を第１表に示す。The results are shown in Table 1.
（″Ｊｌ施例１２）
前記比較例２の■で得られた固体触媒成分を用い、かつ
前記実施例１の■のトリインブチルアルミニウム３０ミ
リモル／時間の代わりに，トリイソブチルアルミニウム
２５ミリモル／時間およびジエチルアルミニウム５ミリ
モル／時間としたこと以外は、前記実施例１と同様にし
てブテン−１重合体組成物を製造した。("Jl Example 12) Using the solid catalyst component obtained in the above Comparative Example 2 (■), and instead of the triisobutylaluminum 30 mmol/hour in the above Example 1 (■), triisobutylaluminum 25 mmol/hour. A butene-1 polymer composition was produced in the same manner as in Example 1 except that the amount of diethylaluminium was 5 mmol/hour.
結果を第１表に示す。The results are shown in Table 1.
（比較例７）
前記実施例１の■と同様の方法で，メルトインデックス
（ＭＩ） ０．０１ｇ／ｌｏ分のブテン−１単独重合体
とＸＩ ８０ｇ／１０分のブテン−１単独重合体とを製
造した。(Comparative Example 7) A butene-1 homopolymer with a melt index (MI) of 0.01 g/lo and a butene-1 homopolymer with an XI of 80 g/10 were prepared in the same manner as in Example 1 above. Manufactured.
次いで、これらのブテン−１単独重合体を前者／後者＝
４０／６Ｇ （ｉ量比）の割合で用いたこと以外は，
前記実施例１と同様にしてブテン−１重合体組成物を得
た。Then, these butene-1 homopolymers were mixed into former/latter=
Except that it was used at a ratio of 40/6G (i amount ratio),
A butene-1 polymer composition was obtained in the same manner as in Example 1 above.
結果を第１表に示す。The results are shown in Table 1.
（以下，余白）
第 １ 表 （続 き ｌ）第 ２
表 （続 き ３）体積固有抵抗二日本ゴム協
会規格５ＲＩＳ ２３０１に準拠。(Hereafter, blank space) Table 1 (Continued l) Part 2
Table (continued 3) Volume specific resistance 2 Compliant with Japan Rubber Association Standard 5RIS 2301.
Claims (1)
２〜４００重量部とを配合してなる組成物であって、ブ
テン−１重合体のメルトインデックスが３〜６０ｇ／１
０分であり、かつ重量平均分子量／数平均分子量が４〜
１５の範囲内のものであることを特徴とするブテン−１
重合体組成物。(1) A composition comprising 100 parts by weight of a butene-1 polymer and 2 to 400 parts by weight of an inorganic filler, the melt index of the butene-1 polymer being 3 to 60 g/1.
0 minutes, and the weight average molecular weight/number average molecular weight is 4 to
Butene-1, characterized in that it is within the range of 15
Polymer composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62063550A JPH0781051B2 (en) | 1987-03-18 | 1987-03-18 | Butene-1 polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62063550A JPH0781051B2 (en) | 1987-03-18 | 1987-03-18 | Butene-1 polymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63230752A true JPS63230752A (en) | 1988-09-27 |
| JPH0781051B2 JPH0781051B2 (en) | 1995-08-30 |
Family
ID=13232448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62063550A Expired - Fee Related JPH0781051B2 (en) | 1987-03-18 | 1987-03-18 | Butene-1 polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0781051B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101496711B1 (en) * | 2013-08-30 | 2015-03-03 | 주식회사 일렘테크놀러지 | Polybutene-1 polymer composition and molded object formed using the same and method of producing polybutene-1 polymer composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6038414A (en) * | 1983-08-12 | 1985-02-28 | Mitsui Petrochem Ind Ltd | Thermoplastic resin copolymer |
| JPS60262804A (en) * | 1984-06-11 | 1985-12-26 | Mitsui Petrochem Ind Ltd | Polybutene-1 resin |
-
1987
- 1987-03-18 JP JP62063550A patent/JPH0781051B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6038414A (en) * | 1983-08-12 | 1985-02-28 | Mitsui Petrochem Ind Ltd | Thermoplastic resin copolymer |
| JPS60262804A (en) * | 1984-06-11 | 1985-12-26 | Mitsui Petrochem Ind Ltd | Polybutene-1 resin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101496711B1 (en) * | 2013-08-30 | 2015-03-03 | 주식회사 일렘테크놀러지 | Polybutene-1 polymer composition and molded object formed using the same and method of producing polybutene-1 polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0781051B2 (en) | 1995-08-30 |
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