CN1190407A - 硼苯环结构的烯烃聚合催化剂 - Google Patents
硼苯环结构的烯烃聚合催化剂 Download PDFInfo
- Publication number
- CN1190407A CN1190407A CN95197369A CN95197369A CN1190407A CN 1190407 A CN1190407 A CN 1190407A CN 95197369 A CN95197369 A CN 95197369A CN 95197369 A CN95197369 A CN 95197369A CN 1190407 A CN1190407 A CN 1190407A
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- catalyzer
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- general formula
- independently selected
- zirconium
- Prior art date
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- Granted
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 2
- 239000002685 polymerization catalyst Substances 0.000 title description 2
- 239000003446 ligand Substances 0.000 claims abstract description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052735 hafnium Chemical group 0.000 claims abstract description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims abstract description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 21
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- 238000006116 polymerization reaction Methods 0.000 claims description 11
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- 239000002585 base Substances 0.000 claims description 9
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- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 7
- 125000002524 organometallic group Chemical group 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002879 Lewis base Substances 0.000 claims description 4
- 150000007527 lewis bases Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 2
- JNFRNXKCODJPMC-UHFFFAOYSA-N aniline;boric acid Chemical compound OB(O)O.NC1=CC=CC=C1 JNFRNXKCODJPMC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- XGCILSHUAUFSLI-UHFFFAOYSA-N dodecalithium;tetraborate Chemical class [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] XGCILSHUAUFSLI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 16
- 125000002877 alkyl aryl group Chemical group 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 125000004663 dialkyl amino group Chemical group 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
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- 230000000694 effects Effects 0.000 description 7
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
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- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- LXDRHVXMGDKBEK-UHFFFAOYSA-N [B].C1=CC=CC=C1 Chemical class [B].C1=CC=CC=C1 LXDRHVXMGDKBEK-UHFFFAOYSA-N 0.000 description 2
- PGECBFAHXKPXSH-UHFFFAOYSA-N [B].c1ccc2cc3ccccc3cc2c1 Chemical class [B].c1ccc2cc3ccccc3cc2c1 PGECBFAHXKPXSH-UHFFFAOYSA-N 0.000 description 2
- JFWBIRAGFWPMTI-UHFFFAOYSA-N [Zr].[CH]1C=CC=C1 Chemical compound [Zr].[CH]1C=CC=C1 JFWBIRAGFWPMTI-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
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- 125000005574 norbornylene group Chemical group 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- PKZCRWFNSBIBEW-UHFFFAOYSA-N 2-n,2-n,2-trimethylpropane-1,2-diamine Chemical compound CN(C)C(C)(C)CN PKZCRWFNSBIBEW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZOZNABORANZNIZ-UHFFFAOYSA-N C1=CC=CC2=CC=CC=C12.[B] Chemical class C1=CC=CC2=CC=CC=C12.[B] ZOZNABORANZNIZ-UHFFFAOYSA-N 0.000 description 1
- BPOFADQMLPMBSL-UHFFFAOYSA-N C1=CC=CCC1.[B] Chemical compound C1=CC=CCC1.[B] BPOFADQMLPMBSL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XJONFIGVOQMBIP-UHFFFAOYSA-L Cl[Zr](Cl)C1C=CC=C1 Chemical compound Cl[Zr](Cl)C1C=CC=C1 XJONFIGVOQMBIP-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
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- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
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- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
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- 229910002027 silica gel Inorganic materials 0.000 description 1
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- 238000006884 silylation reaction Methods 0.000 description 1
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- 150000003512 tertiary amines Chemical group 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
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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
- 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
- C08F4/60—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 together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
-
- 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
- C08F4/60—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 together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- 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
- C08F10/00—Homopolymers and 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
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Abstract
公开了通式(Ⅰ)的催化剂,其中Q是包含环(Ⅱ)的配位体,R是氢、N(R1)2、OR1或R1,每个R1独立地选自C1-C10烷基、C6-C15芳基、C7-C15烷芳基和C7-C15芳烷基,每个X独立地选自氢、卤素、C1-C10烷氧基、C1-C10二烷基氨基、甲基、(Ⅲ),每个R1独立地选自卤素、C1-C10烷氧基和R1、L是(Ⅳ)、(Ⅴ)、(Ⅵ)、(Ⅶ)、(Ⅷ),Q或X,其中L可与Q桥联,B是一种任选的碱,“n”为0—5,和M是钴、锆、铪。
Description
本发明的技术背景
本发明涉及用于乙烯和其它烯烃均聚和共聚的催化剂。更具体地说,本发明涉及含与包含硼苯环结构的配位体成π键的过渡金属催化剂。
至今,聚烯烃主要用传统的齐格勒催化剂体系制备。这些催化剂体系一般都由含过渡金属的化合物和一种或几种有机金属化合物组成。例如,使用齐格勒催化剂例如三氯化钛和氯化二乙基铝,或四氯化钛、三氯化氧钒和三乙基铝的混合物,制备聚乙烯。这些催化剂不贵,但是它们的活性低,因此必须以高浓度使用。结果,有时必须从聚合物中除去催化剂的残留物,这就增加了生产费用。为了克服催化剂残留物的有害影响,必须将中和剂和稳定剂加入聚合物。没有除去的催化剂残留物,使聚合物成黄色或灰色和差的抗紫外线性及低的稳定性。例如,含氯的残留物可以腐蚀聚合物的加工设备。而且,用齐格勒催化剂生产的聚合物有宽的分子量分布,这对某些应用和注塑应用来说是不希望的。在引入α-烯烃共聚单体方面,它们的性能也差。引入共聚单体的差的性质就使得难以控制聚合物的密度。为达到某一密度可能需要大量过剩的共聚单体,而许多较高碳的α-烯烃,例如1-辛烯完全只能以很低的量引入。
自从齐格勒催化剂体系发现以来,虽然进行了相当大的改进,但是现在这些催化剂正被近来发现的茂金属催化剂体系代替。茂金属催化剂通常是由有一个或几个环戊二烯基配位体的过渡金属化合物组成。它们与有机金属化合物如与传统的齐格勒催化剂一起使用的烷基铝一起使用时,活性低,但是它们与作为助催化剂的铝氧烷一起使用时,活性很高。活性通常是这样的高,以致于不需要从聚合物中除去催化剂的残留物。而且,它们生产的聚合物分子量高,且分子量的分布窄。它们引入α-烯烃共聚单体的性能也好。但是,在较高温度下,茂金属催化剂易于产生低分子量的聚合物。这样它们对在约80-约95℃下进行的乙烯气相和浆料聚合有用,但是,它们对在约150-约250℃下在溶液中乙烯的聚合反应通常不能很好地运行。在溶液中乙烯的聚合是希望的,因为允许在分子量和密度宽的范围内,以及使用各种各样的不同共聚单体更灵活的生产聚合物。人们可以生产用于许多不同方面应用的聚合物。例如,高分子量、高密度的聚乙烯(PE)膜用于食品包装的防渗膜,而低密度乙烯共聚物有良好的韧性,和高的抗冲击强度。
本发明的概述
我们已经发现了一类以硼苯环结构为基础和含过渡金属的催化剂。本发明的催化剂有非常高的活性,这就意味着它们可以很少的量使用。在将共聚单体引入聚合物方面,它们的性能也很好。在较高的温度下它们具有高的活性,因此,可预期用于溶液中乙烯的聚合反应。最后,本发明范围内的一些催化剂包含叔胺基。令人惊奇地是,虽然许多含胺化合物已知是催化剂的毒物,但是这些催化剂是有效的。
优选方案的描述
本发明的催化剂通式为:在式中,Q是含硼苯环的配位体。硼苯环的结构为:其中R可以是氢、N(R’)2、OR’或R’,每个R’独立地选自C1-C10烷基、C6-C15芳基、C7-C15烷芳基和C7-C15芳烷基。R基优选为-N(R’)2或苯基,如果R是-N(R’)2,那么-N(R’)2中的R’优选甲基。因为这些催化剂有优良的性质,Q配位体的实例包括:
其中“M”是0-可取代位置的最大数,“m”优选为0,因为这些催化剂很容易制备,每个R1独立地选自卤素,C1-C10的烷氧基,和R’。优选的Q配位体是硼-苯环,硼-萘环和硼-蒽环,因为这些催化剂很容易制备。
其中“n”是0-5,优选是0。X基优选是氯或甲基,因为这些催化剂容易制备并具有优良的性质。
Q或X。优选L是Q、环戊二烯基或氯,因为这些催化剂最容易制备并具有优良性质。
L可以与Q桥联。桥联两个配位体可以使用的基包括亚甲基、亚乙基、1,2-亚苯基、二甲基甲硅烷基、二苯基甲硅烷基、二乙基甲硅烷基和甲基苯基甲硅烷基。通常,在催化剂中只使用一个桥键。据认为桥联的配位体改变了围绕催化活性过渡金属的几何形状,和提高了催化活性和其它性质,例如共聚单体的引入性和热稳定性。
通式中的M基可以是钛、锆或铪,但是优选锆,这是因为这些催化剂具有高活性和优良稳定性的最佳组合。
在通式中,B是一种任选的路易斯碱。可以使用高达等摩尔量(与M\)的碱。使用的路易斯碱通常不优选,因为它倾向于降低催化剂的活性。但是它也倾向于改进催化剂的稳定性,因此包含它是希望的,这取决于所使用它的方法。碱可以是来自催化剂制备所剩余的溶剂,或是为了提高催化剂的性质,单独加入的。可在本发明中使用的碱的实例包括醚类如二乙醚、二丁醚、四氢呋喃和1,2-二甲氧基乙烷、酯类如邻苯二甲酸正丁酯、苯甲酸乙酯和对茴香酸乙酯和膦类如三乙基膦、三丁基膦和三苯基膦。
催化剂Q配位体部分的制备可在文献中找到。例如,参见“硼-苯衍生物21。2,4-戊二烯基硼烷作为新的通往硼环己二烯和硼苯(Boratabenzenes)的关键中间体。〔Li(TMEDA)〕(C5H5BNMe2)的结构”,Gerhard E.Herberich等的论文有机金属(1993),P2891-2893,本文引入参考。在那篇论文中,2,4-戊二烯基硼烷在N,N,N’,N’-四甲基乙二胺(TMEDA)存在下与四氢呋喃中氨基化锂反应,生成式的二甲基氨基硼次苄基锂TMEDA的配合物,同样,参见“9-苯基-9-硼蒽阴离子的反应”,R.Van Veen和F.Bickelhaupt的文章,有机金属化学杂志,(1974),P153-165,这篇文章描述了9-苯基-9-硼蒽基锂的形成。其它的Q配位体可以相似的方法或通过其它的方法制备。催化剂可以由Q配位体通过将适当的四价金属化合物的悬浮液加入Q配位体的溶液来制备。这个反应可在-78-50℃的温度发生,但是优选在0℃以下进行。
由于催化剂通常与有机金属助催化剂配合使用,因此优选将催化剂溶于助催化剂也可溶的溶剂中。例如,如果甲基铝氧烷(MAO)或聚甲基铝氧烷(PMAO)是助催化剂,那么甲苯、二甲苯、苯或乙苯可以用作溶剂。其它适宜的助催化剂包括通式为ALR’x(R2)3-x,其中1≤x≤3和R2是氢、卤化物或C1-C20烷基或烷氧基的烷基铝,例如三乙基铝和二氯乙基铝。优选的助催化剂是MAO,因为它产生高活性,而且聚合物有窄的分子量分布。当在聚合反应中使用时,有机金属助催化剂与催化剂的摩尔比一般为0.01∶1-100,000∶1,优选为1∶1-10,000∶1。
为增强催化剂的性质,催化剂可以与含非配位的不活泼阴离子的酸式盐一起使用(参见美国专利5 064 802号)。酸式盐通常是由附着到硼或铝原子上的松散配位体组成的非亲核化合物,例如四个(五氟苯基)硼酸锂、四个(五氟苯基)铝酸锂,四个(五氟苯基)硼酸苯胺和它们的混合物。当这些化合物与催化剂反应时,生成的阴离子被认为是与金属阳离子的配位。酸式盐与催化剂的摩尔比可为约0.01∶1-约1000∶1,但是优选约1∶1-10∶1。从催化剂和酸式盐制备活性催化剂体系的方法虽没有限制,但是优选在约-78℃-约150℃温度下,在惰性溶剂中混合。如果需要,它们也可在单体存在下混合。酸或盐可以与上述的有机金属助催化剂组合使用。
催化剂和助催化剂可以载持在载体上使用,所述的载体例如硅胶、氧化铝、氧化硅或二氧化钛,但是,因为这些载体都保留在聚合物的污物中,所以它们不优选使用。但是,载体的需要与否取决于所利用的方法。例如,在气相聚合法和浆料聚合反应过程中,为了控制所产生的聚合物的粒径和防止反应器壁的结垢,一般都需要使用载体。为了利用载体,催化剂和促催化剂溶于溶剂,并通过蒸发溶剂的方法,使催化剂和助催化剂沉淀在载体上。助催化剂也可以沉积在载体上,或由载体催化剂独立地引入反应器。
催化剂一但制备,就应当立即使用,尽可能地减少贮存期间可能损失的一些活性。催化剂应当在低温如-100℃-约20℃的温度下贮存。在烯烃单体的聚合反应过程中,催化剂以传统的方式使用。当未饱和单体例如苯乙烯利用本发明的催化剂聚合时,对α-烯烃如丙烯、1-丁烯、1-己烯、1-辛烯和特别是乙烯非常有用。
本发明的催化剂还用于乙烯与未饱和单体如1-丁烯、1-己烯、1-辛烯等混合物的共聚合;乙烯与二烯烃如1,3-丁二烯、1,4己二烯、1,5-己二烯等混合物的共聚合;和乙烯与未饱和的共聚单体如降冰片烯、亚乙基降冰片烯、乙烯基降冰片烯等的混合物的共聚合。
本发明的催化剂可以用于各种不同的聚合方法。它们可以在液相聚合法(浆料、溶液、悬浮液、体相或它们的组合)、高压流体相或气相聚合法中使用。这些方法可以串联使用,或单独一个方法使用。在聚合反应区中的压力为约15磅/平方英寸-约50000磅/平方英寸,而温度可为约-100℃-约300℃。催化剂以传统的方式用于烯烃单体如乙烯、丙烯、1-丁烯、1-辛烯、1-己烯、降冰片烯和降冰片二烯的共聚合。
用下述的实例进一步地描述本发明。
实施例1
这个实施例描述(B-二甲基氨基硼苯)二氯化环戊二烯基锆的合成,它的通式为:其中Cp是环戊二烯基,Me是甲基。
在-78℃,将含0.61g(2.51mmol)二甲基氨基硼次苄基锂四甲基亚乙基二胺的配合物(按上述的G.E.Herberich的有关论文制备)的10ml醚溶液加入含0.56g(2.13mmol)三氯化环戊二烯基锆(购于StremChemicals)的15ml无水醚的悬浮液中。混合物升温到室温后,再搅拌一小时。在真空中除去挥发物后,残留物用30ml己烷洗涤,并用30ml甲苯提取。在减压下蒸发甲苯提取物,得0.23g黑色固体。质子核磁共振光谱表明在产品中存在一起杂质。
实施例2
通过在-78℃向含0.47g(1.6mmol)9-基硼蒽的18ml二乙醚溶液加入1.0ml 1.6M的正丁基锂的己烷溶液,升温到室温,并继续搅拌二小时制备9-基硼蒽基锂的二乙醚溶液。将溶液冷却到-10℃后,添加0.42g(1.6mmol)的三氯化环戊二烯基锆(StremChemicals)。然后使浴槽达室温后,反应混合物搅拌过夜。在真空下除去挥发物,得到带红褐色的粉末。向这种粉末中加入20ml干燥的甲苯后,过滤该混合物,得到透明的黄-桔色过滤液,并将其浓缩,得到棕色泡沫。这种物质用干燥己烷(20ml)处理后,过滤混合物,得0.26g浅棕褐色固体。产品的质子核磁共振光谱表明,存在一些杂质。
实施例3-17
使用实施例1和2的催化剂进行乙烯聚合。(实施例3-13和实施例20使用实施例1制备的催化剂,实施例14-19使用实施例2制备的催化剂。)聚合反应是在1.7升高压釜中于80℃或110℃下进行。干燥无氧甲苯(840ml)加入清洁干燥的无氧反应器。在一些聚合反应中,使用Ethyl有限公司的MAO(10%甲苯)。其它的聚合反应是使用AkzoChemical的PMAO(25%甲苯)进行。在30℃用注射器加入得到表中所示比率的MAO或PMAO的所需要量。反应器加热到所要求的温度后,添加足够的乙烯使反应器的压力达150磅/平方英寸〔表压〕。使反应器在所要求的温度和压力下达到平衡。通过将0.100g的产品溶于100ml甲苯中制备催化剂溶液。使用得到表中所示的催化剂量所需要的这种溶液量开始聚合反应。为了保持反应器的压力稳定在150磅/平方英寸〔表压〕,按照产生聚合物所需要的量,使乙烯流入反应器。
在一小时(如果活性很高小于一小时)的结尾,停止乙烯流入反应器,反应器迅速冷却到室温。打开反应器后,从甲苯中滤出聚合物。产品在真空炉中干燥过夜。下表给出了反应条件和聚合反应的结果。
根据ASTM D-1238,条件E和F测量聚合物的熔体指数。MI2是用2.16kg重量(条件E)测是的熔体指数。MI20是用21.6kg重量(条件F)测量的熔体指数。MFR是MI20与MI2的比。按照ASTMD-1505测量聚合物密度。聚合物的分子量的分布使用Waters 150C凝胶渗透色谱仪,在135℃用1,2,4-三氯代苯作溶剂测量。使用重均分子量(Mw)和Mw与Mn(数均分子量)的比表征分子量的分布。表示出了在80℃时高活性,在110℃时活性几乎没有下降(实施例9与实施例2比较)。
实施例 | 反应器温度(℃) | 时间(分) | H2数量(mmoles) | 共聚单体 | 共聚单体(ml) | 催化剂(mmoles) | Al/Zr(原子比) | 助催化剂 |
3 | 80 | 60 | 0 | 无 | 0 | 9.00E-03 | 1430 | PMAO |
4 | 80 | 60 | 0 | 无 | 0 | 4.50E-03 | 2870 | PMAO |
5 | 80 | 60 | 180 | 无 | 0 | 4.50E-03 | 2870 | PMAO |
6 | 80 | 60 | 0 | 丁烯-1 | 20 | 4.50E-03 | 2870 | PMAO |
7 | 110 | 60 | 0 | 无 | 0 | 4.50E-03 | 2870 | PMAO |
8 | 110 | 60 | 0 | 无 | 0 | 4.50E-03 | 2870 | MAO |
9 | 110 | 30 | 30 | 无 | 0 | 4.50E-03 | 2870 | MAO |
10 | 110 | 60 | 0 | 丁烯-1 | 20 | 4.50E-03 | 2870 | MAO |
11 | 110 | 60 | 90 | 丁烯-1 | 20 | 4.50E-03 | 2870 | MAO |
12 | 110 | 30 | 90 | 己烯-1 | 20 | 4.50E-03 | 2870 | MAO |
13 | 110 | 60 | 0 | 辛烯-1 | 20 | 4.50E-03 | 2870 | MAO |
14 | 80 | 30 | 30 | 丁烯-1 | 17 | 4.79E-03 | 1570 | MAO |
15 | 80 | 15 | 30 | 丁烯-1 | 17 | 4.79E-03 | 1570 | MAO |
16 | 80 | 30 | 30 | 丁烯-1 | 17 | 4.79E-03 | 1570 | MAO |
17 | 80 | 30 | 30 | 丁烯-1 | 17 | 4.79E-03 | 2190 | MAO |
18 | 110 | 10 | 0 | 丁烯-1 | 17 | 4.79E-03 | 2190 | MAO |
19 | 110 | 30 | 0 | 丁烯-1 | 17 | 2.87E-03 | 2190 | MAO |
20 | 80 | 60 | 0 | 5-乙烯基-2-降冰片烯 | 30 | 3.00E-03 | 4500 | MAO |
实施例 | wt.PE(g) | 催化剂生产率(kg/g/hr) | WI2(dg/min) | WI20(dg/min) | WFR | 密度(g/ml) | Mw/Mn |
3 | 77.1 | 93.9 | 0.17 | 2.37 | 13.9 | 0.9574 | 2.00 |
4 | 81.3 | 198.1 | 0.14 | 2.57 | 18.0 | 0.9587 | 1.75 |
5 | 92.5 | 225.4 | 10.28 | 333 | 32.4 | 0.9720 | - |
6 | 71.7 | 174.7 | 1.11 | 24.92 | 22.5 | 0.9323 | - |
7 | 70.4 | 171.5 | 1.10 | 22.64 | 20.6 | 0.9616 | 1.70 |
8 | 80.1 | 195.2 | 1.50 | 35.81 | 23.9 | 0.9637 | 1.84 |
9 | 105.0 | 511.7 | 18.40 | 539 | 29.3 | 0.9714 | 4.194 |
10 | 96.5 | 235.1 | 7.92 | 152 | 19.2 | 0.9448 | - |
11 | 110.0 | 536.1 | 41.94 | 1202 | 28.7 | 0.9521 | - |
12 | 138.9 | 676.9 | 16.27 | 588 | 36.1 | 0.9584 | 4.85 |
13 | 65.0 | 158.4 | 9.29 | 185 | 19.9 | 0.9515 | - |
14 | 31.8 | 145.7 | 549 | - | - | - | - |
15 | 34.5 | 316.1 | <0.01 | 2.89 | - | - | - |
16 | 44.5 | 203.8 | 106 | - | - | - | - |
17 | 83.6 | 383.0 | 25.8 | 588 | 22.8 | - | - |
18 | 66.1 | 908.4 | <0.01 | 49.1 | - | - | - |
19 | 33.2 | 253.5 | <0.01 | 31.9 | - | - | - |
20 | 49.1 | 179.4 | 0.07 | 1.18 | 17.1 | 0.9415 | - |
催化剂有优良的共聚单体引入特性。在实施例6和10中记录的异常高的丁烯-1引入产生了较低密度的聚合物。此时,催化剂易于引入通常难以共聚的共聚单体。这是以实施例20中乙烯与5-乙烯基-2-降冰片烯的共聚反应为例。在实施例3中,表明分子量分布的重均分子量与数均分子量的比测量为2.00。Mw/Mn为2.00表明很窄的分子量分布。
Claims (21)
2.按权利要求1的催化剂,其中M是锆。
3.按权利要求1的催化剂,其中每个X是氯。
4.按权利要求1的催化剂,其中每个X是甲基。
5.按权利要求1的催化剂,其中L是环戊二烯基。
6.按权利要求1的催化剂,其中L是氯。
9.按权利要求1的催化剂,其中Q是其中“m”为0-7。
11.按权利要求1的催化剂,每摩尔上述催化剂与约0.01-约100,000的有机金属助催化剂组合使用。
12.按权利要求11的催化剂,其中上述的有机金属助催化剂是甲基铝氧烷或聚甲基铝氧烷。
13.按权利要求1的催化剂,每摩尔上述催化剂与约0.01-1000mol的含非配位不活泼的阴离子的酸式盐组合使用。
14.按权利要求13的催化剂,其中上述酸式盐选自由四个(五氟苯基)硼酸锂、四个(五氟苯基)铝酸锂、四个(五氟苯基)硼酸苯胺和它们的混合物组成的组。
15.α-烯烃的一种聚合方法,包括在权利要求1的催化剂存在下,加热上述的α-烯烃。
18.按权利要求17的催化剂,其中R是-NC(CH3)2。
19.按权利要求17的催化剂,其中R是三甲基苯基。
20.按权利要求17的催化剂,包括B-二甲基氨基一硼苯二氯代环戊二烯锆。
21.按权利要求17的催化剂,包括二氯化环戊二烯基(9-基硼蒽基)锆。
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Families Citing this family (209)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW330217B (en) | 1994-12-20 | 1998-04-21 | Kimberly Clark Co | Low gauge films and film/nonwoven laminates |
US6309736B1 (en) | 1994-12-20 | 2001-10-30 | Kimberly-Clark Worldwide, Inc. | Low gauge films and film/nonwoven laminates |
ZA9510604B (en) | 1994-12-20 | 1996-07-03 | Kimberly Clark Co | Low gauge films and film/nonwoven laminates |
US6228958B1 (en) | 1995-04-25 | 2001-05-08 | Equistar Chemicals, L.P. | Azaborolinyl metal complexes as olefin polymerization catalysts |
JPH11504361A (ja) * | 1995-04-25 | 1999-04-20 | ライオンデル ペトロケミカル カンパニー | オレフィンの重合の触媒としてのアザボロリニル金属錯体 |
KR19990028461A (ko) * | 1995-06-28 | 1999-04-15 | 알베르투스 빌헬무스 요아네스 ㅔ스트라텐 | 유기금속 화합물을 포함한 촉매 조성물 |
EP0784062A3 (en) * | 1995-12-15 | 1998-04-22 | Union Carbide Chemicals & Plastics Technology Corporation | Process for production of long-chain branched polyolefins |
JP2000503001A (ja) * | 1995-12-22 | 2000-03-14 | タルゴル、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング | 遷移金属化合物 |
US6274752B1 (en) | 1996-02-20 | 2001-08-14 | Northwestern University | Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations |
US6291695B1 (en) | 1996-02-20 | 2001-09-18 | Northwestern University | Organo-Lewis acids of enhanced utility, uses thereof, and products based thereon |
KR20000005030A (ko) * | 1996-03-27 | 2000-01-25 | 그레이스 스티븐 에스. | 헤테로사이클릭 금속 착체 및 올레핀 중합 방법 |
CN1216996A (zh) | 1996-03-29 | 1999-05-19 | 陶氏化学公司 | 金属茂助催化剂 |
US6166161A (en) * | 1996-06-24 | 2000-12-26 | The Dow Chemical Company | Incorporation of functionalized comonomers in polyolefins |
US6262200B1 (en) | 1996-08-19 | 2001-07-17 | Northwestern University | (Polyfluoroaryl)fluoroanions of aluminum, gallium, and indium of enhanced utility, uses thereof, and products based thereon |
US6130302A (en) | 1996-08-19 | 2000-10-10 | Northwestern University | Synthesis and use of (polyfluoroaryl)fluoroanions of aluminum, gallium and indium |
US6451938B1 (en) | 1997-02-25 | 2002-09-17 | Exxon Mobil Chemical Patents Inc. | Polymerization catalyst system comprising heterocyclic fused cyclopentadienide ligands |
US6045900A (en) | 1997-09-15 | 2000-04-04 | Kimberly-Clark Worldwide, Inc. | Breathable filled film laminate |
DE19757218A1 (de) * | 1997-12-22 | 1999-06-24 | Bayer Ag | Verfahren zur Herstellung von Elastomeren |
CA2330529A1 (en) | 1998-06-12 | 1999-12-16 | Univation Technologies Llc | Olefin polymerization process using activated lewis acid-base complexes |
EP1097175B1 (en) | 1998-07-16 | 2007-02-28 | Univation Technologies LLC | Aluminum-based lewis acid cocatalysts for olefin polymerization |
CA2243775C (en) * | 1998-07-21 | 2007-06-12 | Nova Chemicals Ltd. | Phosphinimine/heteroatom catalyst component |
US5914408A (en) * | 1998-08-07 | 1999-06-22 | Equistar Chemicals, Lp | Olefin polymerization catalysts containing benzothiazole |
US6114270A (en) * | 1998-08-07 | 2000-09-05 | Equistar Chemicals, L.P. | Polymerization-stable anionic ancillary ligand containing alkylimido catalysts and method of using the same |
US6008394A (en) * | 1998-08-07 | 1999-12-28 | Arco Chemicals Technology, L.P. | Sulfonyl catalysts and method of using the same |
US6121181A (en) * | 1998-08-07 | 2000-09-19 | Equistar Chemicals, L.P. | Cyclic oligomeric oxo- and imido- metal complexes as olefin polymerization catalysts |
CA2245375C (en) | 1998-08-19 | 2006-08-15 | Nova Chemicals Ltd. | Dual reactor polyethylene process using a phosphinimine catalyst |
CA2247703C (en) | 1998-09-22 | 2007-04-17 | Nova Chemicals Ltd. | Dual reactor ethylene polymerization process |
US6454989B1 (en) | 1998-11-12 | 2002-09-24 | Kimberly-Clark Worldwide, Inc. | Process of making a crimped multicomponent fiber web |
US6723669B1 (en) * | 1999-12-17 | 2004-04-20 | Kimberly-Clark Worldwide, Inc. | Fine multicomponent fiber webs and laminates thereof |
DE19903695A1 (de) * | 1999-02-01 | 2000-08-03 | Elenac Gmbh | Verfahren zur Herstellung von Polyolefinen mit breiter Molekulargewichtsverteilung |
US6180552B1 (en) | 1999-04-07 | 2001-01-30 | Equistar Chemicals, L.P. | Transition metal complexes containing neutral, multidentate azacyclic ligands |
US6204216B1 (en) | 1999-04-15 | 2001-03-20 | Equistar Chemicals, L.P. | Olefin polymerization catalysts containing amine derivatives |
US6127484A (en) * | 1999-04-29 | 2000-10-03 | Equistar Chemicals, Lp | Olefin polymerization process |
US6201076B1 (en) | 1999-04-29 | 2001-03-13 | Equistar Chemicals, L.P. | Olefin polymerization process with fatty amine additives for improved activity and reduced fouling |
US6020493A (en) * | 1999-05-06 | 2000-02-01 | Equistar Chemicals, Lp | Single-site catalyst preparation |
US6211311B1 (en) * | 1999-05-25 | 2001-04-03 | Equistar Chemicals, L.P. | Supported olefin polymerization catalysts |
US6265504B1 (en) * | 1999-09-22 | 2001-07-24 | Equistar Chemicals, Lp | Preparation of ultra-high-molecular-weight polyethylene |
US6194527B1 (en) | 1999-09-22 | 2001-02-27 | Equistar Chemicals, L.P. | Process for making polyolefins |
CA2285723C (en) | 1999-10-07 | 2009-09-15 | Nova Chemicals Corporation | Multimodal polyolefin pipe |
US6777056B1 (en) | 1999-10-13 | 2004-08-17 | Kimberly-Clark Worldwide, Inc. | Regionally distinct nonwoven webs |
US6613704B1 (en) * | 1999-10-13 | 2003-09-02 | Kimberly-Clark Worldwide, Inc. | Continuous filament composite nonwoven webs |
US6232260B1 (en) | 1999-10-14 | 2001-05-15 | Equistar Chemicals, L.P. | Single-site catalysts for olefin polymerization |
US6228959B1 (en) | 1999-10-15 | 2001-05-08 | Equistar Chemicals, L.P. | Single-site catalysts containing homoaromatic ligands |
US6794024B1 (en) | 1999-11-01 | 2004-09-21 | Kimberly-Clark Worldwide, Inc. | Styrenic block copolymer breathable elastomeric films |
US6479154B1 (en) | 1999-11-01 | 2002-11-12 | Kimberly-Clark Worldwide, Inc. | Coextruded, elastomeric breathable films, process for making same and articles made therefrom |
US6294626B1 (en) | 1999-11-15 | 2001-09-25 | Equistar Chemicals, Lp | Olefin polymerization catalysts containing modified boraaryl ligands |
US6281155B1 (en) | 1999-11-19 | 2001-08-28 | Equistar Chemicals, L.P. | Supported olefin polymerization catalysts |
US6281306B1 (en) | 1999-12-16 | 2001-08-28 | Univation Technologies, Llc | Method of polymerization |
US6340771B1 (en) | 1999-12-22 | 2002-01-22 | Nova Chemicals (International) S. A. | “Sweet” MAO |
US6239239B1 (en) | 2000-02-17 | 2001-05-29 | Equistar Chemicals, L.P. | Quinolinoxy and pyridinoxy single-site catalysts containing benzyl ligands |
US6255415B1 (en) * | 2000-02-29 | 2001-07-03 | Equistar Chemicals, L.P. | Ethylene polymerization process |
US6476165B1 (en) | 2000-03-08 | 2002-11-05 | Equistar Chemicals, Lp | Olefin polymerization process using fatty amine additives and boron-modified supported catalyst |
US6498221B1 (en) * | 2000-03-30 | 2002-12-24 | Equistar Chemicals, Lp | Single-site catalysts containing chelating N-oxide ligands |
US6812304B2 (en) | 2000-06-14 | 2004-11-02 | Equistar Chemicals, Lp | Process for producing improved premixed supported boraaryl catalysts |
US6444765B1 (en) | 2000-06-14 | 2002-09-03 | Equistar Chemicals, Lp | Olefin polymerization process for producing broad MWD polymers |
US6403736B1 (en) | 2000-06-14 | 2002-06-11 | Equistar Chemicals, Lp | Ethylene polymerization process |
US6414099B1 (en) | 2000-10-18 | 2002-07-02 | Equistar Chemicals, Lp | Single-site catalysts based on caged diimide ligands |
US6982231B1 (en) | 2000-10-27 | 2006-01-03 | Kimberly-Clark Worldwide, Inc. | Elastomeric, breathable laminate with enhanced breathability upon extension |
US6660678B1 (en) | 2000-11-21 | 2003-12-09 | Equistar Chemicals, Lp | Single-site catalysts for olefin polymerization |
US6583082B2 (en) * | 2000-12-01 | 2003-06-24 | The Governors Of The University Of Alberta | Functional organic particles for catalyst supports |
US6582810B2 (en) | 2000-12-22 | 2003-06-24 | Kimberly-Clark Worldwide, Inc. | One-step method of producing an elastic, breathable film structure |
US6410764B1 (en) * | 2001-01-18 | 2002-06-25 | Equistar Chemicals, L.P. | Method for preparation of boratabenzene derivatives |
CA2334049C (en) | 2001-02-02 | 2010-03-23 | Nova Chemicals Corporation | Halosulfonic acid treated catalyst support for olefin polymerization |
US6673882B2 (en) | 2001-02-12 | 2004-01-06 | Equistar Chemicals, Lp | Supported single-site catalysts useful for olefin polymerization |
CA2338094C (en) | 2001-02-23 | 2009-09-15 | Nova Chemicals Corporation | Catalyst for olefin polymerization |
US6541578B2 (en) | 2001-03-22 | 2003-04-01 | Nova Chemicals (International) S.A. | Increased space-time yield in gas phase polymerization |
US6664349B2 (en) | 2001-03-29 | 2003-12-16 | Equistar Chemicals, Lp | Ethylene polymerization process |
US6414162B1 (en) | 2001-04-05 | 2002-07-02 | Equistar Chemicals, Lp | Bimetallic catalysts for olefin polymerization |
US6579957B2 (en) * | 2001-04-11 | 2003-06-17 | Equistar Chemicals, Lp | Single-site catalysts based on anionic thiopyran dioxide ligands |
US6391988B1 (en) | 2001-04-18 | 2002-05-21 | Equistar Chemicals L.P. | Tris(pyrazoyl) based anions |
US6583240B2 (en) | 2001-05-23 | 2003-06-24 | Equistar Chemicals, Lp | Ethylene polymerization process |
US6759361B2 (en) * | 2001-06-04 | 2004-07-06 | Equistar Chemicals, Lp | Aluminoboronate activators for single-site olefin polymerization catalysts |
US6489414B1 (en) * | 2001-06-06 | 2002-12-03 | Equistar Chemicals, Lp | Chelating pyrimidines as ligands for single-site olefin polymerization catalysts |
US6544918B1 (en) | 2001-07-17 | 2003-04-08 | Equistar Chemicals, Lp | Olefin polymerization catalysts containing chelating dianionic ligands |
US6583242B2 (en) | 2001-08-02 | 2003-06-24 | Equistar Chemicals, Lp | Supported olefin polymerization catalysts |
US6562973B1 (en) | 2001-08-15 | 2003-05-13 | Equistar Chemicals, Lp | Method for making late transition metal catalysts for olefin polymerization |
CA2364756A1 (en) | 2001-12-10 | 2003-06-10 | Nova Chemicals Corporation | Catalyst activator |
US6596826B1 (en) | 2001-12-20 | 2003-07-22 | Equistar Chemicals, Lp | Olefin polymerization catalysts containing 1,3-diboretanyl ligands |
US6586545B1 (en) | 2001-12-20 | 2003-07-01 | Equistar Chemicals, Lp | Complexes based on four-membered cyclic anionic six-electron-donor ligands |
US6780807B2 (en) | 2002-02-04 | 2004-08-24 | Equistar Chemicals L.P. | Acyclic anionic six-electron-donor ancillary ligands |
US6689848B2 (en) | 2002-03-04 | 2004-02-10 | Equistar Chemicals, Lp | Late transition metal polymerization catalysts |
AU2003230726A1 (en) * | 2002-04-12 | 2003-10-27 | Dow Global Technologies Inc. | Azaborolyl group 4 metal complexes, catalysts and olefin polymerization process |
US6908972B2 (en) | 2002-04-16 | 2005-06-21 | Equistar Chemicals, Lp | Method for making polyolefins |
US7094723B2 (en) * | 2002-04-18 | 2006-08-22 | Equistar Chemicals Lp | Catalysts containing at least one heterocyclic ligand for improving the catalysts' performance of olefin polymerization |
US6642326B1 (en) | 2002-05-03 | 2003-11-04 | Equistar Chemicals, Lp | Use of silanes to enhance activity in single-site polymerizations |
US6630547B1 (en) | 2002-06-11 | 2003-10-07 | Equistar Chemicals, Lp | Use of silanes to control molecular weight in olefin polymerizations |
US20040002273A1 (en) * | 2002-07-01 | 2004-01-01 | Kimberly-Clark Worldwide, Inc. | Liquid repellent nonwoven protective material |
US6559251B1 (en) | 2002-08-02 | 2003-05-06 | Equistar Chemicals, Lp | Process for making low-density polyolefins |
US6677038B1 (en) | 2002-08-30 | 2004-01-13 | Kimberly-Clark Worldwide, Inc. | 3-dimensional fiber and a web made therefrom |
US6896843B2 (en) * | 2002-08-30 | 2005-05-24 | Kimberly-Clark Worldwide, Inc. | Method of making a web which is extensible in at least one direction |
US6881375B2 (en) * | 2002-08-30 | 2005-04-19 | Kimberly-Clark Worldwide, Inc. | Method of forming a 3-dimensional fiber into a web |
CA2405241C (en) * | 2002-09-24 | 2011-07-26 | Nova Chemicals Corporation | Olefin polymerization catalyst system |
US6765074B2 (en) | 2002-09-27 | 2004-07-20 | Equistar Chemicals, Lp | Olefin polymerization process |
JP4972284B2 (ja) | 2002-10-15 | 2012-07-11 | エクソンモービル・ケミカル・パテンツ・インク | オレフィン重合のための複数触媒系及びそれらから生成されたポリマー |
US7223822B2 (en) | 2002-10-15 | 2007-05-29 | Exxonmobil Chemical Patents Inc. | Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom |
US6630548B1 (en) | 2002-11-01 | 2003-10-07 | Equistar Chemicals, Lp | Static reduction |
US20040102123A1 (en) * | 2002-11-21 | 2004-05-27 | Bowen Uyles Woodrow | High strength uniformity nonwoven laminate and process therefor |
US6989125B2 (en) * | 2002-11-21 | 2006-01-24 | Kimberly-Clark Worldwide, Inc. | Process of making a nonwoven web |
US6841500B2 (en) * | 2002-12-03 | 2005-01-11 | Equistar Chemicals, Lp | Bimetallic indenoindolyl catalysts |
US7666410B2 (en) | 2002-12-20 | 2010-02-23 | Kimberly-Clark Worldwide, Inc. | Delivery system for functional compounds |
US7320739B2 (en) * | 2003-01-02 | 2008-01-22 | 3M Innovative Properties Company | Sound absorptive multilayer composite |
US20040131836A1 (en) * | 2003-01-02 | 2004-07-08 | 3M Innovative Properties Company | Acoustic web |
US20040231914A1 (en) * | 2003-01-02 | 2004-11-25 | 3M Innovative Properties Company | Low thickness sound absorptive multilayer composite |
US6713576B1 (en) | 2003-02-25 | 2004-03-30 | Equistar Chemicals, Lp | Olefin polymerization catalysts based on convex, polcyclic ligands |
US20040176241A1 (en) * | 2003-03-04 | 2004-09-09 | Sandor Nagy | Benzoindenoindolyl metal catalysts for olefin polymerization |
RU2339650C2 (ru) | 2003-03-21 | 2008-11-27 | Дау Глобал Текнолоджиз, Инк. | Способ полимеризации олефинов с регулируемой морфологией |
CA2423921A1 (en) * | 2003-03-28 | 2004-09-28 | Nova Chemicals Corporation | Halogenated organic particles for catalyst supports |
US6812183B1 (en) * | 2003-04-23 | 2004-11-02 | Equistar Chemicals, Lp | Triple-decker catalysts based on delocalized dianionic ligands |
US6984599B2 (en) * | 2003-04-23 | 2006-01-10 | Equistar Chemicals, Lp | Olefin polymerization catalysts based on hydroxyl-depleted calixarene ligands |
US6774078B1 (en) | 2003-04-23 | 2004-08-10 | Equistar Chemicals, Lp | Olefin polymerization catalysts based on annulated cyclopentadienyl ligands |
US6995216B2 (en) * | 2003-06-16 | 2006-02-07 | Equistar Chemicals, Lp | Process for manufacturing single-site polyolefins |
US6818713B1 (en) | 2003-08-11 | 2004-11-16 | Equistar Chemicals, Lp | Process for making polyethylene |
US7932196B2 (en) | 2003-08-22 | 2011-04-26 | Kimberly-Clark Worldwide, Inc. | Microporous stretch thinned film/nonwoven laminates and limited use or disposable product applications |
US6939930B2 (en) * | 2003-09-09 | 2005-09-06 | Equistar Chemicals, Lp | Hydrosilane additives for increased polyolefin molecular weight |
US7005489B2 (en) * | 2003-09-29 | 2006-02-28 | Equistar Chemicals, Lp | Zwitterionic Metallocycles |
US6903170B2 (en) * | 2003-09-29 | 2005-06-07 | Equistar Chemicals, Lp | Olefin polymerization process using triisobutylaluminum as a scavenger |
US6958377B2 (en) * | 2003-10-15 | 2005-10-25 | Equistar Chemicals, Lp | Olefin polymerization process |
US7438875B2 (en) | 2003-10-16 | 2008-10-21 | Kimberly-Clark Worldwide, Inc. | Method for reducing odor using metal-modified silica particles |
US7678367B2 (en) | 2003-10-16 | 2010-03-16 | Kimberly-Clark Worldwide, Inc. | Method for reducing odor using metal-modified particles |
US7413550B2 (en) | 2003-10-16 | 2008-08-19 | Kimberly-Clark Worldwide, Inc. | Visual indicating device for bad breath |
US7754197B2 (en) | 2003-10-16 | 2010-07-13 | Kimberly-Clark Worldwide, Inc. | Method for reducing odor using coordinated polydentate compounds |
US7879350B2 (en) | 2003-10-16 | 2011-02-01 | Kimberly-Clark Worldwide, Inc. | Method for reducing odor using colloidal nanoparticles |
US7837663B2 (en) | 2003-10-16 | 2010-11-23 | Kimberly-Clark Worldwide, Inc. | Odor controlling article including a visual indicating device for monitoring odor absorption |
US7794737B2 (en) | 2003-10-16 | 2010-09-14 | Kimberly-Clark Worldwide, Inc. | Odor absorbing extrudates |
US7488520B2 (en) | 2003-10-16 | 2009-02-10 | Kimberly-Clark Worldwide, Inc. | High surface area material blends for odor reduction, articles utilizing such blends and methods of using same |
US20050118435A1 (en) * | 2003-12-01 | 2005-06-02 | Kimberly-Clark Worldwide, Inc. | Films and methods of forming films having polyorganosiloxane enriched surface layers |
US7326751B2 (en) * | 2003-12-01 | 2008-02-05 | Kimberly-Clark Worlwide, Inc. | Method of thermally processing elastomeric compositions and elastomeric compositions with improved processability |
US7985811B2 (en) * | 2004-01-02 | 2011-07-26 | Univation Technologies, Llc | Method for controlling sheeting in gas phase reactors |
US20050148742A1 (en) * | 2004-01-02 | 2005-07-07 | Hagerty Robert O. | Method for controlling sheeting in gas phase reactors |
US20070073012A1 (en) * | 2005-09-28 | 2007-03-29 | Pannell Richard B | Method for seed bed treatment before a polymerization reaction |
US6982305B2 (en) * | 2004-01-26 | 2006-01-03 | Equistar Chemicals, Lp | Olefin polymerization in the presence of a dehydrogenation catalyst |
US7309741B2 (en) * | 2004-06-01 | 2007-12-18 | Nova Chemicals (International) S.A. | Polyolefin blends and pipe |
US20060003154A1 (en) * | 2004-06-30 | 2006-01-05 | Snowden Hue S | Extruded thermoplastic articles with enhanced surface segregation of internal melt additive |
US7285595B2 (en) * | 2004-06-30 | 2007-10-23 | Kimberly-Clark Worldwide, Inc. | Synergistic fluorochemical treatment blend |
US7402546B2 (en) * | 2004-09-23 | 2008-07-22 | Equistar Chemicals, Lp | Magnesium chloride support |
US7500541B2 (en) | 2004-09-30 | 2009-03-10 | Kimberly-Clark Worldwide, Inc. | Acoustic material with liquid repellency |
US7323523B2 (en) * | 2004-12-07 | 2008-01-29 | Nova Chemicals (International) S.A. | Adjusting polymer characteristics through process control |
US7064096B1 (en) * | 2004-12-07 | 2006-06-20 | Nova Chemicals (International) Sa | Dual catalyst on a single support |
BRPI0517210B1 (pt) | 2004-12-17 | 2017-01-24 | Dow Global Technologies Inc | composição adequada para tubos, composição adequada para películas sopradas, composição adequada para artigos moldados soprados, tubo, película, artigo moldado por sopro e método para melhorar o comportamento de fluxo de fluência de uma resina |
US20060189769A1 (en) * | 2005-02-22 | 2006-08-24 | Nova Chemicals (International) S.A. | Broad/bimodal resins with controlled comonomer distribution |
CA2503461A1 (en) * | 2005-04-01 | 2006-10-01 | Nova Chemicals Corporation | Modified (mao + aluminum alkyl) activator |
DE112006001733T5 (de) | 2005-07-01 | 2008-07-31 | Albemarle Corporation | Aluminoxanatsalzzusammensetzungen mit verbesserter Stabilität in aromatischen und aliphatischen Lösungsmitteln |
US7273914B2 (en) * | 2005-08-03 | 2007-09-25 | Equistar Chemicals, Lp | Olefin polymerization methods |
US20070060724A1 (en) * | 2005-09-13 | 2007-03-15 | Nova Chemicals Corporation And Innovene Europe Ltd. | Enhanced catalyst productivity |
US7531602B2 (en) * | 2005-10-05 | 2009-05-12 | Nova Chemicals (International) S.A. | Polymer blends |
US20070141352A1 (en) | 2005-12-15 | 2007-06-21 | Calhoun Patricia H | Cross-directional elastic films with machine direction stiffness |
US7608327B2 (en) * | 2005-12-20 | 2009-10-27 | Equistar Chemicals, Lp | High tear strength film |
EP1803747A1 (en) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films |
CN101356226B (zh) | 2006-05-02 | 2012-09-05 | 陶氏环球技术有限责任公司 | 高密度聚乙烯组合物、其制备方法、由其制得的制品以及该制品的制备方法 |
US7456244B2 (en) * | 2006-05-23 | 2008-11-25 | Dow Global Technologies | High-density polyethylene compositions and method of making the same |
US7399809B1 (en) | 2007-01-11 | 2008-07-15 | Equistar Chemicals, Lp | Modifying polyethylene made by Ziegler or single-site catalyst with free radical initiator |
MX2009000711A (es) * | 2007-05-02 | 2009-04-22 | Dow Global Technologies Inc | Composiciones de polietileno de alta densidad, metodo para hacer las mismas, articulos moldeados por inyeccion hechos a partir de las mismas y metodo para hacer tales articulos. |
CA2588352A1 (en) * | 2007-05-11 | 2008-11-11 | Nova Chemicals Corporation | Method to estimate pent values |
US20080289274A1 (en) * | 2007-05-22 | 2008-11-27 | Nova Chemicals (International) S.A | Half panel |
US7981517B2 (en) * | 2007-08-28 | 2011-07-19 | Dow Global Technologies Inc. | Bituminous compositions and methods of making and using same |
CA2605077C (en) * | 2007-10-01 | 2014-07-08 | Nova Chemicals Corporation | A co-supported catalyst system |
CA2605044C (en) * | 2007-10-01 | 2014-12-02 | Nova Chemicals Corporation | Polymerization process using a mixed catalyst system |
JP2009270976A (ja) * | 2008-05-08 | 2009-11-19 | Hitachi High-Technologies Corp | 欠陥レビュー方法および欠陥レビュー装置 |
US7544825B1 (en) | 2008-06-12 | 2009-06-09 | Basell Polyolefine Gmbh | Preparation of siloxy-bridged metallocenes |
RU2515900C2 (ru) | 2008-12-18 | 2014-05-20 | Юнивейшн Текнолоджиз, Ллк | Способ обработки зародышевого слоя реакции полимеризации |
BRPI1005286A2 (pt) | 2009-01-30 | 2016-07-05 | Dow Global Technologies Llc | composição de polietileno de alta densidade, método para produzir uma composição de polietileno de alta densidade, dispositivo de fechamento e método para produzir um dispositivo de fechamento |
US20100239796A1 (en) * | 2009-03-23 | 2010-09-23 | Gagne Joseph Donald | Lap sealable laminate and packaging made therefrom |
CA2713042C (en) | 2010-08-11 | 2017-10-24 | Nova Chemicals Corporation | Method of controlling polymer architecture |
EP2643366B1 (en) | 2010-11-22 | 2015-03-25 | Albemarle Corporation | Activator compositions, their preparation, and their use in catalysis |
CA2724943A1 (en) | 2010-12-10 | 2012-06-10 | Nova Chemicals Corporation | Catalyst activation in a dual reactor process |
US8895126B2 (en) | 2010-12-31 | 2014-11-25 | Kimberly-Clark Worldwide, Inc. | Segmented films with high strength seams |
CA2736443C (en) | 2011-04-06 | 2018-07-10 | Nova Chemicals Corporation | Improved reactor continuity |
CA2736685C (en) | 2011-04-07 | 2018-07-10 | Nova Chemicals Corporation | Supported phosphinimine-heteroligand catalyst systems |
CA2736674C (en) | 2011-04-07 | 2018-05-01 | Nova Chemicals Corporation | Supported phosphinimine catalyst systems |
CA2739969C (en) | 2011-05-11 | 2018-08-21 | Nova Chemicals Corporation | Improving reactor operability in a gas phase polymerization process |
US9127106B2 (en) | 2011-06-09 | 2015-09-08 | Nova Chemicals (International) S.A. | Modified phosphinimine catalysts for olefin polymerization |
US9315591B2 (en) | 2011-06-09 | 2016-04-19 | Nova Chemicals (International) S.A. | Modified phosphinimine catalysts for olefin polymerization |
CA2742454C (en) | 2011-06-09 | 2018-06-12 | Nova Chemicals Corporation | Methods for controlling ethylene copolymer properties |
US9221935B2 (en) | 2011-06-09 | 2015-12-29 | Nova Chemicals (International) S.A. | Modified phosphinimine catalysts for olefin polymerization |
US9243092B2 (en) | 2011-06-09 | 2016-01-26 | Nova Chemicals (International) S.A. | Modified phosphinimine catalysts for olefin polymerization |
US9321859B2 (en) | 2011-06-09 | 2016-04-26 | Nova Chemicals (International) S.A. | Modified phosphinimine catalysts for olefin polymerization |
CA2742461C (en) | 2011-06-09 | 2018-06-12 | Nova Chemicals Corporation | Modified phosphinimine catalysts for olefin polymerization |
US9127094B2 (en) | 2011-06-09 | 2015-09-08 | Nova Chemicals (International) S.A. | Modified phosphinimine catalysts for olefin polymerization |
EP2841471B1 (en) | 2012-04-27 | 2020-05-06 | W. R. Grace & Co. - Conn. | Activator compositions, their preparation, and their use in catalysts |
CA2783494C (en) | 2012-07-23 | 2019-07-30 | Nova Chemicals Corporation | Adjusting polymer composition |
ES2823768T3 (es) | 2012-12-28 | 2021-05-10 | Univation Tech Llc | Métodos para integrar la producción de aluminoxano en la producción de catalizador |
EP2945737B1 (en) | 2013-01-14 | 2019-03-13 | Univation Technologies, LLC | Methods for preparing catalyst systems with increased productivity |
CA2809718C (en) | 2013-03-15 | 2020-03-24 | Nova Chemicals Corporation | Improved energy utilization in a solution polymerization plant |
CA2827839C (en) | 2013-09-19 | 2019-12-24 | Nova Chemicals Corporation | A solution polymerization process with improved energy utilization |
CN106604778B (zh) | 2014-06-24 | 2018-12-18 | 诺瓦化学品(国际)股份有限公司 | 控制搅拌反应器中的局部流体年龄 |
CA2857456C (en) | 2014-07-22 | 2022-05-03 | Nova Chemicals Corporation | Improved control over particulate feed |
US10399052B2 (en) | 2014-11-25 | 2019-09-03 | Univation Technologies, Llc | Methods of controlling polyolefin melt index |
CA2874344C (en) | 2014-12-15 | 2021-08-31 | Nova Chemicals Corporation | Spheroidal catalyst for olefin polymerization |
US20160215112A1 (en) | 2015-01-23 | 2016-07-28 | Nova Chemicals (International) S.A. | Enhanced foam resin |
WO2016182920A1 (en) | 2015-05-08 | 2016-11-17 | Exxonmobil Chemical Patents Inc. | Polymerization process |
CA2891002C (en) | 2015-05-13 | 2022-09-06 | Veronica Rose Zimmerman | Modeling a bed plate and its use |
TW201800424A (zh) | 2016-02-18 | 2018-01-01 | 努發化工(國際)公司 | 溶液聚合法 |
WO2018063765A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018063767A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018063764A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018118155A1 (en) | 2016-12-20 | 2018-06-28 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2019086987A1 (en) | 2017-11-06 | 2019-05-09 | Nova Chemicals (International) S.A. | Polyolefin preparation process |
US11591417B2 (en) | 2017-12-13 | 2023-02-28 | Exxonmobil Chemical Patents Inc. | Deactivation methods for active components from gas phase polyolefin polymerization processes |
WO2019173030A1 (en) | 2018-03-08 | 2019-09-12 | Exxonmobil Chemical Patents Inc. | Methods of preparing and monitoring a seed bed for polymerization reactor startup |
US11459408B2 (en) | 2018-05-02 | 2022-10-04 | Exxonmobil Chemical Patents Inc. | Methods for scale-up from a pilot plant to a larger production facility |
EP3788081A1 (en) | 2018-05-02 | 2021-03-10 | ExxonMobil Chemical Patents Inc. | Methods for scale-up from a pilot plant to a larger production facility |
WO2020014138A1 (en) | 2018-07-09 | 2020-01-16 | Exxonmobil Chemical Patents Inc. | Polyethylene cast films and methods for making the same |
US11383483B2 (en) | 2018-07-26 | 2022-07-12 | Exxonmobil Chemical Patents Inc. | Multilayer foam films and methods for making the same |
EP3880739A1 (en) | 2018-11-13 | 2021-09-22 | ExxonMobil Chemical Patents Inc. | Polyethylene films |
EP3880738A1 (en) | 2018-11-13 | 2021-09-22 | ExxonMobil Chemical Patents Inc. | Polyethylene blends and films |
WO2020163079A1 (en) | 2019-02-06 | 2020-08-13 | Exxonmobil Chemical Patents Inc. | Films and backsheets for hygiene articles |
WO2021126458A1 (en) | 2019-12-17 | 2021-06-24 | Exxonmobil Chemical Patents Inc. | Films made of polyethylene blends for improved sealing performance and mechanical properties |
WO2021183337A1 (en) | 2020-03-12 | 2021-09-16 | Exxonmobil Chemical Patents Inc. | Films made of polyethylene blends for improved bending stiffness and high md tear resistance |
CN117098785A (zh) | 2021-04-30 | 2023-11-21 | 埃克森美孚化学专利公司 | 用于聚合反应器中不同聚合催化剂之间的转变的方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1231774B (it) * | 1989-08-03 | 1991-12-21 | Enichem Anic Spa | Catalizzatore e procedimento per la polimerizzazione e per la copolimerizzazione di alfa olefine. |
US5064802A (en) * | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
DE4203753A1 (de) * | 1992-02-10 | 1993-08-12 | Basf Ag | Katalysatorsysteme zur polymerisation von c(pfeil abwaerts)2(pfeil abwaerts)-bis c(pfeil abwaerts)1(pfeil abwaerts)(pfeil abwaerts)0(pfeil abwaerts)-alkenen |
US5468889A (en) * | 1994-06-20 | 1995-11-21 | The University Of Toledo | Boryl zirconocene organic 1,1-dimetallic compounds |
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- 1995-12-20 EP EP95943891A patent/EP0804490B1/en not_active Expired - Lifetime
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- 1995-12-20 AU AU45243/96A patent/AU692985B2/en not_active Ceased
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EP0804490A2 (en) | 1997-11-05 |
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AU4524396A (en) | 1996-08-14 |
US5554775A (en) | 1996-09-10 |
DE69503070T2 (de) | 1999-05-27 |
EP0804490B1 (en) | 1998-06-17 |
CN1118479C (zh) | 2003-08-20 |
AU692985B2 (en) | 1998-06-18 |
WO1996023004A2 (en) | 1996-08-01 |
KR19980702204A (ko) | 1998-07-15 |
TW338045B (en) | 1998-08-11 |
CA2210496C (en) | 2005-09-13 |
BR9510293A (pt) | 1998-06-30 |
FI119735B (fi) | 2009-02-27 |
JPH11501339A (ja) | 1999-02-02 |
WO1996023004A3 (en) | 1998-01-22 |
FI973710A0 (fi) | 1997-09-17 |
ES2126336T3 (es) | 1999-03-16 |
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