CN1117737A - 具有低熔体粘度和低光衰减的环烯共聚物 - Google Patents
具有低熔体粘度和低光衰减的环烯共聚物 Download PDFInfo
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- CN1117737A CN1117737A CN94191172A CN94191172A CN1117737A CN 1117737 A CN1117737 A CN 1117737A CN 94191172 A CN94191172 A CN 94191172A CN 94191172 A CN94191172 A CN 94191172A CN 1117737 A CN1117737 A CN 1117737A
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- 150000001925 cycloalkenes Chemical class 0.000 title claims abstract 6
- 230000003287 optical effect Effects 0.000 title claims description 23
- 229920000089 Cyclic olefin copolymer Polymers 0.000 title abstract description 20
- 230000004927 fusion Effects 0.000 title description 8
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- -1 C1-C8 alkyl radical Chemical class 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 125000004429 atom Chemical group 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 239000010955 niobium Substances 0.000 claims abstract description 6
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002015 acyclic group Chemical group 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 5
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 125000004122 cyclic group Chemical group 0.000 claims abstract 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 11
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 125000005574 norbornylene group Chemical group 0.000 claims description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- UPWXJBUKAOHZMD-UHFFFAOYSA-N 9-cyclopenta-1,3-dien-1-yl-9h-fluorene Chemical compound C1C=CC=C1C1C2=CC=CC=C2C2=CC=CC=C21 UPWXJBUKAOHZMD-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 230000003311 flocculating effect Effects 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 229920001169 thermoplastic Polymers 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 abstract 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 abstract 1
- 125000002877 alkyl aryl group Chemical group 0.000 abstract 1
- 125000005018 aryl alkenyl group Chemical group 0.000 abstract 1
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 1
- 150000005840 aryl radicals Chemical class 0.000 abstract 1
- 125000004104 aryloxy group Chemical group 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 229910052782 aluminium Inorganic materials 0.000 description 14
- 239000011162 core material Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000004411 aluminium Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000007704 transition Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012780 transparent material Substances 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000010748 Photoabsorption Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- AIXAANGOTKPUOY-UHFFFAOYSA-N carbachol Chemical group [Cl-].C[N+](C)(C)CCOC(N)=O AIXAANGOTKPUOY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010451 perlite Substances 0.000 description 2
- 235000019362 perlite Nutrition 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- NPHFFBWJNRVQNH-UHFFFAOYSA-H NN.S(=O)(=O)([O-])[O-].[Al+3].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].[Al+3] Chemical group NN.S(=O)(=O)([O-])[O-].[Al+3].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].[Al+3] NPHFFBWJNRVQNH-UHFFFAOYSA-H 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000001970 hydrokinetic effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 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
- 230000035484 reaction time Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000002268 wool Anatomy 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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
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Abstract
制备有低熔融粘度的环烯共聚物(COC)的方法，将0.1-99.9％(重量)(以单体总量计)的至少一种单体，R1、R2、R3、R4、R5、R6、R7和R8相同或不同，它们是氢原子或C1-C8烷基或芳基、而各式中相同基团可以有不同意义；0-99.9％(重量)(以单体总量计)式V的环烯，n是2-10的数字；与0.1-99.9％(重量)(以单体总量计)的至少一种式VI无环1-烯烃，R9、R10、R11和R12相同或不同，它们是氢原子或C1-C8烷基，
在溶液中，在悬浮液中，在液态的环烯单体或环烯单体混合物中或在气相中，于-78-150℃的温度区间和在0.5-64bar的压力范围并在催化剂的存在下进行共聚，该催化剂包含作为过渡金属成分的金属茂和式VII(适合于线型)和/或式VIII(环型)的铝噁烷。在式VII和VIII的铝噁烷中，R13是C1-C6烷基或苯基或苄基，n是2-50的整数。催化剂的过渡金属成分是式IX的至少一种化合物，在式IX中，
M1是钛、锆、铪、钒、铌或钽，R14和R15相同或不同，它们是氢原子、卤原子、C1-C10烷基、C1-C10烷氧基、C6-C10芳基、C6-C10芳氧基、C2-C10链烯基、C7-C40芳烷基、C7-C40烷芳基或C8-C40芳基链烯基，和m是1或2，取决于中心原子M1的价位。R18是＝BR19、＝AIR19、-Ge-、-Sn-、-O-、-S-、＝SO、＝SO2、＝NR19、＝CO、＝PR19或＝P(O)R19，其中R19、R20和R21相同或不同，它们是氢原子、卤原子、C1-C10烷基、C1-C10氟烷基、C6-C10氟芳基、C6-C10芳基、C1-C10烷氧基、C2-C10链烯基、C1-C40芳烷基、C8-C40芳基链烯基或C7-C40烷芳基或R19和R20或R19和R21与与其相连的原子形成环。M2是硅、锗或锡，R16和R17相同或不同，它们是单环或多环烃基，该烃基可与中心原子M1形成夹心结构，这里，式IX的金属茂关于配位体R16和R17和关于与其相连的中心原子M1有C2-对称性。
Description
本发明涉及具有低熔体粘度和低光衰减的热塑性环烯共聚物(COCs)，它们的制备工艺及其作为光波导管(光导纤维)的用途。
光波导管用于光的输送，例如照射或单波发射。通常它们包含圆筒形的透光芯，该芯由具有较低的折射率、同样是透明材料的覆盖层包绕着。例如，薄膜光波导管含三层透明材料，较靠外的二层比中间层折射率低，光传导在界面通过全反射发生。能使用的透明材料有玻璃或(有机或无机)聚合物。
最普遍用于光波导管的聚合物—聚甲基丙烯酸甲酯(PMMA)只能在至多约85℃使用，因为它的玻璃化温度低，仅为约106℃。其它已知的有较高玻璃化温度的透明热塑性塑料(例如聚碳酸酯或芳香聚酯)在分子中含有芳香单元，这将导致在短波光谱区的光吸收增加。这些用于光波导管的聚合物其用途在A.Tanaka等人所著的SPIE，Vol.840(1987)一书中以说明性词语有所描述。
通过聚甲基丙烯酸酯的反应可以改善耐热变形性。可提及的例子是聚合物相似物的转化：聚甲基丙烯酸甲酯转化成聚甲基丙烯酰亚胺。聚(甲基)丙烯酸酯与诸如甲基丙烯酸酐或甲基丙烯腈这样的共聚单体共聚，也能得到比未改性的PMMA耐热性更高的聚合物。得到具有提高了玻璃化温度的透明聚合物的另一条途径是使用(全)卤化或多环脂肪醇或取代酚的(甲基)丙烯酸酯。后者由于芳香单元的存在，在短波光谱区的光吸收增加。前面的化合物虽然能产生有高玻璃化温度的透明聚合物，但由于其固有脆性，很难甚至不能转变成光导纤维。
上述各类物质由于其极性而吸湿。在升高温度时，聚合物中所含水分在转化期间会引起不希望的降解反应，降低了实际使用价值。
然而，热塑性COCs显示出较低的吸水性，其耐热变形性也有所提高。完全没有发色团，如所有类型的双键，则意味着这些聚合物表现为特别适于光学应用，在光导领域中使用这些塑料也是可能的(EP—A0355682和EP—A0485893)。
COCs可以用特殊的Ziegler催化剂制备(EP—A0355682)，通常用烷基铝或烷基铝的氯化物作助催化剂。但是在所述加工工艺中，这些化合物水解，产生极细的、很难过滤的胶状化合物。如果使用烷基铝氯化物，加工时形成象盐酸或盐这样的含氯化合物也难于分离，如果加工时使用了盐酸(EP—A0355 682和EP—A0485893)，同样出现类似问题。特别是在此法制备COCs的工艺中，还会出现棕色。此外，在制备含乙烯的环烯共聚物时，一个已知的问题是部分结晶的乙烯聚合物作为付产物而形成。例如EP—AU447072叙述了由钒催化剂(参见EP—AO154464)制备的环烯共聚物通过复杂的多步过滤如何避免了部分结晶的乙烯聚合。在EP404870中描述的金属茂催化剂，除了异丙烯(9—芴基)环戊二烯合锆二氯化物和二苯基二价碳基(9—芴基)环戊二烯合锆二氯化物之外，也都产生作为环烯共聚物副产品的部分结晶的乙烯聚合物，正如我们自己的详细研究所证明的。但是，部分结晶乙烯聚合物的含量越高，材料的光衰减就越高。
为了生产聚合光导纤维或光波导管，所用聚合物除了优良的透明度外，另一个重要前提便是要求低熔体粘度以改善工艺条件。
本发明的目的是开发制备COCs的方法，此方法与先前的工艺比较，由于其改善了的熔体粘度、较低的光衰减、提高了的玻璃化温度和低吸水性而独具特色。本发明另一个目的是生产光波导管，它的芯材料含有该COCs。
业已发现，使用含至少一种金属茂催化剂和至少一种助催化剂的催化体系，若再用具某种对称性的金属茂催化剂，共聚合低级的α—烯烃、环烯和多环烯，便能够制备出具有低熔体粘度的COCs。如果共聚后形成的反应混合物经历特殊的加工工艺，具有0.1—5dB/km，优选为0.2—2dB/km、尤其优选为0.3—1.5dB/km的低光衰减的光波导管便可由纯化的COC和折光率低于COC折光率的透明聚合物来制备。
因此本发明涉及通过以下的聚合及工艺条件制备有低熔体粘度的环烯共聚物(COCs)的方法：将0.1—99.9％(重量)(以单体总量计)的式I、II、III或IV的至少一种单体
这里，R1、R2、R3、R4、R5、R6、R7和R8相同或不同，它们是氢原子或C1—C8烷基或C6—C16芳基，在各式中相同的基团可以有不同的定义，
0—99.9％(重量)(以单体总量计)的式V的环烯
这里，n是2—10的数字，与0.1—99.9％(重量)至少一种式VI的无环1—烯烃(以单体总量计)
这里，R9、R10、R11和R12相同或不同，它们是氢原子或C1—
C8烷基或C6—C16芳基，在溶液中、在悬浮液中，在液态环烯单体或环烯单体混合物中或在气相中，于-78—150℃的温度区间并在0.5—64巴的压力范围和在催化剂的存在下进行聚合，该催化剂包含作为过渡金属成分的金属茂以及式VII(适用于线型)和/或式VIII(适用于环型)的铝恶烷
在式VII和VIII中，R13是C1—C6烷基或苯基或苄基，n是2—50的整数。其中在催化剂的存在下进行聚合反应。该催化剂的过渡金属成分是式IX的至少一种化合物，
这里，M1是钛、锆、铪、钒、铌或钽，
R14和R15相同或不同，它们是氢原子、卤原子，C1—C10烷基、C1—C10烷氧基、C6—C10芳基、C6—C10芳氧基、C2—C10链烯基、C7—C40芳烷基、C7—C40烷芳基或C8—C40芳基链烯基，
n可以是1或2，取决于中心原子M1的价位，
R18是
＝BR19、＝AIR19、—Ge—、—Sn—、—O—、—S—、＝SO、=SO2、＝NR19、＝CO、＝PR19、或＝P(O)R19、R19和R20和R21相同或不同，它们是氢原子、卤原子、C1—C10烷基、C1—C10氟烷基、C6—C10氟芳基、C6—C10芳基、C1—C10烷氧基、C2—C10链烯基、C7—C40芳烷基、C8—C40芳基链烯基或C7—C40烷芳基、或R19和R20或R19和R21，在每种情况下都与其相连的原子形成环，
M2是硅、锗或锡，
R16和R17不同，它们是可与中心原子M1形成夹心结构的单环或多环烃基，这里，式IX的金属茂关于配位体R16和R17、关于与其相连的中心原子M1有Cs对称性。
在聚合作用中，式I、II、III或IV的至少一个多环烯，优选为式I或III的环烯发生聚合 
这里，R1、R2、R3、R4、R5、R6、R7和R8相同或不同，它们是氢原子或C1—C8烷基或C1—C16芳基，在各式中相同的基团可以有不同的定义。
使用式V的单环烯也是可能的这里，n是2—10的数。另一个共聚用单体是式VI的无环1—烯烃，
这里，R9、R10、R11和R12相同或不同，它们是氢原子或C1—C8烷基，也可含双键或C6—C16芳基。优选为乙烯、丙烯、丁烯、己烯、辛烯或苯乙烯，尤其优选为乙烯。此外，还可使用二烯。
具体地说，制备了式I和II的多环烯的共聚物。
多环烯(I到IV)的用量为0.1—99.9％(重量)，单环烯(V)的用量为0.1—99.9％(重量)和无环1—烯烃(VI)的用量为0.1—99.9％(重量)，每种情况均以单体总量计。
单体最好以下列比例混合a)在相应聚合物中，多环烯(I—IV)：1—烯烃(VI)单体的摩尔比为1∶99—99∶1，优选为20∶80—80∶20；b)在含多环烯(I—IV)和单环烯(V)的聚合物中，多环烯：单环烯的摩尔比是10∶90—90∶10；c)在含多环烯(1—IV)、单环烯(V)和1—烯烃(VI)的聚合物中，多环烯：单环烯：1—烯烃单体的摩尔比是93∶5∶2—5∶93∶2—5∶5∶90，即摩尔比是在三个角分别由摩尔比93∶5∶2、5∶93∶2和5∶5∶90确定的混合物三角形内；d)在(a)、(b)、(c)中，多环烯、单环烯和1—烯烃也可取二个或多个具体类型的烯烃的平均混合物。
聚合时所用催化剂包含铝恶烷和式IX的至少一种金属茂
式IX中，M1是取自包括钛、锆、铪、钒、铌和钽的金属，优选为锆和铪。
R14和R15相同或不同，它们是氢原子、C1—C10优选为C1—C3烷基、C1—C10优选为C1—C3烷氧基、C6—C10优选为C6—C8芳基、C6—C10优选为C6—C8芳氧基、C2—C10优选为C2—C4链烯基、C7—C40优选为C7—C10芳烷基，C7—C40优选为C7—C12烷芳基、C8—C40优选为C8—C12芳基链烯基或卤原子优选为氯原子。
R16和R17不同，它们是能与中心原子M1形成夹心结构的单环或多环烃基。
式IX的金属茂关于配位体R16和R17及关于与其相连的中心原子M1有Cs—对称性。
R16最好是芴基，R17优选为环戊二烯基。
R18是连接R16和R17的一元或多元桥，它是＝BR19、＝AIR19、—Ge—、—Sn—、—O—、—S—、＝SO、=SO2、＝NR19、＝CO、＝PR19、或＝P(O)R19，其中R19和R20和R21相同或不同，它们是氢原子、卤原子、(优选为氯)、C1—C10优选为C1—C3烷基(特别是甲基)、C1—C10氟烷基(优选为CF3基)、C6—C10氟芳基(优选为五氟苯基)、C6—C10优选为C6—C8芳基、C1—C10优选为C1—C4烷氧基(尤其是甲氧基)、C2—C10优选为C2—C4链烯基、C7—C40优选为C7—C10芳烷基、C8—C40优选为C8—C12芳基链烯基或C7—C40优选为C7—C12烷芳基或R19和R20或R19和R21，在每种情况下，都与与其相连的原子形成环。
M2是硅、锗或锡，优选为硅或锗。
R18优选为＝CR19R20、＝SiR19R20、＝GeR19R20、—O—、—S—、＝SO、＝PR19或＝P(O)R19。
金属茂可根据下列反应体系制备
上述反应体系自然也适用于R16＝R17和/或R19＝R20和/或R14＝R15的情况。
优选的金属茂是：
二苯基亚甲基(9—芴基)(环戊二烯)合锆二氯化物，
异丙烯(9—芴基)(环戊二烯)合锆二氯化物，
甲苯基二价碳基(9—芴基)(环戊二烯)合锆二氯化物
或它们的混合物。
尤其优选的是：
异丙烯(9—芴基)(环戊二烯)合锆二氯化物或其混合物。
助催化剂是为线型所用的式VII和/或为环型所用的式VIII的铝恶烷 
在这些式中，R13是C1—C6烷基，优选为甲基、乙基、异丁基、丁基或新戊基、或苯基或苄基，尤其优选为甲基，n是2—50的整数，优选为5—40。但铝恶烷的确切结构尚不清楚。
铝恶烷可用几种方法制备：
在其中一种方法中，细末状的五水合硫酸铜在甲苯中成浆状物，在惰性气氛下约-20℃，将足量三烷基铝加入玻璃烧瓶使每四个Al原子有约1mol CuSO4·5H2O。随着烷烃的消除，缓慢水解后，反应混合物于室温静置24—48小时，在此期间可能需冷却，以使温度不超过30℃。然后，将溶于甲苯的铝恶烷过滤与硫酸酮分离，溶液真空蒸发。据认为此制备工艺涉及到随三烷基铝的消除，低分子量铝恶烷缩聚成较高分子量的低聚物的缩合反应。
此外，如果溶于惰性脂族或芳香族溶剂中(优选为庚烷或甲苯)的三烷基铝(优选为三甲基铝)与含结晶水的铝盐(优选为硫酸铝)在-20—100℃下反应，也能得到铝恶烷。在此反应中，溶剂和所用烷基铝之间的体积比是1∶1—50∶1，优选为5∶1。可由烷烃的消除而监测到的反应时间是1—200小时，优选为10—40小时。
含结晶水的铝盐具体讲是有高含量结晶水的铝盐，特别优选的是水合硫酸铝，尤其是化合物Al2(SO4)3·16H2O和Al2(SO4)3·18H2O每mol Al2(SO4)3分别有16和18mol的特别高的结晶水含量。
铝恶烷的另一个不同的制备方法包含：在聚合反应器中于庚烷或甲苯中将三烷基铝(优选为三甲基铝)溶于悬浮介质(优选为液态单体)中，然后使该铝化合物与水反应。
除了上面概述的制备铝恶烷的方法外，还有其它可以使用的方法，无论哪种制备方法，所有铝恶烷溶液，一般都有不同含量的未反应的三烷基铝以游离形式或作为加成物存在。该含量对催化活性有影响，该催化活性还没有精确的解释，其活性变化取决于所用金属茂化合物。
金属茂在用于聚合反应之前通过式II和/或式III的铝恶烷对其预活化也是可能的。这可以极大地提高聚合反应活性。
过渡金属化合物的预活化在溶液中进行。这里，优选的方法是：将金属茂溶解于已溶于惰性烃中的铝恶烷溶液，合适的惰性烃是脂族或芳香烃，最好是甲苯。
溶液中铝恶烷的浓度在1％(重量)至饱和限度范围内，最好是5—30％(重量)，每种情况均以总溶液计。金属茂可以相同浓度使用，但优选的用量为每mol铝恶烷使用10-4—1mol金属茂。预活化时间是5分钟—60小时，优选为5—60分钟。反应温度是-78—150℃，优选为20—100℃。
长时间预活化是可能的，但一般来说，它既不提高也不降低活性，对贮存也许较合适。
对于Ziegler低压工艺，习惯上聚合反应在惰性溶剂中进行，例如在脂肪烃或环状脂肪烃中；可提及的烃有丁烷、戊烷、己烷、庚烷、异辛烷、环己烷和甲基环己烷。此外，还可以使用仔细除去了氧、硫化合物和水分的汽油或氢化柴油馏分，也可以用甲苯、萘烷和二甲苯。
最后，需聚合的单体也可用作溶剂或悬浮介质，在降冰片烯的情况下，这类本体聚合在45℃以上进行，聚合物的分子量可用已知的方法调整，为此目的最好使用氢。
聚合反应用已知的方法在溶液中，在悬浮液中，在液态环烯单体或环烯单体混合物中或在气相中，连续或分批，一步或多步、在-78—150℃优选为20—100℃的温度范围内进行。压力为0.5—64巴，压力可用气态烯烃或辅以惰性气体来确定。
具体的优点是连续和多步工艺，因为它们可以有效的使用多环烯烃，该多环烯烃可作为残余单体与反应混合物一起进料。
这里用的金属茂化合物浓度以过渡金属计，每dm3反应器体积10-3—10-7mol，优选为10-5—10-6mol过渡金属。所用铝恶烷浓度以铝含量计，为10-4—10-1mol铝/dm3反应器体积，优选为10-4—2×10-2mol铝/dm3反应器体积，但原则上，为了使用各种金属茂的聚合性能，较高浓度也可以。
在共聚物的制备中，所用多环烯和1—烯烃之间的摩尔比变化范围很大，选择聚合温度，催化剂成分的浓度和使用的摩尔比，可实际根据需要来保证控制的共聚用单体的混合比例。在降冰片烯的情况下，能够达到大于40mol％的混合比。
形成的共聚物的平均分子量能用已知的方法通过改变催化剂浓度或温度来改变。
共聚物的多分散性Mw/Mn极窄，取值为1.9—3.5，这导致了其特别适于挤出用的聚合物性能等级。
多环烯与无环烯(尤其是与丙烯)的共聚产生了粘度指数大于20cm3/g的聚合物，降冰片烯与无环烯(特别是乙烯)的共聚物，玻璃化温度高于100℃。
为了制备具有低光衰减0.1—5dB/m的COCs，反应混合物需纯化。提纯最好由下述工艺进行：第一步，反应混合物与助滤剂和一种使反应混合物中的有机金属化合物沉淀的物质一起悬浮；第二步，滤出非均相成分；第三步，提纯的COC借助于沉淀剂从COC滤物中沉淀出来，或者蒸发掉COC滤物的溶剂。
在第三步，使用如借助于闪蒸室、薄膜蒸发器、ListR混合器(List，England)、排气挤出机或DiskpackR(Farrel，USA)的蒸发方法也是可能的。
在反应混合物中沉淀有机金属化合物的物质，最好是极性化合物，如水、乙二醇、甘油和乙酸。悬浮介质最好是烃。特别合适的助滤剂是硅藻土(例如RCelite545(LuV.Hamburg)、珍珠岩(例如Celite Perlite J-100(LuV)、改性纤维素(例如Diacel(LuV))，多孔碳和吸附石棉绒也适用。
在过滤步骤中使用助滤剂能获得良好的深度过滤，可以用连续或分批过滤技术。过滤可以通过压力过滤或离心过滤来完成，最好用例如滤过无纺材料的压力过滤或撇乳器离心的方法。也可用其它常规过滤技术。滤过的COC溶液可以连续或分批多次输入同一过滤器以便强化过滤效果。适用的沉淀剂是丙酮、异丙醇或甲醇。
为了生产光波导管，经过上述提纯步骤并干燥得到的聚合物用柱塞式或螺杆挤压机熔融使其通过口模。通过共挤压或溶液涂布将第二种聚合物的覆盖层涂于得到的纤丝上，第二种聚合物的折射率低于芯材料的折射率。合适的覆盖层材料是：4—甲基戊烯(特别是烯烃)的聚合物和共聚物、乙烯和1，1—二氟乙烯的共聚物，加或不加其它共聚单体(如六氟丙烯，四氟乙烯)、四氟乙烯和六氟丙烯和1，1—二氟乙烯的三元共聚物(若需要也可有乙烯)，甲基丙烯酸甲酯和(部分)氟化的醇的甲基丙烯酸酯(例如甲基丙烯酸四氟正丙酯)的共聚物。
为了生产平膜光波导管，由上述工艺提纯的聚合物在挤压机中熔融，并受力作用下通过平膜模头，表面的反射层通过共挤压或溶液涂布覆盖上第二种聚合物，它的折射率低于芯材料。
本发明通过以下实例来描述。实施例1：
装有搅拌器的清洁干燥的75dm3聚合反应器用氮气再用乙烯吹洗，然后装入22,000g熔融降冰片烯(Nb)和6升甲苯，在搅拌下反应器热至70℃，注入3.4巴乙烯，将500cm3甲基铝恶烷的甲苯溶液(根据冰点降低法测定：10.1％(重量)的甲基铝恶烷分子量是1300g/mol)计量加入反应器，混合物在70℃搅拌15分钟，在此期间，乙烯压力保持在3.4巴。类似地，将350mg二苯基二价碳基(环戊二烯)(9—芴基)合锆二氯化物溶于500cm3甲基铝恶烷的甲苯溶液(浓度和质量见上)，静置15分钟预活化。然后将配合物溶液(催化剂溶液)计量加入反应器。为了调整分子量，在开始时引入0.7升氢气。聚合反应期间，连续计量输入氢气780ml/h。混合物在70℃于搅拌下(750转/分)聚合1.5小时，在此期间，乙烯压力始终保持在3.4巴。
反应液放料到一个150升的搅拌反应器中，该反应器中装有500g硅藻土(RCelite545 LuV，Hamburg)或纤维素助滤剂(Di-acel，LuV.Hamburg)，200ml水，溶于50升氢化柴油馏分(REx-Sol，沸程100—120℃，Exxon)中的0.5g过氧化物分解剂(HostanoxR3，Hoechst)和0.5g抗氧化剂(HostanoxR03，Hoechst)，该混合物再于60℃搅拌30分钟。
悬浮于10升RExsol中的500gR Celite(或换用500g纤维素)在120升压力过滤器的滤器织物上形成滤饼，聚合物溶液以下面方式滤过压力过滤器，即最初15分钟，滤液返回滤器，溶液上方形成最多2.8巴的氮气压。
然后，滤液滤过7只安装在钢套中的滤筒(流体动力学，Dy-nalloy XS64，5μm，0.1m2/筒)，聚合物溶液用分散器(RUl-traturax)搅拌加入500升丙酮并沉淀。在此期间，丙酮悬浮液在680升打开底阀的搅拌式压力过滤器中循环。然后关紧底阀，产品用200升丙酮洗三次，最后一次洗涤时加入50g稳定剂(RIrganox1010，Ciba)。最后一次过滤之后，产品在氮气流中于100℃预干燥，再于干燥箱中在0.2巴下干燥24小时，得到4160g产品，产品的粘度指数(V1)是62cm3/g(DIN53728)，玻璃化温度(Tg)是181℃，熔体粘度是400PaS。实施例2(与实施例1对比的实施例，EP407870)。
装有搅拌器的清洁干燥的75dm3聚合反应器用氮气再用乙烯吹洗，然后装入22000g熔融降冰片烯(Nb)和6升甲苯。反应器在搅拌下加热到70℃，注入3.4巴乙烯，将500cm3甲基铝恶烷的甲苯溶液(根据冰点降低法测定：10.1％(重量)分子量是1300g/mol的甲基铝恶烷)计量加入反应器，混合物于70℃搅拌15分钟，在此期间，乙烯压力保持在3.4巴。类似地，将350mg二苯基二价碳基(环戊二烯基)(9—芴基)合锆二氯化物溶于500cm3甲基铝恶烷的甲苯溶液(浓度和质量见上)中，静置15分钟预活化，然后将配合物溶液(催化剂溶液)计量加入反应器。为了调整分子量，起始加入0.7升氢气。聚合反应期间，连续计量输入780ml/hr氢气。混合物在70℃于搅拌下(750转/分)聚合1.5小时，在此期间，乙烯压力保持在3.4巴。
然后将反应器的内容物迅速倒进一只150升带搅拌的容器中，容器内有200cm3溶在10升Exsol中的异丙醇，混合物在500升丙酮中沉淀，搅拌10分钟，滤出悬浮的聚合物固体，将滤出的聚合物加到200升含二份3当量浓度盐酸和一份乙醇的混合物中，搅拌此悬浮液2小时，再过滤聚合物，用水洗至中性，在80℃、0.2巴干燥15小时，得到4320g产品，粘度指数(V1)为60cm3(DIN53728)玻璃化温度(Tg)是182℃。在DSC中未发现熔体吸热。实施例3(与实施例1对比的实施例，EP407870)
工艺类似于实施例1，但所用催化剂是1200mgrac—二甲基甲硅烷基双(1—茚基)合锆二氯化物，在3.2巴的乙烯压力下，使用实施例1描述的加工方法反应150分钟，得到5070g聚合物，粘度指数VI为61cm3/g(DIN53728)，Tg为179℃。
表1
(以零剪切粘度测试，即在0.1S-1的剪切速率下的近似粘度用毛细管粘度计在T＝Tg＋120℃下测试)实施例4
| COC(实施例1) | COC(实施例3) | |
| 熔体粘度(Pa*S) | 400 | 2000 |
由实施例1得到的聚合物在柱塞式挤压机中于210—260℃机筒温度下熔融，令其以610cm3/h的流速通过内径为2mm的口模。在265℃、11kg负荷下熔体流动指数为32g/10min的四氟乙烯、1，1—二氟乙烯和六氟丙烯三元聚合物在柱塞式挤压机中熔融，并以39cm3/hr的流速输进环绕模芯同心排列的环形狭缝，产生的芯/覆盖层纤维在抽丝浴槽中冷却，并以35m/min的速度卷取。为改善机械性能，纤维再于190℃在热风炉中以1∶2.5的比例拉伸，然后卷紧。于是得到了芯直径为970μm、覆盖层直径为1mm的芯/覆盖层纤维。撕裂强度： 4.5CN/tex(DIN(缺漏))断裂伸长： 27％(DIN(缺漏))光衰减： 1.2dB/m(650nm)实施例5
由实施例2得到的聚合物在柱塞式挤压机中于210—260℃机筒温度下熔融，令其以610cm3/h的流速通过内径为2mm的口模。在265℃、11kg负荷下熔体流动指数为32g/10min的四氟乙烯、1，1—二氟乙烯和六氟丙烯三元聚合物在柱塞式挤压机中熔触，同样以39cm3/hr的流速输送至环绕芯模同心排列的环形狭缝。产生的芯/覆盖层纤维在抽丝浴槽中冷却，并以5.5m/min的速度卷取。为改善机械性能，纤维再在190℃下于热风炉中以1∶2.5的比例拉伸，然后卷紧。于是得到芯直径为970μm，覆盖层直径为1mm的芯/覆盖层纤维。撕裂强度： 5.2CN/tex(DIN(缺漏))断裂伸长： 28％(DIN(缺漏))光衰减： 12.2dB/m(650nm)实施例6
聚合溶液类似于实施例3制备，但该溶液类似于实施例2进行加工，即聚合物溶液不过滤。
除玻璃化温度(Tg＝178℃)外，DSC在127℃显示出熔体热焓为1J/g的熔体吸热，这是富含部分结晶的乙烯的聚合物的贡献，此值相当于在干燥的纯品中，0.5—1％(重量)的聚乙烯含量。具有1mm厚度的压片是混浊的(压制条件：240℃，10min，50巴压力)。
Claims (13)
1.一种制备具有低熔体粘度的环烯烃共聚物(COC)的方法，通过将0.1—99.9％(重量)(以单体总量计)式I、II、III或IV中的至少一种单体 
这里，R1、R2、R3、R4、R5、R6、R7和R8相同或不同，它
们是氢原子或C1—C8烷基或芳基，在各式中相同的基团可以
有不同的定义，0—99.9％(重量)(以单体总量计)的式V的环烯烃
这里，n是2—10的数，和0.1—99.9％(重量)(以单体总量计)的至少一种式VI的无环1—烯烃进行共聚合
这里，R9、R10、R11和R12相同或不同，它们是氢原子或C1—
C8烷基，聚合条件是：在溶液中、在悬浮液中、在液态环烯单体或环烯单体混合物中或在气相中，于一78—150℃的温度区间，在0.5—64巴的压力范围，在催化剂的存在下进行反应，该催化剂包含作为过渡金属组分的金属茂和线型时为式VII和/或环式时为式VIII的铝恶烷
在式VII和VIII中，R13是C1—C6烷基或苯基或苄基，n是2—50的整数，聚合反应在催化剂存在下进行，该催化剂的过渡金属成分是至少一种式IX化合物，
这里，M1是钛、锆、铪、钒、铌或钽，
R14和R15相同或不同，它们是氢原子、卤原子、C1—C10烷基、C1—10烷氧基、C6—C10芳基、C6—C10芳氧基、C2—C10链烯基、C7—C40芳烷基、C7—C40烷芳基或C8—C40芳基链烯基，
m是1或2，取决于中心原子M1的价位，
R18是＝BR19、＝AIR19、—Ge—、—Sn—、—O—、—S—、＝SO、=SO2、＝NR19、＝CO、＝PR19或＝P(O)R19，R19、R20和R21相同或不同，它们是氢原子、卤原子、C1—C10烷基，C1—C10氟烷基、C6—C10氟芳基、C6—C10芳基、C1—C10烷氧基、C2—C10链烯基、C7—C40芳烷基、C8—C40芳基链烯基或C7—C40烷芳基、或R19和R20或R19和R21，在每种情况下都与与其相连的原子形成环，
M2是硅、锗或锡，
R16和R17不同，它们是可与中心原子M1形成夹心结构的单环或多环烃基，其中，式IX的金属茂关于配位体R16和R17及关于与其相连的中心原子M16有C17—对称性。
2.如权利要求1所述的方法，其中，当共聚合反应完成时，共聚物需经过加工处理，而使该材料的光衰减为0.1—5dB/m，优选为0.2—2dB/m，尤其优选为0.3—1.5dB/m。
3.如权利要求1所述的方法，其中，所用催化剂是式XI的金属茂，其中R16是芴基，R17是环戊二烯基。
4.如权利要求3所述的方法，其中，所用金属茂是二苯基亚甲基(9—芴基)环戊二烯合锆二氯化物，优选为异丙烯(9—芴基)环戊二烯合锆二氯化物。
5.如权利要求1所述的方法，其中，使用的1—烯烃是乙烯。
6.如权利要求1所述的方法，其中，使用的1—烯烃是乙烯，使用的多环烯烃是降冰片烯。
7.如权利要求2所述的方法，其中，在提纯工艺的第一步，反应混合物与助滤剂和使反应混合物中的有机金属化合物沉淀的物质一起悬浮；第二步滤出非均相组分；第三步，借助于沉淀剂从COC滤液中沉淀出提纯的COC，或者蒸发除去COC滤液的溶剂。
8.如权利要求2所述制备的环烯共聚物(COC)。
9.使用权利要求8所述的COC用于平膜式和筒式光波导管的方法。
10.一种光波导管，包含透光芯或透光层和透明聚合物的覆盖层，该透明聚合物的折射率小于透光介质的折射率，其中，透光芯或透光层和/或覆盖层含有权利要求8所述的COC。
11.如权利要求10所述的光波导管，其中，覆盖层包含具有1.34—1.47(在589nm处)的折射率的热塑性聚合物。
12.如权利要求10所述的光波导管，其中，覆盖层包含四甲基戊烯和其它烯烃的聚合物或共聚物，乙烯和1,1—二氟乙烯的共聚物，加或不加其它共聚用单体(如六氟丙烯和/或四氟乙烯)，四氟乙烯，六氟丙烯和1,1—二氟乙烯，若需要还可有乙烯，的共聚物，甲基丙烯酸甲酯和氟化的或部分氟化的醇的甲基丙烯酸酯，例如，甲基丙烯酸四氟正丙酯的共聚物。
13.如权利要求1所述制备的环烯烃共聚物，其中，在聚合期间形成了小于0.1％(重量)的部分结晶的乙烯聚合物(以聚合物总量计)。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4304291A DE4304291A1 (de) | 1993-02-12 | 1993-02-12 | Cycloolefincopolymere mit niedriger Schmelzeviskosität und niedriger optischer Dämpfung |
| DEP4304291.0 | 1993-02-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1117737A true CN1117737A (zh) | 1996-02-28 |
Family
ID=6480340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94191172A Pending CN1117737A (zh) | 1993-02-12 | 1994-01-31 | 具有低熔体粘度和低光衰减的环烯共聚物 |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5637400A (zh) |
| EP (1) | EP0683797B1 (zh) |
| JP (1) | JP3361808B2 (zh) |
| KR (1) | KR100306351B1 (zh) |
| CN (1) | CN1117737A (zh) |
| AU (1) | AU693083B2 (zh) |
| BR (1) | BR9405831A (zh) |
| CA (1) | CA2155936C (zh) |
| DE (2) | DE4304291A1 (zh) |
| ES (1) | ES2132378T3 (zh) |
| WO (1) | WO1994018251A1 (zh) |
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| JPS5342260B2 (zh) * | 1973-11-22 | 1978-11-10 | ||
| DE3922546A1 (de) * | 1989-07-08 | 1991-01-17 | Hoechst Ag | Verfahren zur herstellung von cycloolefinpolymeren |
| US5371158A (en) * | 1990-07-05 | 1994-12-06 | Hoechst Aktiengesellschaft | Bulk polymerization using specific metallocene catalysts for the preparation of cycloolefin polymers |
| TW227005B (zh) * | 1990-11-14 | 1994-07-21 | Hoechst Ag | |
| DE4104392A1 (de) * | 1991-02-14 | 1992-08-20 | Hoechst Ag | Polymere optische fasern auf der basis von fluor- und fluoralkylsubstituierten poly(norbornen)- und poly(norbornadien)-derivaten und verfahren zu deren herstellung |
| ATE173746T1 (de) * | 1991-02-27 | 1998-12-15 | Ticona Gmbh | Verfahren zur herstellung von cycloolefin(co)polymeren mit enger molekulargewichtsverteilung |
| EP0729977B1 (de) * | 1991-03-09 | 2002-09-04 | Basell Polyolefine GmbH | Metallocen und Katalysator |
| DE4304285A1 (de) * | 1993-02-12 | 1994-08-18 | Hoechst Ag | Cycloolefincopolymere mit hoher Reißfestigkeit und niedriger optischer Dämpfung |
-
1993
- 1993-02-12 DE DE4304291A patent/DE4304291A1/de not_active Withdrawn
-
1994
- 1994-01-31 EP EP94905734A patent/EP0683797B1/de not_active Expired - Lifetime
- 1994-01-31 CN CN94191172A patent/CN1117737A/zh active Pending
- 1994-01-31 AU AU59724/94A patent/AU693083B2/en not_active Ceased
- 1994-01-31 DE DE59408117T patent/DE59408117D1/de not_active Expired - Lifetime
- 1994-01-31 BR BR9405831A patent/BR9405831A/pt not_active Application Discontinuation
- 1994-01-31 KR KR1019950703346A patent/KR100306351B1/ko not_active IP Right Cessation
- 1994-01-31 WO PCT/EP1994/000263 patent/WO1994018251A1/de active IP Right Grant
- 1994-01-31 CA CA002155936A patent/CA2155936C/en not_active Expired - Fee Related
- 1994-01-31 JP JP51760794A patent/JP3361808B2/ja not_active Expired - Fee Related
- 1994-01-31 US US08/492,106 patent/US5637400A/en not_active Expired - Lifetime
- 1994-01-31 ES ES94905734T patent/ES2132378T3/es not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE4304291A1 (de) | 1994-08-18 |
| AU5972494A (en) | 1994-08-29 |
| EP0683797B1 (de) | 1999-04-14 |
| AU693083B2 (en) | 1998-06-25 |
| CA2155936C (en) | 2006-05-30 |
| ES2132378T3 (es) | 1999-08-16 |
| BR9405831A (pt) | 1995-12-26 |
| US5637400A (en) | 1997-06-10 |
| CA2155936A1 (en) | 1994-08-18 |
| KR100306351B1 (ko) | 2001-11-30 |
| DE59408117D1 (de) | 1999-05-20 |
| KR960701111A (ko) | 1996-02-24 |
| JPH08507800A (ja) | 1996-08-20 |
| WO1994018251A1 (de) | 1994-08-18 |
| EP0683797A1 (de) | 1995-11-29 |
| JP3361808B2 (ja) | 2003-01-07 |
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