CN1214699A - 高度可溶性烯烃聚合反应催化活化剂 - Google Patents
高度可溶性烯烃聚合反应催化活化剂 Download PDFInfo
- Publication number
- CN1214699A CN1214699A CN97193268A CN97193268A CN1214699A CN 1214699 A CN1214699 A CN 1214699A CN 97193268 A CN97193268 A CN 97193268A CN 97193268 A CN97193268 A CN 97193268A CN 1214699 A CN1214699 A CN 1214699A
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- CN
- China
- Prior art keywords
- titanium
- phenyl
- cyclopentadienyl
- alkyl
- group
- 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
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- 239000012190 activator Substances 0.000 title claims abstract description 35
- 150000001336 alkenes Chemical class 0.000 title description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 5
- 239000002685 polymerization catalyst Substances 0.000 title description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007848 Bronsted acid Substances 0.000 claims abstract description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 9
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002585 base Substances 0.000 claims description 73
- 125000000217 alkyl group Chemical group 0.000 claims description 44
- 239000004327 boric acid Substances 0.000 claims description 40
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000004711 α-olefin Substances 0.000 claims description 15
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000003760 tallow Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 150000007527 lewis bases Chemical class 0.000 claims description 7
- 239000002879 Lewis base Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 150000004696 coordination complex Chemical class 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 abstract description 7
- 150000001768 cations Chemical class 0.000 abstract 1
- -1 metal complex compound Chemical class 0.000 description 90
- 239000000203 mixture Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 29
- 239000010936 titanium Substances 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 22
- 229910052719 titanium Inorganic materials 0.000 description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 15
- 239000003426 co-catalyst Substances 0.000 description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 14
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 13
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 13
- 229910052796 boron Inorganic materials 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 12
- 235000002639 sodium chloride Nutrition 0.000 description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 229910052726 zirconium Inorganic materials 0.000 description 11
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 7
- 230000000737 periodic effect Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- NHYFQMARGINDIH-UHFFFAOYSA-N C[Ti]C.C[SiH2]C Chemical compound C[Ti]C.C[SiH2]C NHYFQMARGINDIH-UHFFFAOYSA-N 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 5
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical compound CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 description 5
- 229910052752 metalloid Inorganic materials 0.000 description 5
- 150000002738 metalloids Chemical class 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate 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
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000021615 conjugation Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- CMWCOKOTCLFJOP-UHFFFAOYSA-N titanium(3+) Chemical compound [Ti+3] CMWCOKOTCLFJOP-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- UDXZTOMJCFOTHN-UHFFFAOYSA-N C(C)P(CC)CC.[Ti] Chemical compound C(C)P(CC)CC.[Ti] UDXZTOMJCFOTHN-UHFFFAOYSA-N 0.000 description 2
- VHFQMLPFQRATTO-UHFFFAOYSA-N C1(C=CC=C1)C=C(C=C(C)C)C Chemical compound C1(C=CC=C1)C=C(C=C(C)C)C VHFQMLPFQRATTO-UHFFFAOYSA-N 0.000 description 2
- NEHOLHBKMCQNRG-UHFFFAOYSA-N CP(C)C.[Ti] Chemical class CP(C)C.[Ti] NEHOLHBKMCQNRG-UHFFFAOYSA-N 0.000 description 2
- COOXAWDWHWRVRD-UHFFFAOYSA-N C[Ti]C Chemical compound C[Ti]C COOXAWDWHWRVRD-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XZKIGLCKKVCVAB-UHFFFAOYSA-N [SiH3][Zr] Chemical compound [SiH3][Zr] XZKIGLCKKVCVAB-UHFFFAOYSA-N 0.000 description 2
- GDIDZHMLNKUJJG-UHFFFAOYSA-N [Ti].C=CC=CC.CC=1C(C2=CC=CC=C2C1)[SiH](C)C Chemical compound [Ti].C=CC=CC.CC=1C(C2=CC=CC=C2C1)[SiH](C)C GDIDZHMLNKUJJG-UHFFFAOYSA-N 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001399 aluminium compounds Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000078 germane Inorganic materials 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- GUDXVVMHJSJXBR-UHFFFAOYSA-N (1,2,3,4,5-pentamethylcyclopenta-2,4-dien-1-yl)methanol Chemical compound CC1=C(C)C(C)(CO)C(C)=C1C GUDXVVMHJSJXBR-UHFFFAOYSA-N 0.000 description 1
- AHASZRJISOIMNB-UHFFFAOYSA-N (2,3-dimethyl-1H-inden-1-yl)-dimethylsilane Chemical compound CC=1C(C2=CC=CC=C2C=1C)[SiH](C)C AHASZRJISOIMNB-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
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- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
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- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- BXMZEPVYHFTJJK-UHFFFAOYSA-N cyclopenta-1,3-diene;ethane Chemical compound CC.C1C=CC=C1 BXMZEPVYHFTJJK-UHFFFAOYSA-N 0.000 description 1
- YPYFWQGTUZSRIA-UHFFFAOYSA-N cyclopenta-2,4-dien-1-ylmethanol Chemical compound OCC1C=CC=C1 YPYFWQGTUZSRIA-UHFFFAOYSA-N 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005131 dialkylammonium group Chemical group 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical class N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- JQZUMFHYRULBEN-UHFFFAOYSA-N diethyl(methyl)silicon Chemical compound CC[Si](C)CC JQZUMFHYRULBEN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- FZTMUIDAMRKQPP-UHFFFAOYSA-N dimethyl-(2-methyl-1H-inden-1-yl)silane Chemical compound C1=CC=C2C([SiH](C)C)C(C)=CC2=C1 FZTMUIDAMRKQPP-UHFFFAOYSA-N 0.000 description 1
- AKPKJLLXVRTRKJ-UHFFFAOYSA-N dimethylsilane 2-methylbuta-1,3-diene titanium Chemical compound [Ti].C=CC(C)=C.C[SiH2]C AKPKJLLXVRTRKJ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 150000008282 halocarbons Chemical group 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- SZEGKVHRCLBFKJ-UHFFFAOYSA-N n-methyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNC SZEGKVHRCLBFKJ-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- OXUCOTSGWGNWGC-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2-] OXUCOTSGWGNWGC-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical group 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- TZPUFQUQYUYVQC-UHFFFAOYSA-N phenylsilylmethanamine Chemical compound NC[SiH2]C1=CC=CC=C1 TZPUFQUQYUYVQC-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005353 silylalkyl group Chemical group 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical class [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
催化活化剂包含了阳离子,该阳离子为可以提供质子的布鲁斯台德酸,和惰性的、可相容的非配位的阴离子,该催化活化剂的特征为在25℃下在己烷、环己烷或甲基环己烷中至少为5wt%的溶解度常数性。
Description
本发明涉及到催化活化剂。更具体地,本发明涉及到特别适用于α-烯烃聚合反应的溶液聚合反应过程中的催化活化剂。在用于连续的溶液聚合反应过程中,该活化剂是特别有利的,其中的催化剂、催化活化剂和至少一种可聚合反应的单体被连续地加入到在溶液聚合反应条件下操作的反应器中,并且聚合的产品被连续地从反应器中移走。
目前技术上已经知道,通过采用布鲁斯台德酸盐来活化齐格勒-纳塔聚合反应催化剂,特别是这种催化剂包含含有离域的π-键合的配位基团的第4族金属络合物,该布鲁斯台德酸盐可以转移一个质子形成该第4族金属络合物的阳离子衍生物。优选的布鲁斯台德酸盐为含有未配位阴离子的化合物,该阴离子可以稳定形成的第4族金属阳离子,特别是四(五氟代苯基)硼酸盐。为离子活化剂类的这些布鲁斯台德酸盐活化剂的例子为在US-A-5,198,401,US-A-5,132,380,US-A-5,470,927和US-A-5,153,157中公开的质子化的铵盐、硫鎓盐或磷鎓盐。
由于这些活化剂被完全离子化并且相应的阴离子为高度未配位化的事实,这些活化剂作为聚合反应催化活化剂是特别有效的。但是,由于它们是离子盐,不利的是这些活化剂很难溶于脂肪烃中,并且在芳香性溶剂中仅可少量溶解。由于这些溶剂与单体的相容性并且为了降低形成的聚合物产物中芳香烃的含量,需要在脂肪烃溶剂中进行大多数α-烯烃的聚合反应。通常,需要以在芳香性溶剂例如甲苯中的溶液形式将离子盐活化剂加入到聚合反应中。为此目的,即使采用少量的这种芳香性溶剂也是不期望的,因为必须在脱挥发份的步骤中除去它和从其它挥发性组分中分离它,对于任何商业化的过程,该过程大大增加了费用和复杂性。另外,前述的离子型共催化剂通常以油性的难以处理的物质形式存在,这是不容易处理和计量,或者是精确地加入到反应混合物中。
相应地,如果提供了离子性的催化活化剂,它可以用于采用了包括缩合的α-烯烃单体的脂族溶剂的溶液聚合反应中,这将是有利的。另外,有利的是提供了新形式的离子型催化活化剂,它特别适用于连续的溶液聚合反应中,其中需要控制特定量的这种活化剂的加入。
根据本发明,现在提供了一种催化活化剂,它包括可以提供质子的为布鲁斯台德酸的阳离子,和惰性的、可相容的非配位的阴离子,其特征是在25℃在己烷、环己烷或甲基环己烷中的至少5wt%,优选地至少7.5wt%的溶解度。另外,根据本发明,提供了α-烯烃的溶液聚合反应,它包括在非必须的惰性脂族、脂环族或芳香族烃的存在下,用包括上述催化活化剂的催化剂体系接触一种或多种α-烯烃。
通过采用前述的催化活化剂,得到了提高的催化活性。更具体地,获得了提高了的催化效率和聚合反应速率,特别是在溶液聚合反应的条件下,更特别地在连续的溶液聚合反应条件下。
在这里对属于某一族的元素的所有参考指的是由CRC出版公司在1989年发表和要求版权的元素周期表。同时,对于族的任何参考应该是在采用IUPAC体系的用于编号族的该元素周期表中反映的族。
本发明的催化活化剂以下面的方式被进一步特征化。优选的阴离子为含有一个配位络合物的阴离子,该络合物包含带电荷的金属或准金属核,其中的阴离子可以平衡活性催化剂物种(金属阳离子)的电荷,当两种组分结合时,形成了活性催化剂物种。同样,所述的阴离子应该足够易于被烯烃、二烯烃和炔属不饱和化合物或中性路易斯碱,例如醚、胺或腈所取代。适当的金属包括但并不限定于铝、金和铂。适当的准金属包括但并不限定于硼、磷和硅。显然,包含配位络合物的含有阴离子的化合物是广为人知的,该配位络合物含有单一金属或准金属原子,并且特别地,在阴离子部分含有单一硼原子的许多这种化合物可以在商业上获得。因此,所述的单一硼原子的化合物是优选的。
优选地,本发明的共催化剂可以由下面的一般结构式表示:(L*-H)d +(Ad-),其中:
L*为中性路易斯碱;
(L*-H)+为布鲁斯台德酸;
Ad-为具有电荷d-的未配位的相容性阴离子,并且
d为从1到3的整数。
其中:
S为烷基、氟代烷基、芳基或氟代芳基(并且其中的两个S基团另外代表氢),
ArF为氟代芳基,并且
X1为氢或卤素中的一种。
适当的二硼阴离子在US-A-5,447,895中公开了。
另外,Ad-阴离子的其它例子为对应于结构式[M’K+Qn’]d-的那些阴离子,其中:
k为从1到3的整数;
n’为从2到6的整数;
n’-k=d;
M’为从元素周期表的13族中选出的元素,并且
独立地每次出现的Q是从氢化基、二烷基酰氨基、卤素、烷氧化合物基团、芳氧化合物基团、烃基和卤代烃基团中选出的,所述的Q具有最多20个碳原子,只要保证Q卤化物出现不超过一个。
在更优选的具体实施方案中,d为1,即反离子具有单一个负电荷并且对应于结构式A-。特别适用于本发明的包含硼的活化共催化剂可以由下面的一般结构式表示:[L*-H]+[BQ’4]-,其中:
L*为含有氮、硫或磷的中性路易斯碱;
B为氧化态3的硼,并且
Q’为氟化的C1-20的烃基。
最优选地,每次出现的Q’为氟代芳基,特别是五氟代苯基。
一般,通过将一个或多个亲油基团,例如长链烷烃基,长链链烯基团,或卤代、烷氧基、氨基、甲硅烷基或甲锗烷基取代的长链烷基或长链链烯基结合到布鲁斯台德酸L中,本发明的催化活化剂在脂族化合物中的溶解度增加。“长链”一词表明在该基团中具有从10到50个非氢原子的基团,优选地以非支化的形式。优选地,这种L基团含有从1到3个C10-40正烷基的总共有12到100个碳,更优选地2个C10-40的烷基和从21到90的总碳数。确信这种亲油基的存在使活化剂更易于溶解在脂族液体中,因此提高了催化剂活化的有效率。可以明确的是催化活化剂可以包含不同长度的亲油基团的混合形式。例如,一种适当的活化剂为质子化的铵盐,它是从可以在商业上得到的包括两个C14、C16或C18的烷基和一个甲基的混合基团的长链的胺衍生来的。这些胺是从Witco公司的商品名KemamineTM T9701下,以及从Akzo-Nobel在商品名ArmeenTM M2HT下得到的。基于金属络合物的用量,相对于目前需要的前面已知共催化剂的用量,该共催化剂可以以低的浓度来采用,同时保持相同或提高了的催化剂效率。
可以用作本发明中的离子型活化共催化剂的硼酸合物的说明性的,但并非限定性的例子为三取代的铵盐,例如:
四(五氟代苯基)硼酸癸基二(甲基)铵,
四(五氟代苯基)硼酸十二烷基二(甲基)铵,
四(五氟代苯基)硼酸十四烷基二(甲基)铵,
四(五氟代苯基)硼酸十六烷基二(甲基)铵,
四(五氟代苯基)硼酸十八烷基二(甲基)铵,
四(五氟代苯基)硼酸二十烷基二(甲基)铵,
四(五氟代苯基)硼酸甲基二(癸基)铵,
四(五氟代苯基)硼酸甲基二(十二烷基)铵,
四(五氟代苯基)硼酸甲基二(十四烷基)铵,
四(五氟代苯基)硼酸甲基二(十六烷基)铵,
四(五氟代苯基)硼酸甲基二(十八烷基)铵,
四(五氟代苯基)硼酸甲基二(二十烷基)铵,
四(五氟代苯基)硼酸三癸基铵,
四(五氟代苯基)硼酸三个十二烷基铵,
四(五氟代苯基)硼酸三个十四烷基铵,
四(五氟代苯基)硼酸三个十六烷基铵,
四(五氟代苯基)硼酸三个十八烷基铵,
四(五氟代苯基)硼酸三个二十烷基铵,
四(五氟代苯基)硼酸癸基二(正丁基)铵,
四(五氟代苯基)硼酸十二烷基二(正丁基)铵,
四(五氟代苯基)硼酸十八烷基二(正丁基)铵,
四(五氟代苯基)硼酸N,N-二个十二烷基苯胺盐,
四(五氟代苯基)硼酸N-甲基-N-十二烷基苯胺盐,
四(五氟代苯基)硼酸N,N-二(十八烷基)(2,4,6-三甲基苯胺)盐,
四(五氟代苯基)硼酸环己基二(十二烷基)铵,和
四(2,3,4,6-四氟代苯基)硼酸甲基二(十二烷基)铵,
适当的类似的取代硫鎓或磷鎓盐,例如也可以采用四(五氟代苯基)硼酸二(癸基)硫鎓盐,
四(五氟代苯基)硼酸(正丁基)十二烷基硫鎓盐,
四(五氟代苯基)硼酸三癸基磷鎓盐,
四(五氟代苯基)硼酸二(十八烷基)甲基磷鎓盐,和
四(五氟代苯基)硼酸三(十四烷基)磷鎓盐。
优选的活化剂为甲基四(五氟代苯基)硼酸二(十八烷基)铵和四(五氟代苯基)硼酸二(十八烷基)(正丁基)铵。
M*为Ni(Ⅱ)或Pd(Ⅱ);
K为卤素、烃基、或烃氧基;
Ar*为芳基,特别是2,6-二异丙基苯基或苯胺基;
CT-CT为1,2-乙烷二基、2,3-丁烷二基,或形成了稠环的体系,其中的两个T基一起为1,8-萘二基;并且
A-为惰性的非配位的阴离子。
前述的催化剂被M.Brookhart等在J.Am.Chem.Soc.(美国化学会杂志),118,267-268页(1996)和美国化学会杂志,117,6414-6415页(1995)中介绍了,它被用作活性聚合反应的催化剂,特别是单独地或与极性共聚单体例如氯乙烯、丙烯酸烷基酯和甲基丙烯酸烷基酯一起的α-烯烃的聚合反应的催化剂。
另外的催化剂包括处于+2、+3或+4式符氧化态的第3、4族或镧系金属的衍生物。优选的化合物包括含有1到3个π-键的阴离子或中性配位基团的金属络合物,它们可以是环状或非环状的离域的π-键阴离子配位基。这些π-键阴离子配位基的例子是共轭或非共轭的、环状或非环状的二烯基、烯丙基、硼杂苯基和芳烃基。“π-键”一词表示配位基通过从部分离域的π-键分配电子而键合在过渡金属上。
在离域的π-键基团上的每个原子可彼此无关地被基团取代,该基团是从包括氢、卤素、烃基、卤代烃基、烃基取代的准金属基团,其中的准金属是从元素周期表的14族中选出的,并且这些烃基或烃基取代的准金属基团进一步被含有15或16族杂原子的基团所取代。包括在“烃基”一词范围内的有C1-20的直链、支链和环状烷基,C6-20的芳香基,C7-20的烷基取代的芳香基和C7-20的芳基取代的烷基。另外,两个或多个这样的基团可以一起形成稠环体系,包括部分或全部氢化的稠环体系,或者它们可与金属形成金属环。适当的烃基取代的有机准金属基团包括一、二或三取代的14族元素的有机准金属基团,其中每个烃基含有1到20个碳原子。适当的烃基取代的有机准金属基团的例子包括三甲基甲硅烷基、三乙基甲硅烷基、乙基二甲基甲硅烷基、甲基二乙基甲硅烷基、三苯基甲锗烷基和三甲基甲锗烷基。含有15或16族杂原子的基团的例子包括胺、膦、醚或硫醚基团或它们的二价衍生物,如键合到过渡金属或镧系金属,和键合到烃基或键合到烃基取代的含准金属的基团上的酰胺、磷化物、醚或硫醚基团。
适当的阴离子型离域的π-键基团的例子包括环戊二烯基、茚基、芴基、四氢茚基、四氢芴基、八氢芴基、戊二烯基、环己二烯基、二氢蒽基、六氢蒽基、十氢蒽基团,和硼杂苯基,以及它们的C1-10的烃基取代或C1-10烃基取代的甲硅烷基取代的衍生物。优选的阴离子型离域的π-键基团为环戊二烯基、五甲基环戊二烯基、四甲基环戊二烯基、四甲基甲硅烷基环戊二烯基、茚基、2,3-二甲基茚基、芴基、2-甲基茚基、2-甲基-4-苯基茚基、四氢芴基、八氢芴基和四氢茚基。
硼杂苯为阴离子配位体,它是含有硼的苯的同系物。它们目前在文献中是已知的,它已被G.Herberich等在Organometallics(有机金属),14,1,471-480页(1995)中介绍了。优选的硼杂苯对应于下面的结构式:其中R”是从包括烃基、甲硅烷基或甲锗烷基的种类中选出的,所述的R”具有不超过20个非氢原子。在包含这种离域的π-键基团的二价衍生物的络合物中,它的一个原子是通过共价键或共价键键合的二价基团键合到络合物的另一个原子上,因此形成了桥接体系。
催化剂的适当的种类为对应于下面结构式的过渡金属络合物:
LlMXmX’nX”p,或它的二聚体
其中:
L为阴离子型离域的π-键基团,它被键合到M上,它含有不超过50个非氢原子,非必须地两个L基团可以结合到一起形成桥接结构,并且进一步非必须地,一个L可以键合到X上;
M为处于+2、+3或+4式符氧化态的元素周期表的4族中的金属;
X为非必须的不超过50个非氢原子的二价取代基,它与L一起形成与M的金属环;
X’为非必须的具有不超过20个非氢原子的中性配位基;
每次出现的X”为具有不超过40个非氢原子的一价阴离子基团,非必须地,两个X”基团可以共价键结合在一起形成二价的双阴离子基团,两者都具有与M结合的键,或非必须地,两个X”基团可以共价键结合在一起,形成中性的共轭或非共轭的二烯,该二烯被π-键键合到M上(因此M处于+2的氧化态),或者进一步非必须地,一个或多个X”和一个或多个X’基团可以键合在一起,因此形成了两者都以共价键键合到M上的基团,并且以路易斯碱官能团的方式与M配位;
l为0,1或2;
m为0或1;
n为从0到3的数;
p为从0到3的整数;并且
l+m+n的总数等于M的式符氧化态,除了当2X”基团一起形成中性的共轭或非共轭二烯,该二烯被π-键键合到M上,在这种情况下,l+m的总数等于M的式符氧化态。
优选的络合物包括含有一个或两个L基团的络合物。后一种络合物包含带有连接两个L基团的桥接基团的那些。优选的桥接基团为对应于结构式(ER* 2)x的那些,其中E为硅、锗、锡或碳,每次独立地出现的R*为氢或从甲硅烷基、烃基、烃氧基和它们的组合中选出的基团,所述的R*具有最多30个碳原子或硅原子,并且x为1到8。优选地,每次独立地出现的R*为甲基、乙基、丙基、苄基、叔丁基、苯基、甲氧基、乙氧基或苯氧基。
含有两个L基团的络合物的例子为对应于下面结构式的化合物:
M为锆,锆或铪,优选地为处于+2或+4式符氧化态的锆或铪。
每个彼此无关出现的R3为从包含氢、烃基、甲硅烷基、甲锗烷基、氰基、卤素和它们的组合的种类中选出的,所述的R3具有不超过20个非氢原子,或者相邻的R3基团一起形成了二价衍生物(即烃二基、甲硅烷二基、甲锗烷二基),因此形成了稠环体系,并且
各自彼此无关地出现的X”为不超过40个非氢原子的阴离子配位体,或者两个X”基团一起形成了不超过40个非氢原子的二价阴离子配位基团,或者它们一起为具有从4到30个非氢原子的共轭二烯,它们与M形成了π-络合物,因此M为+2的式符氧化态,并且
R*、E和x与前面的定义相同。
前述的金属络合物特别适合用于制备具有立构规整的分子结构的聚合物。在这个能力上,优选的是络合物具有Cs对称或具有手性的立体刚性的结构。第一种类型的例子是具有不同离域的π-键体系的化合物,例如一个环戊二烯基和一个芴基。基于Ti(Ⅳ)或Zr(Ⅳ)的类似体系在Ewen等的美国化学会杂志,110,6255-6256页(1980)中被公开用于制备间同立构的烯烃聚合物。手性结构的例子包括外消旋双茚基络合物。基于Ti(Ⅳ)或Zr(Ⅳ)的类似体系在Wild等的J.Organomet.Chem.(有机金属化学杂志),232,233-47页,(1982)中被公开用于制备全同立构的烯烃聚合物。
含有两个π-键合基团的举例性桥接配体为:(二甲基甲硅烷基-双(环戊二烯基))、(二甲基甲硅烷基-双(甲基环戊二烯基))、(二甲基甲硅烷基-双(乙基环戊二烯基))、(二甲基甲硅烷基-双(叔丁基环戊二烯基))、(二甲基甲硅烷基-双(四甲基环戊二烯基))、(二甲基甲硅烷基-双(茚基))、(二甲基甲硅烷基-双(四氢茚基))、(二甲基甲硅烷基-双(芴基))、(二甲基甲硅烷基-双(四氢芴基))、(二甲基甲硅烷基-双(2-甲基-4-苯芴基))、(二甲基甲硅烷基-双(2-甲基茚基))、(二甲基甲硅烷基-环戊二烯基-芴基)、(二甲基甲硅烷基-环戊二烯基-八氢芴基)、(二甲基甲硅烷基-双环戊二烯基-四氢芴基)、(1,1,2,2-四甲基-1,2-二甲硅烷基-双环戊二烯基)、(1,2-双(环戊二烯)乙烷)和(亚异丙基-环戊二烯-芴基)。
优选的X”基团选自氢化基、烃基、甲硅烷基、甲锗烷基、卤代烃基、卤代甲硅烷基、甲硅烷基烃基和氨基烃基,或者两个X”基团一起形成共轭二烯烃的二价衍生物,或者它们一起形成中性的π-键的共轭二烯烃。最优选的X”基团是C1-20的烃基。
用于本发明的另一类金属络合物对应于前面结构式:LlMXmX’nX”p,或它们的二聚体,其中X为具有最多50个非氢原子的二价取代基,它与L一起形成了与M的金属环。
优选的二价X取代基包括含有至多30个非氢原子的基团,该基团包括至少一个原子,该原子为直接与离域π-键合基团连接的氧、硫、硼或元素周期表14族的元素;和一个不同的原子,它选自氮、磷、氧或硫,并以共价键键合到M上。
根据本发明采用的该第4族金属配位络合物的优选的类型对应于下面的结构式:
其中:
M为钛或锆,优选地为处于+2、+3或+4价式符氧化态的钛;
R3各自独立地选自氢、烃基、甲硅烷基、甲锗烷基、氰基、卤素和其结合的基团,所述的R3具有至多20个非氢原子,或相邻的R3基团一起形成二价衍生物(即烃二基、硅烷二基或锗烷二基),因此形成了稠环体系;
每个X”为卤素、烃基、烃氧基或甲硅烷基,所述的基团具有至多20个非氢原子,或者两个X”基团一起形成了中性的C5-30的共轭二烯或它们的二价衍生物;
Y为-O-、-S-、-NR*-、-PR*-;和
Z为SiR* 2、CR* 2、SiR* 2SiR* 2、CR* 2CR* 2、CR*=CR*、CR* 2SiR* 2或GeR* 2,其中:R*为前面定义的。
可用于实施本发明的说明性4族金属配位物包括:
环戊二烯基三甲基钛,
环戊二烯基三乙基钛,
环戊二烯基三异丙基钛,
环戊二烯基三苯基钛,
环戊二烯基三苄基钛,
环戊二烯基2,4-二甲基戊二烯基钛,
环戊二烯基2,4-二甲基戊二烯基钛·三乙基膦,
环戊二烯基2,4-二甲基戊二基钛·三甲基膦,
环戊二烯基二甲基甲醇钛,
环戊二烯基二甲基氯化钛,
五甲基环戊二烯基三甲基钛,
茚基三甲基钛,
茚基三乙基钛,
茚基三丙基钛,
茚基三苯基钛,
四氢茚基三苄基钛,
五甲基环戊二烯基三异丙基钛,
五甲基环戊二烯基三苄基钛,
五甲基环戊二烯基二甲基甲醇钛,
五甲基环戊二烯基二甲基氯化钛,
双(η5-2,4-二甲基戊二烯基)钛,
双(η5-2,4-二甲基戊二烯基)钛·三甲基膦,
双(η5-2,4-二甲基戊二烯基)钛·三乙基膦,
八氢芴基三甲基钛,
四氢茚基三甲基钛,
四氢芴基三甲基钛,
(叔丁基酰氨基)(1,1-二甲基-2,3,4,9,10-η-1,4,5,6,7,8-六氢萘基)二甲基硅烷二甲基钛,
(叔丁基酰氨基)(1,1,2,3-四甲基-2,3,4,9,10-η-1,4,5,6,7,8-六氢萘基)二甲基硅烷二甲基钛,
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)二甲基硅烷二苄基钛,
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)二甲基硅烷二甲基钛,
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)-1,2-乙烷二基二甲基钛,
(叔丁基酰氨基)(四甲基-η5-茚基)二甲基硅烷二甲基钛,
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)二甲基硅烷2-(二甲氨基)苄基钛(Ⅲ),
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)二甲基硅烷烯丙基钛(Ⅲ),
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)二甲基硅烷2,4-二甲基戊二烯基钛(Ⅲ),
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)二甲基硅烷1,4-二苯基-1,3-丁二烯钛(Ⅲ),
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)二甲基硅烷1,3-戊二烯钛(Ⅱ),
(叔丁基酰氨基)(2-甲基茚基)二甲基硅烷1,4-二苯基-1,3-丁二烯钛(Ⅱ),
(叔丁基酰氨基)(2-甲基茚基)二甲基硅烷2,4-己二烯钛(Ⅱ),
(叔丁基酰氨基)(2-甲基茚基)二甲基硅烷2,3-二甲基-1,3-丁二烯钛(Ⅳ),
(叔丁基酰氨基)(2-甲基茚基)二甲基硅烷异戊二烯钛(Ⅳ),
(叔丁基酰氨基)(2-甲基茚基)二甲基硅烷1,3-丁二烯钛(Ⅳ),
(叔丁基酰氨基)(2,3-二甲基茚基)二甲基硅烷2,3-二甲基-1,3-丁二烯钛(Ⅳ),
(叔丁基酰氨基)(2,3-二甲基茚基)二甲基硅烷异戊二烯钛(Ⅳ),
(叔丁基酰氨基)(2,3-二甲基茚基)二甲基硅烷二甲基钛(Ⅳ),
(叔丁基酰氨基)(2,3-二甲基茚基)二甲基硅烷二苄基钛(Ⅳ),
(叔丁基酰氨基)(2,3-二甲基茚基)二甲基硅烷1,3-丁二烯钛(Ⅳ),
(叔丁基酰氨基)(2-甲基茚基)二甲基硅烷1,3-戊二烯钛(Ⅱ),
(叔丁基酰氨基)(2,3-二甲基茚基)二甲基硅烷1,4-二苯基-1,3-丁二烯钛(Ⅱ),
(叔丁基酰氨基)(2-甲基茚基)二甲基硅烷1,3-戊二烯钛(Ⅱ),
(叔丁基酰氨基)(2-甲基茚基)二甲基硅烷二甲基钛(Ⅳ),
(叔丁基酰氨基)(2-甲基茚基)二甲基硅烷二苄基钛(Ⅳ),
(叔丁基酰氨基)(2-甲基-4-苯基茚基)二甲基硅烷1,4-二苯基-1,3-丁二烯钛(Ⅱ),
(叔丁基酰氨基)(2-甲基-4-苯基茚基)二甲基硅烷1,3-戊二烯钛(Ⅱ),
(叔丁基酰氨基)(2-甲基-4-苯基茚基)二甲基硅烷2,4-己二烯钛(Ⅱ),
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)二甲基硅烷1,3-丁二烯钛(Ⅳ),
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)二甲基硅烷2,3-二甲基-1,3-丁二烯钛(Ⅳ),
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)二甲基硅烷异戊二烯钛(Ⅳ),
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)二甲基硅烷1,4-二苄基-1,3-丁二烯钛(Ⅱ),
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)二甲基硅烷2,4-己二烯钛(Ⅱ),
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)二甲基硅烷3-甲基-1,3-戊二烯钛(Ⅱ),
(叔丁基酰氨基)(2,4-二甲基戊二烯-3-基)二甲基硅烷二甲基钛,
(叔丁基酰氨基)(6,6-二甲基环己二烯基)二甲基硅烷二甲基钛,
(叔丁基酰氨基)(1,1-二甲基-2,3,4,9,10-η-1,4,5,6,7,8-六氢萘-4-基)二甲基硅烷二甲基钛,
(叔丁基酰氨基)(1,1,2,3-四甲基-2,3,4,9,10-η-1,4,5,6,7,8-六氢萘-4-基)二甲基硅烷二甲基钛。
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)甲基苯基硅烷二甲基钛(Ⅳ),
(叔丁基酰氨基)(四甲基-η5-环戊二烯基)甲基苯基硅烷1,4-二苯基-1,3-丁二烯钛(Ⅱ),
1-(叔丁基酰氨基)-2-(四甲基-η5-环戊二烯基)乙烷二基二甲基钛(Ⅵ),和
1-(叔丁基酰氨基)-2-(四甲基-η5-环戊二烯基)乙烷二基1,4-二苯基-1,3-丁二烯钛(Ⅳ)。
适合用于本发明的包括桥接配位物的含双L基的配合物包括:
双(环戊二烯基)二甲基锆,
双(环戊二烯基)二苄基锆,
双(环戊二烯基)甲基苄基锆,
双(环戊二烯基)甲基苯基锆,
双(环戊二烯基)二苯基锆,
双(环戊二烯基)烯丙基钛,
双(环戊二烯基)甲基甲醇锆,
双(环戊二烯基)甲基氯化锆,
双(五甲基环戊二烯基)二甲基锆,
双(五甲基环戊二烯基)二甲基钛,
双(茚基)二甲基锆,
茚基芴基二甲基锆,
双(茚基)甲基(2-(二甲氨基)苄基)锆,
双(茚基)甲基三甲基甲硅烷基锆,
双(四氢茚基)甲基三甲基甲硅烷基锆,
双(五甲基环戊二烯基)甲基苄基锆,
双(五甲基环戊二烯基)二苄基锆,
双(五甲基环戊二烯基)甲基甲醇锆,
双(五甲基环戊二烯基)甲基氯化锆,
双(甲基乙基环戊二烯基)二甲基锆,
双(丁基环戊二烯基)二苄基锆,
双(叔丁基环戊二烯基)二甲基锆,
双(乙基四甲基环戊二烯基)二甲基锆,
双(甲基丙基环戊二烯基)二苄基锆,
双(三甲基甲硅烷基环戊二烯基)二苄基锆,
二甲基甲硅烷基-双(环戊二烯基)二甲基锆,
二甲基甲硅烷基-双(四甲基环戊二烯基)烯丙基钛(Ⅲ),
二甲基甲硅烷基-双(叔丁基环戊二烯基)二氯化锆,
二甲基甲硅烷基-双(正丁基环戊二烯基)二氯化锆,
亚甲基-双(四甲基环戊二烯基)2-(二甲氨基)苄基钛(Ⅲ),
亚甲基-双(正丁基环戊二烯基)2-(二甲氨基)苄基钛(Ⅲ),
二甲基甲硅烷基-双(茚基)苄基氯化锆,
二甲基甲硅烷基-双(2-甲基茚基)二甲基锆,
二甲基甲硅烷基-双(2-甲基-4-苯基茚基)二甲基锆,
二甲基甲硅烷基-双(2-甲基茚基)1,4-二苯基-1,3-丁二烯锆,
二甲基甲硅烷基-双(2-甲基-4-苯基茚基)-1,4-二苯基-1,3-丁二烯锆(Ⅱ),
二甲基甲硅烷基-双(四氢茚基)1,4-二苯基-1,3-丁二烯锆(Ⅱ),
二甲基甲硅烷基-双(芴基)甲基氯化锆,
二甲基甲硅烷基-双(四氢芴基)二(三甲基甲硅烷基)锆,
(异亚丙基)(环戊二烯基)(芴基)二苄基锆,和
二甲基甲硅烷基(四甲基环戊二烯基)(芴基)二甲基锆。
显然,其它催化剂,特别是含其它4族金属的催化剂对本领域熟练技术人员是显而易见的。
如果需要,本发明的共催化剂也可以与在每个烃基上带有1到10个碳原子的三(烃基)铝化合物、齐聚或聚合的铝氧烷化合物、在每个烃基或烃氧基上带有1到20个碳原子的二(烃基)(烃氧基)铝化合物或前述这些化合物的混合物一起使用。这些铝化合物被采用,因为它们有益地从聚合反应混合物中除去杂质的能力,例如除去氧、水和醛。
适当的二(烃基)(烃氧基)铝化合物对应于结构式T1 2AlOT2,其中T1为C3-6的仲或叔烷基,最优选的为异丙基、异丁基或叔丁基;并且T2为C12-30的烷芳基或芳烷基,最优选的为2,6-二(叔丁基)-4-甲基苯基、2,6-二(叔丁基)-4-甲基甲苯基、2,6-二(异丁基)-4-甲基苯基或4-(3’,5’-二叔丁基甲苯基)-2,6-二叔丁基苯基。
优选的铝化合物包括C2-6的三烷基铝化合物,特别是其中的烷基为乙基、丙基、异丙基、正丁基、异丁基、戊基、新戊基或异戊基的那些;二烷基(芳氧基)铝化合物,它在烷基上含有1-6个碳原子并且在芳基上含有6到8个碳原子(特别是(3,5-二(叔丁基)-4-甲基苯氧基)二异丁基铝),甲基铝氧烷,改性的铝氧烷和二异丁基铝氧烷。铝化合物与金属配位物的摩尔比优选地从1∶10,000到1000∶1,更优选地从1∶5000到100∶1,最优选地从1∶100到100∶1。
采用的催化剂/共催化剂的摩尔比优选地处于从1∶10到10∶1,更优选地从1∶5到1∶1,最优选地从1∶1.5到1∶1。如果需要,也可以采用本发明的活性共催化剂混合物。
适当的可加成聚合反应的单体包括烯属不饱和单体、炔属化合物、共轭或非共轭二烯以及多烯。优选的单体包括烯烃,例如带有2到20,000个、优选地从2到20个、更优选地从2到8个碳原子的α-烯烃,以及两个或多种这种α-烯烃的组合。特别适合的α-烯烃包括,例如乙烯、丙烯、1-丁烯、1-戊烯、4-甲基戊烯-1、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、1-十一烯、1-十二烯、1-十三烯、1-十四烯、1-十五烯或者它们的组合,以及在聚合反应过程中形成的长链端乙烯基的齐聚或聚合的反应产物,并且C10-30的α-烯烃被特别地加入到反应混合物中,以产生在得到的聚合物中的相当长的支链。优选地,α-烯烃为乙烯、丙烯、1-丁烯、4-甲基-戊烯-1、1-己烯、1-辛烯、以及乙烯和/或丙烯与一个或多种这种其它α-烯烃的组合。其它优选的单体包括苯乙烯、卤代或烷基取代的苯乙烯、四氟乙烯、乙烯基环丁烯、1,4-己二烯、双环戊二烯、亚乙基降冰片烯和1,7-辛二烯。也可以采用上述单体的混合物。
一般,可以在目前技术上广为人知的用于齐格勒-纳塔或Kaminsky-Sinn类聚合反应的条件下进行聚合反应。如果需要,可以采用悬浮、溶液、淤浆、气相或高压聚合反应,不管它们是否以以间歇或连续方式还是其它的操作条件来采用。这些广为人知的聚合反应过程的实例在WO88/02009,美国专利号5,084,534,5,405,922,4,588,790,5,032,652,4,543,399,4,564,647,4,522,987以及其它场合中描述了。优选的聚合反应温度是从0到250℃。优选的聚合反应压力是从常压到3000个大气压。
但是,当该催化剂体系是在脂族或脂环类液体稀释剂的存在下用于溶液聚合反应,更优选地连续的溶液聚合反应过程中时,本发明的优点被特别地体现出。“连续的聚合反应”一词表示至少聚合反应的产物是连续地从反应混合物中分离出的,例如通过对反应混合物的一部分进行脱挥发份。优选地,在聚合反应过程中,一种或多种反应物也被连续地加入到聚合反应混合物中的。适当的脂族或脂环类液体稀释剂的例子包括直链或支链的烃,例如异丁烷、丁烷、戊烷、己烷、庚烷、辛烷和它们的混合物;脂环烃,例如环己烷、环庚烷、甲基环己烷、甲基环庚烷和它们的混合物;以及过氟代烃,例如过氟代C4-10的烷烃,等等。适当的稀释剂也可以包括芳香烃(特别是与芳香α-烯烃一起采用,例如苯乙烯或环烷基取代的苯乙烯),包括甲苯、乙苯或二甲苯,以及液体烯烃(它可作为单体或共聚单体),包括乙烯、丙烯、丁二烯、环戊烯、1-己烯、3-甲基-1-戊烯、4-甲基-1-戊烯、1,4-己二烯、1-辛烯、1-癸烯、苯乙烯、二乙烯基苯、烯丙基苯、乙烯基甲苯(包括所有单独的或混合的异构体),等等。也可以采用前述的混合物。
在大多数聚合反应中,催化剂:所采用的可聚合的化合物的摩尔比是从10-12∶1到10-1∶1,更优选地从10-12∶1到10-5∶1。
本发明的催化剂体系也可以与至少一种其它的均相或非均相的聚合反应催化剂一起用于以连续或平行地连接的独立的反应器中,以制备具有所需性能的聚合物混合物。该过程的实例在WO94/00500中被公开了,它与美国专利流水号07/904,770是相同的。更具体的过程在待审的美国专利流水号08/10958中公开了,1993年1月29日申请。
分子量调节剂也可以与该共催化剂一起采用。这些分子量调节剂的实例包括氢、三烷基铝化合物或其它已知的链转移剂。采用本发明的共催化剂的独特的优点是以大大提高的催化剂效率制备出窄分子量分布的α-烯烃的均聚物和共聚物的能力(取决于反应条件)。优选的聚合物具有小于2.5的Mw/Mn,更优选的小于2.3。由于提高了抗张强度性能,这些窄分子量分布的聚合物产品是非常受欢迎的。
已经认识到本发明可以在不存在还没有被特别公开的任何具体组分下进行。提供下面的实施例以进一步说明本发明,并且不被它们所限制。除非特别说明,所有的份数及百分数都用重量基准表示。实施例1
四(五氟代苯基)硼酸双(十八烷基)甲基铵的制备((C18H37)2N(Me)H+B(C6F5)4 -)
双(十八烷基)甲基氯化铵((C18H37)2N(Me)H+Cl-)
将0.50克双(十八烷基)甲基胺((C18H37)2N(Me))(Aldrich化学公司)溶解在50毫升的己烷中。通过注射器加入在乙醚中的HCl(1M,Aldrich,1.17毫升),结果立即生成白色沉淀。将混合物搅拌数小时,然后通过一中等孔隙度(10-15μm)的玻璃料过滤。用另外的己烷冲洗保留在玻璃料上的固体,然后在玻璃料上干燥并最终在真空下干燥。大约得到了0.56克白色固体。制备A)
在干燥箱中,在小缸中以固态混合0.50克的LiB(C6F5)4和0.38克的(C18H37)2N(Me)H+Cl-。从干燥箱中移出小缸并加入30毫升的蒸馏水。看起来LiB(C6F5)4溶解了,但是胺的盐酸盐漂浮在液体的上部。将混合物放置在机械震荡器中1个小时。在此期间,胺的盐酸盐缓慢消失,并且取而代之的是粘结在缸壁上的粘性白色沉淀。1小时以后,加入20毫升甲苯,并再次将混合物放置在震荡器中10分钟。然后将混合物倒入另外的漏斗中并加入20毫升的饱和碳酸钠水溶液。分层并弃去水层。用20毫升的水冲洗有机层、用MgSO4干燥并过滤到小的Schlenk管中。在真空下除去挥发性物质,留下浅棕色粘性油状物。将Schlenk管放入干燥箱中,并且油状物溶解在环己烷中。采用容量瓶使溶液变为10毫升。通过在用环己烷移出产物之前或之后称量Schlenk管的重量,产物的重量测定为0.80克。假定(C18H37)2N(Me)H+B(C6F5)4 -的分子量为1216.08克/摩尔,计算出溶液的浓度为0.066M,10.3wt%。制备B)
在干燥箱中,使0.50克LiB(C6F5)4和0.42克(C18H37)2N(Me)H+Cl-在一小的瓶中的25毫升甲苯中成浆。从干燥箱中移出瓶子并加入20毫升蒸馏水。将瓶子放置在震荡器上并剧烈搅拌1小时。结束后,加入20毫升饱和碳酸钠水溶液,并将混合物转移到另外的漏斗中。分层并弃去水层。用20毫升饱和碳酸钠接着用20毫升水冲洗有机层,用硫酸镁干燥并过滤。然后,在真空下除去发挥性物质,留下0.71克浅棕色油状物。将烧瓶放置在干燥箱中,并使油状物溶解在10毫升混合的烷烃中(IsoparTME,从Exxon化学股份有限公司得到),得到浓度0.0075M,9.0wt%的溶液,然后进一步稀释到0.0075M的最终溶液浓度。制备C)
在干燥箱中,使0.50克LiB(C6F5)4和0.42克(C18H37)2N(Me)H+Cl-在20毫升的环己烷中成浆。加热混合物至回流1.5小时。开始加热后不久,溶液变得透明。在回流时间结束时,使混合物冷却到室温,并通过一中等孔隙度(10-15毫米)的采用硅藻土过滤助剂(CeliteTM)的玻璃料漏斗进行过滤。将溶液转移到4盎司瓶中并从干燥箱中移出,用氮气简单地冲洗然后放回到干燥箱中。移出等分试样并用重量分析测定浓度。得到了0.022M,3.4wt%的溶液浓度。聚合反应
向1加仑的搅拌的反应器中加入IsoparTM E溶剂、1-辛烯和5毫摩尔的氢气。将反应器加热到130℃并用乙烯饱和到450磅/平方英寸(表压,3.1MPa)。在干燥箱中,通过同时注射2.5毫摩尔的(叔丁基酰氨基)二甲基(η5-四甲基环戊二烯基)(η4-1,3-戊二烯)钛催化剂、四(五氟代苯)硼酸双(十八烷基)甲基铵共催化剂(通过前面制备A)、B)或C)中的一个制备的)和非必须的第三组分(三异丁基铝改性的甲基铝氧烷(MMAO)、三异丁基铝(TIBA)、或(2,6-二(叔丁基)-4-甲基苯氧基)二(异丁基)铝(DIBAL-BOT)),制备了催化剂组合物。然后,通过注射器将该混合物转移到加料旁通支管并在大约4分钟内注射到反应器中。使聚合反应进行10分钟,同时加入乙烯,要求保持450磅/平方英寸(3.1MPa)的压力。要么将聚合物溶液从反应器中转移到玻璃釜中,然后采用真空烘箱干燥,要么扔掉。在分离并干燥聚合物的情况下,以每克钛的千克聚合物来计算催化剂效率。在聚合物没有保留的情况下,以每克钛在反应过程中消耗的千克乙烯来计算效率。聚合反应的详细结果如表1所示。
表1
实施例2四(五氟代苯基)硼酸双(氢化动物脂烷基)甲基铵((C18-22H37-45)2N+(Me)HB-(C6F5)4)的制备
编号 | 共催化剂 | (微摩尔) | 第3组分 | (微摩尔) | 溶剂(克) | 辛烯(克) | 效率(千克乙烯/克钛) |
12345 | AAAAA | 2.53.753.155.01.5 | MMAO““““ | 25““““ | 14261423141514101433 | 138132138136137 | 0.81.00.91.00.5 |
678910 | AAAAB | 3.75““““ | 无MMAOTIBADIBAL-BOT“ | 025““50 | 14321462145914701427 | 130137133130139 | 0.50.60.70.91.5 |
11 | C | “ | “ | “ | 1420 | 140 | 0.9 |
除了铵盐是从双(氢化动物脂烷基)甲基胺(一种含有从动物脂衍生来的混合C18-22烷基的三烷基胺,从Witco公司或Akzo Nobel获得)制备的以外,基本上重复实施例1制备C的合成步。制备A)
将双(氢化动物脂烷基)甲基胺(从Witco联合公司来的KEMAMINET-9701,由商家介绍的“总的胺值”计算出胺的分子量为513.8)(5.65克,11.0毫摩尔)溶解在50毫升的己烷中。通过注射器加入在醚中的HCl(1M,13.75毫升),得到了白色沉淀。使混合物搅拌30分钟,然后采用具有孔尺寸10-5微米的玻璃料过滤。采用己烷洗涤保留的固体并在真空下干燥。
在干燥箱中,使1.20克上面得到的胺HCl盐(2.18毫摩尔)和1.57克LiB(C6F5)4(2.29毫摩尔)在己烷中混合并在25℃下搅拌2小时。搅拌结束后,加入环己烷(10-15毫升),并采用具有孔尺寸10-15微米并且顶部有硅藻土过滤助剂(CeliteTM)的玻璃料过滤,采用重量法测得溶液的浓度为6.3wt%。制备B)
双(氢化动物脂烷基)甲基胺(从Akzo Nobel公司得到的ARMEENM2HT;由商家提供的分析证明书报告了胺的分子量为521.1)(5.00克,9.6毫摩尔)溶解在50毫升的己烷中。通过注射器加入在醚中的HCl(1M,10.1毫升),得到白色沉淀。用手旋动混合物10分钟,然后采用具有孔尺寸10-15微米的玻璃料进行过滤,用己烷冲洗保留的白色固体并在真空下干燥。
在干燥箱中,上面得到的2.00克的胺HCl盐(3.59毫摩尔)和2.58克的LiB(C6F5)4(3.77毫摩尔)以固态进行混合。加入环己烷(30毫升)并搅拌混合物2小时。搅拌结束后,采用具有孔尺寸10-15微米的并且顶部有CetiteTM过滤助剂的玻璃漏斗过滤混合物,得到浅棕色透明溶液。用重量法测得溶液的浓度为10.3wt%。制备C)(原位生成盐酸盐)
将双(氢化动物脂烷基)甲基胺(ARMEENM2HT,1.0克,1.92毫摩尔)溶解在25毫升的甲基环己烷中。通过注射器加入水性HCl(1M,1.92毫升)。将混合物搅拌30分钟,然后加入溶解在20毫升水中的LiB(C6F5)4(1.32克,1.92毫摩尔)溶液。使混合物另外搅拌30分钟。然后倒入到另外的漏斗中并加入50毫升饱和的氯化钠水溶液。分层后弃去水层。有机层用硫酸镁干燥一个晚上。然后采用具有孔尺寸10-15微米的玻璃料进行过滤,得到浅棕色透明溶液。将溶液转移到瓶中,用氮气彻底冲洗,然后放回到干燥箱中。用重量法测得溶液的浓度为17.5wt%。制备D:放大实验
将甲基环己烷(1200毫升)放入2升的圆柱型烧瓶中。在搅拌下将双(氢化动物脂烷基)甲基胺(ARMEENM2HT,104克,磨成粉末状)加入到烧瓶中并搅拌至完全溶解。将水性HCl(1M,200毫升)加入到烧瓶中,并搅拌混合物30分钟。立即形成白色沉淀。结束后,将LiB(C6F5)4·Et2O·3LiCl(Mw=887.3;177.4克)加入到烧瓶中。溶液开始变成乳白色。在烧瓶上装上顶部有蒸馏设备的6”Vigreux柱并加热混合物(内壁温度140℃)。从烧瓶中蒸出乙醚和甲基环己烷。这时两相溶液稍微变得模糊。使混合物冷却到室温,并将内含物放置到4升的另外的漏斗中。移出水层并弃掉,并且用水洗涤有机层两次并再次弃掉水层。产物溶液分成两等份,以评价两种操作过程。这些水饱和的甲基环己烷溶液经测定含有0.48wt%的乙醚(Et2O)。操作过程b 13X分子筛技术
将溶液(600毫升)转移到1升的烧瓶中,用氮气彻底清洗,并转移到干燥箱中。使溶液通过一含有13X分子筛的柱子(1”直径,6”高度)。这使乙醚的含量从0.48wt%降低到0.28wt%。然后,在新鲜的13X分子筛(20克)上搅拌材料4小时。然后测定乙醚的含量为0.19wt%。然后,搅拌混合物一个晚上,得到进一步降低的乙醚含量,达到大约40ppm。采用配有具有孔尺寸10-15微米的玻璃料的漏斗过滤混合物,得到透明的溶液(通过另外的干的甲基环己烷来冲洗分子筛)。采用重量分析测定浓度,得到16.7wt%的数值。操作过程b算空技术
将溶液(600毫升)转移到1升的烧瓶中并加入35克硫酸镁。搅拌混合物5分钟,然后通过配有具有孔尺寸10-15微米的玻璃料的漏斗过滤到第二个1升的烧瓶。用氮气彻底清洗透明的溶液并转移到干燥箱中。在真空下除去挥发性材料,留下透明的、浅棕色油状物。将该油状物再次溶解在干燥的、脱氧的甲基环己烷中,并通过重量分析(23.5wt%)测定其浓度。通过GC分析表明溶液含有<20ppm的乙醚。聚合反应
以上面的动物脂铵盐衍生物作为活化剂并且以不同的过渡金属络合物作为催化剂,基本上重复实施例1的聚合反应条件。结果包括在表2中。
表2编 催化剂* 制备的共催化剂 第3组分(微摩尔) 溶剂(克) 辛烯(克) 效率(千克号(微摩尔) (微摩尔) 乙烯/克钛12 A(1.5) A(2.25) DIBAL-BOT(15) 1461 135 1.3513 A(1.5) B(2.25) DIBAL-BOT(15) 1461 137 1.3514 A(1.5) C(2.25) DIBAL-BOT(15) 1453 139 1.9015 B(0.5) C(0.75) DIBAL-BOT(5) 1444 137 3.2916 A(0.5) C(0.75) DIBAL-BOT(5) 1462 140 4.0217 B(0.5) C(0.75) DIBAL-BOT(5) 1456 137 2.5118 C(0.5) C(0.75) DIBAL-BOT(5) 1450 138 2.77
*A=(叔丁基酰氨基)二甲基(η5-四甲基环戊二烯基)(η4-1,3-戊二烯)钛
B=(异丙基酰氨基)(二甲基)(η5-2,3,4,6-四甲基茚基)二甲基钛
C=(叔丁基酰氨基)(二甲基)(η5-2,3,4,6-四甲基茚基)二甲基钛实施例3甲基三(五氟代苯基)苯基硼酸双(氢化动物脂烷基)甲基铵((C18-22H37-45)2N(Me)H+B(C6H5)(C6F5)3 -)的制备
除了硼盐为甲基三(五氟苯基)硼酸锂盐外,基本上重复实施例2的合成步。聚合反应
向1加仑搅拌的反应器中加入1440毫升IsoparTM E溶剂、126克1-辛烯和氢气(在35Δ磅/平方英寸,0.24ΔMPa下大约25毫升)。将反应器加热到130℃并用乙烯饱和到450磅/平方英寸(3.1MPa)。在干燥箱中,通过混合(叔丁基酰氨基)二甲基(η5-四甲基环戊二烯基)(η4-1,3-戊二烯)钛催化剂、三(五氟代苯基)苯基硼酸双(氢化动物脂烷基)甲基铵和三异丁基铝改性的甲基铝氧烷(MMAO),得到了B/Ti为1.5/1和Al/Ti为10/1的原子比制备催化剂组合物。然后,将混合物加入到加料旁通支管中并注射到反应器中。使聚合反应进行10分钟,根据保持450磅/平方英寸(3.1MPa)压力的要求同时加入乙烯。从反应器中将聚合物溶液转移到玻璃釜中并在120℃的真空烘箱中干燥大约16小时。效率为0.6(千克聚合物/克钛金属)。实施例4四(五氟代苯基)硼酸双(二十二烷基)甲基铵(C22H45)2(CH3)NHB(C6F5)4的制备
将(C22H45)2(CH3)NHB(C6F5)4(从Akzo Nobel得到的ARMEENM2HE)(3.87克,5.97毫摩尔)溶解在40毫升的己烷中。通过注射器加入水性HCl(1M,5.97毫升),结果生成了白色沉淀。将混合物放置在机械震荡器中并剧烈震荡30分钟,然后加入在30毫升水和20毫升己烷的混合物中的LiB(C6F5)4(4.30克,6.27毫摩尔)。将混合物再震荡30分钟。然后将它倒入另外的漏斗中并除去水层。用30毫升饱和氯化钠水溶液冲洗两次有机层,接着用水洗两次。用硫酸镁干燥有机层。然后,混合物通过玻璃料(10-15微米)进行过滤,得到透明的浅棕色溶液。将溶液转移到瓶中,用氮气彻底清洗,并放入干燥箱中。在真空下除去己烷,得到固体剩余物。剩余物与10毫升的己烷研制,得到了浅棕色的固体。将该固体再次溶解在35-40毫升的Isopar E中,并采用重量法测定该溶液的浓度为18.0wt%。聚合反应
基本上重复例1的聚合条件,采用1444克混合的烷烃溶剂、124克1-辛烯共聚单体、10微摩尔的(叔丁基酰氨基)二甲基(η5-四甲基环戊二烯基)(η4-1,3-戊二烯)钛催化剂、1.0微摩尔的双(二十二烷基)甲基四(五氟代苯基)硼酸铵共催化剂和10微摩尔的甲基铝氧烷清除剂,结果以3.2千克聚合物/克钛的效率制备了乙烯/1-辛烯的共聚物。
Claims (10)
1.催化活化剂,包含了阳离子,该阳离子为可以提供质子的布鲁斯台德酸,和惰性的、可相容的非配位的阴离子,该催化活性剂特征为在25℃下在己烷、环己烷或甲基环己烷中至少为5wt%的溶解性。
2.根据权利要求1的催化活化剂,其中的活化剂可用下面的一般结构式来表示:(L*-H)+(A-),其中:
L*为含有氮、硫或磷的路易斯碱;并且
A-为未配位的阴离子。
3.根据权利要求2的催化活化剂,其中的未配位的阴离子为四(五氟代苯基)硼酸盐。
4.根据权利要求2的催化活化剂,其中的路易斯碱含有1到3个C10-40的烷基,总共有12到100个碳。
5.根据权利要求2的催化活化剂,其中的路易斯碱含有2个C10-40的烷基,和总共21到90个碳。
6.根据权利要求1的催化活化剂,它为四(五氟代苯基)硼酸双(十八烷基)甲基铵,或四(五氟代苯基)硼酸双(氢化动物脂烷基)甲基铵。
7.用于α-烯烃的聚合反应的催化剂体系,它包含第4族的金属络合物和根据权利要求1-6中任何一项的催化活化剂。
8.聚合反应方法,它包括在聚合反应的条件下,用根据权利要求7的催化剂体系接触一种或多种α-烯烃。
9.根据权利要求8的方法,该方法为溶液聚合反应。
10.根据权利要求9的聚合反应方法,该方法为连续的溶液聚合反应。
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AR006420A1 (es) | 1999-08-25 |
US6121185A (en) | 2000-09-19 |
JP3990458B2 (ja) | 2007-10-10 |
CN1120849C (zh) | 2003-09-10 |
NO323319B1 (no) | 2007-03-12 |
EP0889912A1 (en) | 1999-01-13 |
CA2245839C (en) | 2005-06-14 |
NO984466D0 (no) | 1998-09-25 |
KR20000005028A (ko) | 2000-01-25 |
CA2245839A1 (en) | 1997-10-02 |
ATE194629T1 (de) | 2000-07-15 |
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DE69702506D1 (de) | 2000-08-17 |
JP2000507157A (ja) | 2000-06-13 |
TW387908B (en) | 2000-04-21 |
RU2178422C2 (ru) | 2002-01-20 |
ES2147985T3 (es) | 2000-10-01 |
ID18470A (id) | 1998-04-09 |
BR9708232A (pt) | 1999-08-03 |
WO1997035893A1 (en) | 1997-10-02 |
ZA972618B (en) | 1998-09-28 |
AU2214997A (en) | 1997-10-17 |
KR100437238B1 (ko) | 2004-08-16 |
US5919983A (en) | 1999-07-06 |
EP0889912B1 (en) | 2000-07-12 |
NO984466L (no) | 1998-09-25 |
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