CN1165151A - 长链支化聚烯烃的生产方法 - Google Patents
长链支化聚烯烃的生产方法 Download PDFInfo
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- CN1165151A CN1165151A CN96121362A CN96121362A CN1165151A CN 1165151 A CN1165151 A CN 1165151A CN 96121362 A CN96121362 A CN 96121362A CN 96121362 A CN96121362 A CN 96121362A CN 1165151 A CN1165151 A CN 1165151A
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- hydrocarbon
- cyclopentadienyl
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- 238000006116 polymerization reaction Methods 0.000 claims abstract description 32
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- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
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- 230000003213 activating effect Effects 0.000 description 7
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- 230000000694 effects Effects 0.000 description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 7
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
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- 125000001931 aliphatic group Chemical group 0.000 description 4
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- GOVWJRDDHRBJRW-UHFFFAOYSA-N diethylazanide;zirconium(4+) Chemical compound [Zr+4].CC[N-]CC.CC[N-]CC.CC[N-]CC.CC[N-]CC GOVWJRDDHRBJRW-UHFFFAOYSA-N 0.000 description 3
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- PDZFAAAZGSZIFN-UHFFFAOYSA-N dichloro(2-methylpropyl)borane Chemical compound CC(C)CB(Cl)Cl PDZFAAAZGSZIFN-UHFFFAOYSA-N 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- FAFYLCKQPJOORN-UHFFFAOYSA-N diethylborane Chemical compound CCBCC FAFYLCKQPJOORN-UHFFFAOYSA-N 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- OYCNHLAKDKIJIT-UHFFFAOYSA-N ethyl-bis(2-methylpropyl)borane Chemical compound CC(C)CB(CC)CC(C)C OYCNHLAKDKIJIT-UHFFFAOYSA-N 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- OCNWZQYHJJKOIC-UHFFFAOYSA-J n,n-diethylcarbamate;zirconium(4+) Chemical compound [Zr+4].CCN(CC)C([O-])=O.CCN(CC)C([O-])=O.CCN(CC)C([O-])=O.CCN(CC)C([O-])=O OCNWZQYHJJKOIC-UHFFFAOYSA-J 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 1
- XMGMFRIEKMMMSU-UHFFFAOYSA-N phenylmethylbenzene Chemical group C=1C=CC=CC=1[C]C1=CC=CC=C1 XMGMFRIEKMMMSU-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- KBGJIKKXNIQHQH-UHFFFAOYSA-N potassium;methanidylbenzene Chemical compound [K+].[CH2-]C1=CC=CC=C1 KBGJIKKXNIQHQH-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- LFXWJXWPMAPFOU-UHFFFAOYSA-N tripentylborane Chemical compound CCCCCB(CCCCC)CCCCC LFXWJXWPMAPFOU-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C08F10/02—Ethene
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- 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
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
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- 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
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- 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
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- 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
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Abstract
一种生产具有长链支化的聚乙烯均聚物、共聚物或三元聚合物的方法,包括在聚合条件下在用量足以提供链缠结或长链支化的烃互连化合物存在下,在含金属茂聚合催化剂的反应区中提供乙烯和非必要的具有3至18个碳原子的α-烯烃。
Description
本发明涉及聚烯烃,特别是具有长链支化的聚烯烃,更特别是聚乙烯的聚合方法。
US 5,317,036公开了使用没有担载的催化剂,如过渡金属配位催化剂的气相聚合方法。将催化剂以液体,如溶液形式加入反应器,如流化床中。该专利还公开了使用二烯烃作为共聚单体生产聚烯烃如乙烯-丙烯-二烯烃弹性体。
虽然已经知道使用二烯烃在聚烯烃聚合中作为共聚单体或活化齐格勒(Zieg1er)型催化剂(US 5,021,382),但还不知道使用少量多烯如二烯烃、共轭或非共轭的三烯烃、环烯烃(如环戊二烯)或其它具有二个或多个碳-碳双键或是带有至少一个额外双键的环的互连化合物以在聚合过程中增加或增强聚烯烃的长链支化。
在本发明中已令人吃惊地发现具有长链支化的聚乙烯聚合物可在含有金属茂聚合催化剂的反应区中在烃互连化合物存在下聚合。同时,此聚乙烯产物具有增强的的加工性和改进的挤出性、韧性、强度和耐环境应力开裂性。
根据本发明,提供一种生产具有长链支化的乙烯均聚物、共聚物或三元聚合物的方法,包括在含金属茂催化剂的反应区中在聚合条件下在用量足以提供具有链缠结的聚乙烯聚合物的烃互连化合物存在下提供乙烯和非必要的至少一种具有3至18个碳原子的α-烯烃。
在本发明的一个实施方案中,提供一种生产具有长链支化的聚乙烯的方法,包括将乙烯与非必要的至少一种C3至C8α-烯烃在反应区中在用量足以提供链缠结的烃互连化合物和金属茂催化剂存在下接触,所述金属茂催化剂包括:
(i)具有如下通式的催化剂前体
M为过渡金属,优选Zr或Hf;
L为与M配位的取代或未取代的1-键合配位体,优选环戊二烯基配位体;
Q可以是相同或不同的,且独立地选自-O-、-NR-、-CR2-和-S-;
Y为C或S;
Z选自-OR、-NR2、-CR3、-SR、-SiR3-PR2和-H,条件是当Q为-NR-时,Z选自-OR、-NR2、-SR、-SiR3、-PR2和-H;
n为1或2
当n为2时,A为一价阴离子基团,或当n为1时,A为二价阴离子基团;和
R可以是相同或不同的,并且独立地含有碳、硅、氮、氧和/或磷的基团,其中一个或多个R基团可与L取代基连接,R优选为含有1至20个碳原子的烃基基团,最优选烷基、环烷基或芳基基团或
M为过渡金属,优选Zr或Hf;
L为与M键合的取代或未取代的1-键合配位体,优选环戊二烯基配位体;
Q可以是相同或不同的,且独立地选自-O-、-NR-、-CR2和-S-;
Y为C或S;
Z选自为-OR、-NR2、-CR3、-SR、-SiR3、PR3和-H,条件是当Q为-NR-时,Z选自-OR、-NR2、-SR、-SiR3、-PR2和-H;
n为1或2;
当n为2时,A为一价阴离子基团,或当n为1时,A为二价阴离子基团;
R可以相同或不同的,且可独立地选自碳、硅、氮、氧和/或磷的基团,其中一个或多个R基团可与L取代基连接,R优选为含有1至20个碳原子的烃基基团,最优选烷基环烷基或芳基基团;T为选自含1至10个碳原子的亚烷基或亚芳基基团,所述亚烷基或亚芳基基团可任选地用碳或杂原子、锗、硅和烷基膦取代;和
m为1至7,优选2至6,最优选2或3;及(ii)助催化剂。还提供由本发明方法生产的聚合物,特别是包括乙烯、烃连接化合物和非必要的C3至C8α-烯烃(例如已烯-1或丁烯-1)的聚合物。
在长链支化中,为使链缠结,聚合物具有足够长的支化,即支链长度足够长或含有足够量的碳原子以便与其它聚合分子缠结。通常,长链支化包括至少约6个碳原子,通常10个碳或更多碳原子的链长度。长链分支大约可与聚合物骨架的长度一样长。
本发明的方法特别适合用金属茂催化剂制备低密度乙烯-已烯-1-烃互连化合物三元聚合物、低密度乙烯-是正确的烯-1-烃互连化合物三元聚合物和低密度乙烯-烃互连化合物共聚合物。通过本发明方法制备的聚合物具有与高压低密度乙烯均聚物和聚乙烯-α-烯烃C3-C18)共聚物相似的性能。催化剂
本发明的实施不限于任何特殊类型或种类的金属茂催化剂。用于进行烯烃聚合反应的任何金属茂催化剂都适合用于实施本发明。在淤浆、溶液、本体和气相聚合中使用的金属茂催化剂可用于本发明中。这些金属茂催化剂一般包括金属组分和助催化剂。金属茂催化剂可载在固体载体上、以呈液态的可溶形式如溶液或分散体形式、喷雾干燥形式预聚物形式加入反应区中或在反应区中现场形成。其中特别优选的是喷雾干燥或可溶形式的那些金属茂催化剂。当金属组分被载在载体上时,典型的载体包括(例如)二氧化硅、炭黑、聚乙烯、聚碳酸酯多孔性交联聚苯乙烯、多孔性交联聚丙烯、氧化铝、氧化钍、氧化锆或卤化镁(例如二氯化镁)以及其它公知的载体物质和其混合物。将载在载体上的金属茂催化剂组合物,即催化剂前体和活化助催化剂浸渍入或沉积在惰性载体基料表面上,使催化剂组合物按催化剂组合物和载体的总重量计为1-90%(重量)。
M为元素周期表IIIB至VIII族金属;
Cp为以η5键合方式与M键合的环戊二烯基或取代环戊二烯基;
Z是包括硼,或元素周期表IVB族元素和非必要的硫或氧的部分,此部分具有至多20个非氢原子,且非必要性地Cp与Z一起形成稠合环体系;
X′为具有至多30个非氢原子的阴离子配位体基团或中性路易斯碱配位体基团;
a为0、1、2、3或4,取决于M的价态;和
Y1为与Z和M键合的阴离子或非离子配位体基团,它是具有至多20个非氢原子的氮、磷、氧或硫,且非必要性地Y与Z一起形成稠合环体系。
这些金属配合物是本领域熟练技术人员公知的并公开于(例如)US5,026,798和5,055,438及EPO 416 815 A2中。
上述通式表示的说明性但非限制性的例子如下:
Z Cp Y X M二甲基- 环戊二烯基 叔丁基酰氨基 氯 钛甲硅烷基甲基- 芴基 苯基酰氨基 甲基 锆苯基甲硅烷基二苯基-甲 茚基 环己基酰氨基 铪硅烷基
四甲基- 氧代亚乙基亚乙基 四甲基环
戊二烯基二苯基-亚甲基
除铝氧烷外的适合本发明目的的典型有机金属助催化剂是具有以下通式的任何化合物:
M3M4 VX2 CR3 b-c (IV)其中M3为元素周期表IA、IIA和IIIA族金属;M4为元素周期表IA族金属;V为0至1的数;各X2为任何卤素;c为0至3的数;各R3为单价烃基或氢;b为1至4的数;其中b-c至少为1。
适合实施本发明的仅具有一个IA、IIA或IIIA族金属元素的化合物包括具有如下通式的化合物:
M3R3 K (V)其中:
M3为IA、IIA或IIIA族金属,如锂、钠、铍、钡、硼、铝、锌、镉和镓;
K等于1、2或3,取决于M3的价态,该价态一般最终取决于M3所属的具体的族(即IA、IIA或IIIA族);和
各R3可以为任何单价烃基。适合R3基团的例子包括上述与通式(V)有关的任何R3基团。
完全适合本发明目的的是IA、IIA和IIIA族有机金属化合物,如甲基和丁基锂、二己基锌、丁基镁、二乙基镉、苄基钾、二乙基锌、三正丁基铝、二异丁基乙基硼、二乙基镉、二正丁基锌和三正戊基硼,特别是烷基铝如三己基铝、三乙基铝、三甲基铝和三异丁基铝。
此外,符合通式(VI)的IIA族金属的单有机基卤化物和氢化物,IIIA族金属的单和二有机基卤化物和氢化物也是合适的。这些化合物的具体例子是溴化二异丁基铝、二氯化异丁基硼、氯化甲基镁,氯化乙基铍、溴化乙基钙、氢化二异丁基铝、氢化甲基镉、氢化二乙基硼、氢化己基铍、氢化二丙基硼、氢化辛基镁、氢化丁基锌、氢化二氯合硼、氢化二溴合铝和氢化二溴合镉。这些有机金属助催化剂化合物是本领域熟练技术人员公知的,这些化合物更详细的讨论可在US 3,211,002和5,093,415中找到。
在本发明另一实施方案中,采用一种或多种金属茂与铝氧烷的催化活化反应产物(将其加入气相流化床反应器中)生产聚乙烯。
金属茂是有机金属化合物,该化合物是元素周期表IVB、VB、VIB或VIII族金属的环戊二烯基衍生物并包括单、双和三环戊二烯基化物和其过渡金属衍生物。特别需要的是IVB和VB族金属如钛、锆、铪和钒的金属茂配合物。
通式(VI)表示低聚线型铝氧烷;和
通式VII表示低聚环状铝氧烷;
其中S为1-40,优选10-20;p为3-40;优选3-20;R″为C1-C12烷基基团,优选甲基和芳基基团如取代或未取代的苯基或萘基。
在由(例如)三甲基铝和水制备铝氧烷的过程中,一般得到线型和环状化合物的混合物。
铝氧烷可按各种方式制备。例如,可将烷基铝用水以湿溶剂形式处理。此外,也可将烷基铝如三甲基铝与水合盐如水合硫酸铁接触。后一方法包括用七水合硫酸铁悬浮液处理三甲基铝在(例如)甲苯中的稀释溶液。还可以通过含C2或更高级烷基的四烷基二铝氧烷与用量低于化学计量过量的三烷基铝反应形成甲基铝氧烷。甲基铝氧烷的合成也可以通过含C2或更高级烷基基团的三烷基铝化物或四烷基二铝氧烷与水反应形成聚烷基铝氧烷,然后与三甲基铝反应来实现。此外,甲基铝氧烷(也称为改性的铝氧烷)可通过含C2或更高级烷基基团的聚烷基铝氧烷与三甲基铝反应,然后与水反应来合成(如US 5,041,584中公开的)。
可用于本发明方法中的另一种金属茂可由如下通式表示:
(C5RX)YR′Z(C5Rm)MQn-y-1 (VIII)其中:
M为元素周期表IIIB至VIII族的金属;
(C5Rx)和(C5Rm)是与M键合的相同或不同的环戊二烯基或取代烷戊二烯基基团;R是相同或不同的,且为氢或烃基如含1至20个碳原子的烷基、链烯基、芳基、烷基芳基或芳烷基或两个碳原子相互连接形成C4-C6环;
R′是桥连两个(C5Rx)和(C5Rm)环的C1-C4取代或未取代的亚烷基、二烷基或二芳基镓或硅,或烷基或芳基膦或胺基。
Q是烃基,如具有1-20个碳原子的芳基、烷基、链烯基、烷芳基或芳烷基、具有1-20个碳原子的羧基、卤素,氢,R″CO2-和R″2N,其中R″是1至约20个碳原子的烃基,且可以是相同或不同的。
Z为0或1;Y为0、1或2;当y为0时Z为0;n为0、1、2、3或4,取决于M的价态;和n-y≥1。
上述通式表示的说明性但非限制性的实施例是二烷基金属茂类如双(环戊二烯基)·二甲基合钛、双(环戊二烯基)·二苯基合钛、双(环戊二烯基)·二甲基合锆、双(环戊二烯基)·二苯基合锆、双(环戊二烯基)·二甲基合铪、双(环戊二烯基)·二苯基合铪、双(环戊二烯基)·二新戊基合钛、双(环戊二烯)·二辛戊基合锆、双(环戊二烯基)·二苄基合钛、双(环戊二烯基)·二苄基合锆、双(环戊二烯基)·二甲基合钒;单烷基金属茂类如氯·双(环戊二烯基)·甲基合钛、氯·双(环戊二烯基)·乙基合钛、氯·双(环戊二烯基)·苯基合钛、氯·双(环戊二烯基)·甲基合锆、氯·双(环戊二烯基)·乙基合锆、氯·双(环戊二烯基)·苯基合锆、溴·双(环戊二烯基)·甲基合钛;三烷基金属茂类和如环戊二烯基·三甲基合钛、环戊二烯基·三苯基合锆、环戊二烯基·三新戊基合锆、环戍二烯基·三甲基合锆、环戊二烯基·三苯基合铪、环戊二烯基·三新戊基合铪和环戊二烯基·三甲基合铪;单环戊二烯基钛茂类如三氯·五甲基环戊二烯基合钛、三氯·五甲基环戊二烯基合钛;双(五甲基环戊二烯基)·二苯基合钛、由通式双(环戊二烯基)·钛=CH2表示的碳烯和此试剂的衍生物;取代的双(环戊二烯)合钛(IV)化合物如:双(茚基)·二苯基合钛或双(茚基)·二氯合钛、双(甲基环戊二烯基)·二苯基合钛或双(甲基环戊二烯基)·二卤合钛;二烷基、三烷基、四甲基和五甲基环戊二烯基合钛化合物类如双(1,2-二甲基环戊二烯基)·二苯基或二氯合钛、双(1,2-二乙基环戊二烯基)·二苯基或二氯合钛;硅、膦,胺或碳桥连的环戊二烯基配合物类如二甲基甲硅烷基双环戊二烯基·二苯基或二氯合钛、甲基膦双环戊二烯基·二苯基或二氯合钛、亚甲基双环戊二烯基·二苯基或二氯合钛、和其它二卤合配合物等;以及桥连的金属茂配合物如异丙基(环戊二烯)·(芴基)·二氯合锆、异丙基(环戊二烯基)·(八氢芴基)·二氯合锆、二苯基亚甲基(环戊二烯基)·(芴基)·二氯合锆、二异丙基亚甲基(环戊二烯基)·(芴基)·二氯合锆、二异丁基亚甲基(环戊二烯基)·(芴基)·二氯合锆、二叔丁基亚甲基(环戊二烯基)·(芴基)·二氯合锆、亚环己基(双环戊二烯基)·(芴基)·二氯合锆、二异丙基基亚甲基(2,5-二甲基环戊二烯基)·(芴基)·二氯合锆、异丙基(环戊二烯基)·(芴基)·二氯合铪、二苯基亚甲基(环戊二烯基)·(芴基)·二氯合铪、二异丙基亚甲基(环戊二烯基)·(芴基)·二氯合铪、二异丁基亚甲基(环戊二烯基)·(芴基)·二氯合铪、二叔丁基亚甲基(环戊二烯基)·(芴基)·二氯合铪、亚环已基(环戊二烯基)·(芴基)·二氯合铪、二异丙基亚甲基(2,5-二甲基环戊二烯基)·(芴基)·二氯合铪、异丙基(环戊二烯基)·(芴基)·二氯合钛、二苯基亚甲基(环戊二烯基)·(芴基)·二氯合钛、二异丙基亚甲基(环戊二烯基)·(芴基)·二氯合钛、二异丁基亚甲基(环戊二烯基)·(芴基)·二氯合钛、二叔丁基亚甲基(环戊二烯基)·(芴基)·二氯合钛、亚环已基(环戊二烯基)·(芴基)·二氯合钛、二异丙基亚甲基(2,5-二甲基环戊二烯基) (芴基)、二氯合钛、外消旋-亚乙基双(1-茚基)·二氯合锆(IV)、外消旋-亚乙基双(4,5,6,7-四氢-1-茚基)二氯合锆(IV)、外消旋-二甲基甲硅烷基双(1-茚基)·二氯合锆(IV)、外消旋-二甲基甲硅烷基双(4,5,6,7-四氢-1-茚基)二氯合锆(IV)、外消旋-1,1,2,2-四甲基亚硅烷基双(1-茚基)·二氯合锆(IV)、外消旋-1,1,2,2-四甲基亚硅烷基双(4,5,6,7-四氢-1-茚基)·二氯合锆(IV)、亚乙基(1-茚基四甲基环戊二烯基)二氯合锆(IV)、外消旋-二甲基甲硅烷基双(2-甲基-4-叔丁基-1-环戊二烯基)·二氯合锆(IV)、外消旋-亚乙基双(1-茚基)·二氯合铪(IV)、外消旋-亚乙基双(1-茚基)·二氯合铪(IV)、外消旋-亚乙基双(4,5,6,7-四氢-1-茚基)·二氯合铪(IV)、外消旋-二甲基甲硅烷基双(1-茚基)·二氯合铪(IV)、外消旋-二甲基甲硅烷基双(4,5,6,7-四氢-1-茚基)·二氯合铪、外消旋-1,1,2,2-四甲基亚硅烷基双(1-茚基)·二氯合铪(IV)、外消旋-1,1,2,2,-四甲基亚硅烷基双(4,5,6,7-四氢-1-茚基)·二氯合铪(IV)、亚乙基(1-茚基-2,3,4,5-四甲基-1-环戊二烯基)·二氯合铪(IV)、外消旋-亚乙基双(1-茚基)·二氯合钛(IV)、外消旋-亚乙基双(4,5,6,7-四氢-1-茚基)·二氯合钛(IV)、外消旋-二甲基甲硅烷基双(1-茚基)二氯合钛(IV)、外消旋-二甲基甲硅烷基双(4,5,6,7-四氢-1-茚基)·二氯合钛(IV)、外消旋-1,1,2,2-四甲基亚硅烷基双(1-茚基)·二氯合钛(IV),外消旋-1,1,2,2-四甲基亚硅烷基双(4,5,6,7-四氢-1-茚基)·二氯合钛(IV)、和亚乙基(1-茚基-2,3,4,5-四甲基-1-环戊二烯基)二氯化钛。
通常为固体物质的金属茂与铝氧烷的反应产物当在脂族溶剂的和溶液中生产和在芳族溶剂中生产时可通过公知的方法回收。例如,固体物质可通过真空过滤或滗析从液体中回收。油可通过滗析回收,当干燥时变为玻璃态固体。然后将回收的物质在纯氮气流下干燥、在真空下干燥或通过其它方便的方法干燥。回收的固体是催化活性物质。
用于制备催化活性物质的铝氧烷和金属茂的量,无论该活性物质是在加入气相反应器时现场形成的,或是预先形成并以液态形式加入的,都可在宽范围内变化。铝氧烷中所含的铝原子与金属茂中所含的金属原子的摩尔比一般为约2∶1至约100,000∶1,优选约10∶1至约10,000∶1,更优选约50∶1至约2,000∶1。
金属茂一般用离子化试剂(也称为催化剂活化剂),如前面讨论的铝氧烷,转化为活性催化剂。这种离子化试剂与中性金属茂反应形成起活性催化剂作用的阳离子金属茂。离子化试剂可以为助催化剂化合物如铝氧烷,或可以为离子化的离子化合物,该离子化合物形成与阳离子金属茂不发生化学反应的阴离子。该阴离子不与阳离子金属茂配位或形成松散配位。这类含非反应阴离子的离子化试剂的用途公开于(例如)EP 426637、426638和427697中。生成阳离子金属茂的方法还公开于下列文献中:EP 277003和277004:“Ethylene Polymerization by a CationicDicyclopentadienylzirconium(IV)Alkyl Complex,"R.F.Jordan,C.S.Bajgur,R.Willett,J.Am.Chem.Soc.,P.7410-7411,Vol.108(1986);"Synthesis and Insertion Reactions of CationicAlkylbis(Cyclopentadienyl)titanium Complexes,"M.Bochmann,L.M.Wilson,J.Chem.Soc.Commun.,P.1610-1611(1986);"InsertionReactions of Nitriles in Cationic Alkylbis(Cyclopentadienyl)titanium Complexes,M.Bochmann,L.Wilson,Organometallics,P.1147-1154,Vol 7(1987);和"Multiple Metal-Carbon Bonds,"R.R.Schrock,P.P.Sharp,J.Am.Chem.Soc.P.2389-2399,Vol 100(1978)。
离子化离子试剂一般与等摩尔量的金属茂的中性衍生物混合,产生下列反应:
[C]为碳鎓、氧鎓或锍阳离子
[A]为不与阳离子金属茂配位或仅松散配位的阴离子并且不与阳离子金属茂发生化学反应。
R和R″是相同或不同的并为氢或含有1至20个碳原子的烃基如烷基、链烯基、芳基、烷芳基或芳烷基或两个碳原子相互连接形成C4-C6环;
M为元素周期表IIIB至VIII族金属。
(C5Rx)和(C5Rm)为与M键合的相同或不同的环戊二烯基或取代的环戊二烯基。
R′为桥连两个(C5Rx)和(C5Rm)环的C1-C4取代或未取代亚烷基、二烷基或二芳基锗或硅,或烷基或芳基膦或胺。
Z为0或1;y为0、1或2;当y为0时,Z为0;
含碳鎓、氧鎓或锍阳离子的离子化离子化合物是合适的。优选三苯基甲基四(五氟苯基)硼酸盐。
不需要铝氧烷的催化剂体系包括具有一个或多个取代了负一价环戊二烯基配位体的负二价配位体的金属茂配合物。这些化合物的用途公开于普通转让的美国专利申请流水号814809(申请日1991年12月31日)和美国专利申请流水号814,810(申请日1991年12月31日)。这些聚烯烃催化剂的例子包括:
[(C5(CH3)5][C2B9H11]ZrCH3和[[C5(CH3)5][C2B9H11Zr]2-m-CH2。
正如前面讨论的,当使用两种或多种金属茂化合物是有利的。US 4530914公开了使用至少两种不同的金属茂化合物的混合物来控制分子量分布。均相的单或双环戊二烯基过渡金属化合物催化剂生成具有窄分子分布和窄组成分布的聚烯烃。已经知道单或双环二烯基过渡金属化合物的配位体取代基或金属组分的变化会影响聚合增长和终止速率常数,最终影响所得聚烯烃产品的分子量和共聚单体分布。合适地选择不同单或双环戊二烯基过渡金属化合物的混合物可直接在聚合方法中控制分子量分布和组成分布,不需要在聚合之后的能量集中共混技术。
本发明的最优选催化剂可通过下列通式I或通式II的催化剂前体与助催化剂如MAO或MMAO反应来产生:通式(I)其中:
M是过渡金属,优选Zr或Hf;
L是与M键合的取代或未取代的1-键合配位体,优选取代的环戊二烯配位体;
Q可以是相同或不同的,独立地选自-O-、-NR-、-CR2和-S-,优选氧;
Y是C或S,优选碳;
Z选自-OR、-NR2、-CR3、-SR、-SiR3、-PR2和-H,条件是当Q为-NR-时,Z选自-OR、-NR2、-SR、-SiR3、-PR2和-H,Z优选选自-OR、-CR3和-NR2;
n为1或2;
当n为2时,A为一价阴离子基团,当n为1时,A为二价阴离子基团,W优选为由X、Y和Z相结合描述的氨基甲酸酯、羧酸酯或其它杂烯丙基部分。
R可以为相同或不同的,并独立地是含有碳、硅、氮、氧和/或磷的基团,其中一个或多个R基团可与L取代基连接,R优选为含1-20个碳原子的烃基,最优选烷基,环烷基或芳基基团且一个或多个R基团可与L取代基连接。通式(II)其中:
M为过渡金属,优选Zr或Hf;
L为与M配位的取代或未取代的1-键合配位体;优选取代的环戊二烯基。
Q可以为相同或不同的,并独立地选自-O-、-NR-、-CR2和-S-,优选氧。
Y为C或S,优选碳;
Z选自-OR、-NR2、-CR3、-SR、-SiR3、PR2和-H,条件是当Q为-NR-时,Z选自-OR、-NR2、-SR、-SiR3、-PR2和-H,Z优选选自-OR、-CR3和-NR2;
n为1或2;
当n为2时,A为单价阴离子基团,当n为1时,A为二价阴离子基团,优选由Q、Y和Z相结合描述的氨基甲酸酯、羧酸酯或其它杂烯丙基部分;
R可以是相同或不同的,并独立地含有碳、硅、氮、氧和/或磷的基团,其中一个或多个R基团可与L取代基连接,R优选为含有1至20个碳原子的烃基,最优选烷基、环烷基或芳基基团,且一个或多个R基团可与L取代基连接;
T为桥连基团,选自含有1至10个碳原子的亚烷基或亚芳基基团,这些基团任选地被碳或杂原子,锗、有机硅和烷基膦取代。
m为1至7,优选2至6,最优选2或3。
本发明特别优选的实施方案是茚基三(氨基甲酸二乙酯)锆。
本发明的催化剂前体可用任何常规方法制备;制备方法并不重要。在制备这种催化剂的优选方法中,将环戊二烯型配位体源与通式M(NR2)4的金属化合物反应以便将环戊二烯基型配位体引入金属化合物上,其中M和R为前面所定义的。然后将所得产物溶于惰性溶剂如甲苯中,并将杂累积烯(在此情况下如CO2)与溶解的产品接触以插入一个或多个M-NR2键,(在这种情况下)形成氨基甲酸酯。最后将这些前体与活化剂如铝氧烷反应形成活性催化剂。
其它催化剂前体的例子包括茚基三(新戊酸)锆或茚基三(对甲苯甲酸)锆三(新戊酸)锆、茚基三(对甲苯甲酸)锆、茚基三(苯甲酸)锆、(1-甲基茚基)三(新戊酸)锆、(2-甲基茚基)三(氨基甲酸二乙酯)锆、(甲基环戊二烯基)三(新戊酸)锆、环戊二烯基三(新戊酸)锆、(五甲基环戊二烯基)三(苯甲酸)锆、如上所述,催化剂可以是载在载体上的、喷雾干燥的或液态形式。在特别优选的实施方案中,将催化剂喷雾或以液态形式(如溶液或淤浆形式)使用。
如上所述,为生产聚乙烯,将这些催化剂前体与活化助催化剂结合使用以形成催化剂组合物。
活化助催化剂能够活化金属茂催化剂。活化助催化剂优选为下列之一:(a)含有通式-(Al(R*)O)-的重复单元的支化或环状低聚聚(烃基氧化铝)s,其中R*为氢,含1至约12个碳原子的烷基,或芳基如取代或未取代的苯基或萘基基团;(b)通式[A+][BR** 4-]的离子盐,其中A+是能够吸收来自金属茂催化剂的烷基、卤素或氢原子的阳离子Lewis或Bronsted酸,B为硼,R**为取代的芳烃,优选全氟苯基;和(C)为通式BR** 3的烷基硼,其中R**为上面所定义的。
与通式I和II的金属茂一起使用的活化助催化剂是支化或环状低聚(烃基氧化铝)。活化助催化剂为铝氧烷如甲基铝氧烷(MAO)或异丁基改性的甲基铝氧烷(MMAO)。
如上所述,铝氧烷是本领域公知的,它包括通式表示的低聚线型基铝氧烷,和通式表示的低聚环状烷基铝氧烷,其中S为1-40,优选10-20;p为3-40,优选3-20;R***为含有1-12个碳原子的烷基基团,优选甲基或异丁基如取代或未取代的基团。
催化剂组合物可任选地含有一种或多种非金属茂催化剂。这些非金属茂催化剂包括(例如含元素周期表IV(B)、V(B)或VI(B)族金属的Ziegler-Natta催化剂。Ziegler-Natta催化剂的合适活化剂是本领域公知的并可包含于催化剂组合物中。烃互连化合物
在本方法中使用烃互连化合物以增加或增强长链支化和/或链缠结。烃互连化合物可具有两个或更多碳-碳双键,或是环应变(ring-Strained)的并具有至少两个双键以在聚合过程中使长链支化和/或链结缠。合适的烃互连化合物包括多烯烃,如二烯,共轭或非共轭的,三烯烃,环链烯(例如环戊二烯,环己烯或环辛烯),和它们的混合物。
烃互连化合物是含有至少6或7个碳原子和至少两个非共轭的碳-碳双键的脂族的,环状的,或脂族和环状的烃。当烃互连化合物含有两个以上双键时,这些另外的双键优选为非反应性的,原因在于它们处于稳定的环结构中或因其是空间位阻的。两个非共轭碳-碳双键中每一个独立地为:1)烯属双键,或2)在含有五个或更少碳原子的环中的唯一碳-碳双键。
烃互连化合物的两个非共轭碳-碳双键都是Ziegler-Natta反应性的;换言之,聚合过程中两个非共轭碳-碳双键在催化剂组合物存在下反应并嵌入正在生长的聚合物链中。同时,烃互连化合物的两个非共轭碳-碳双键在聚合条件下在催化剂组合物存在下,具有基本上相等的Ziegler-Natta反应性,即基本相等的嵌入正在生长的聚烯烃链中的趋势。
本发明的有关烃互连化合物是反应性的或显示相等或基本上相等的嵌入正在生长的聚合物链中的趋势的要求,在使用二烯烃作为共聚单体的现有技术中是不必要的,不需要的,也未公开。事实上,在本发明中已发现化合物如二烯烃趋于共聚的反应性可广泛变化。例如,广泛用于制备EPDM橡胶的二烯烃亚乙基降冰片烯(ENB)具有极高反应性的环应变双键和非反应性双键。丁二烯(BD)和二乙烯基苯(DVB)也显示类似于ENB的反应性。相反从下面的结构式可以看出,本发明的烃互连化合物如降冰片二烯(NBD)和1,7-辛二烯(OCTN)基本上具有相同的反应性双键,尽管乙烯基降冰片烯(VNB)具有两个不同反应性的双键。
本发明的烃互连化合物可以是(例如)仅含有两个烯属碳-碳双键的非共轭线型二烯烃,两双键是Ziegler-Natta反应性的。此外,本发明的烃互连化合物除两个非共轭碳-碳反应性双键外,还可含有一个或多个在本发明方法中通常为非反应性的其它双键,即芳族或顺/反式内-C=C-双键。
一个或一个以上烃互连化合物可用于本发明方法中。可用的烃互连化合物的例子包括1,4-己二烯、1,5-己二烯;、1,6-庚二烯、1,6-辛二烯、降冰片二烯(NBD)、1,6-辛二烯、1,7-辛二烯(OCTDN)、1,8-壬二烯、1,9-癸二烯、1,1,1-十二碳二烯、乙烯基降冰片烯如5-乙烯基-2-降冰片烯(VNB)、5-(2-丙烯基)-2-降冰片烯、二环戊二烯、三乙烯基苯、1,4,4a,5,8,8a-六氢-1,4,5,8-二甲桥萘;支化链无环二烯烃如5-甲基-1,4-己二烯;单环脂环族二烯烃如1,3-环戊二烯、1,4-环已二烯、1,5-环己二烯和1,5-环十二碳二烯;和多环脂环族稠合的和桥连的环状二烯烃如双环戊二烯、双环-(2,2,1)-庚-2,5-二烯、链烯基、亚烷基、环链烯基和亚环烷基降冰片烯如5-亚甲基-2-降冰片烯,5-乙烯基-2-降冰片烯、5-(4-环戊烯基)-2-降冰片烯、5-亚环己基2-降冰片烯和降冰片烯。
优选的是烃互连化合物选自1,6-辛二烯、1,11-十二碳二烯,1,9-癸二烯、1,7-辛二烯、降冰片二烯烃、乙烯基降冰片烯如5-乙烯-2-降冰片烯、5-(2-丙烯基)-2-降冰片烯、二环戊二烯及其混合物。
烃互连化合物最优选为降冰片二烯(NBD)、1,7-辛二烯、乙烯基降冰片烯或其混合物。当二烯烃用作烃互连化合物时,它在聚合中优选也不用作共聚单体。
烃互连化合物在气相法中的用量按加入该方法中的总单体量计(即按所用的乙烯和非必要的α-烯烃总量计)为约0.001至约5%(重量)。总单体进料量的约0.05至约4%(重量)是烃互连化合物。最优选的,总单体进料量的约0.1-3.5%(重量)是烃互连化合物。在淤浆聚合法中,烃互连化合物的量可以稍大浓度使用,例如用量范围按总单体加料量计为约0.001至约10%(重量),优选约0.1至约7.5,最优选约0.5至约6%(重量)。
在特别优选的实施方案中,用本领域熟练技术人员公知的工艺,通过用惰性气体(如氮气)清洗体系,或通过用惰性气体和水蒸汽或氧气清洗,或通过真空下加热将未反应的烃互连化合物从聚合物产品中除去。聚合:
使用本文描述的催化剂和烃互连化合物的聚合可在搅拌床或硫化床反应器内在气相中进行,或在淤浆气相反应器中用本领域公知的设备和工艺进行。聚合优选按照US 4,588,790、4,988,783、4,994、534、5,317,036、5,453,471和5,462,999中公开的那样在气相中进行。本发明的聚合最优选按照US 4,528,790和/或5,462,999公开的那样以冷凝模式进行。将乙烯、高级α-烯烃、非必要的其它单体和烃互连化合物在温度和压力足以引发聚合的条件下与有效量的金属茂催化剂接触。聚合方法在单个反应器或串联或分阶段的的两个或多个反应器中进行。聚合方法基本上在无催化剂毒物如湿汽、氧气、二氧化碳和乙炔存在下进行,原因在于仅发现少量(即≤2ppm)这些物质对聚合产生不利影响。此外,本发明的聚合还可以如US 4,994,534中所述在惰性颗粒物质存在下进行。
当在本方法中将氢气用作链转移剂时,其用量按每摩尔总单体进料量计为约0.001至约10mol。同样,正如系统的温度控制所需要的,对催化剂组合物和反应物表现惰性的各种气体也可存在于气流中。
可将有机金属化合物用作毒物的清除剂以增加催化剂的活性。这些化合物的例子是烷基金属化物,优选烷基铝,最优选三异丁基铝。这类清除剂的用法是本领域公知的。聚合产物
可按照本发明生产的聚烯烃是乙烯、烃互连化合物和非必要的含3至约120个碳原子的高级α-烯烃如丙烯、1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯和1-辛烯的聚合物,聚合物的密度为约0.86至约0.96g/cc、优选约0.89至约0.94g/cc。其中,乙烯-烃互连化合物-己烯-1、乙烯-烃互连化合物-丁烯-1和乙烯-烃互连化合物-丙烯是优选的。此外,乙烯-烃互连化合物-丙烯组合物可非必要地含有二烯烃如ENB和惰性颗粒物质如炭黑和/或二氧化硅。
当按本发明的描述进行生产时,由于存在长度上接近聚合物分子骨架的长链支链,因而可增强聚烯烃的加工性。除了LCB外,这些基本上非线型的聚合物可具有短链支链(SCB)、所述SCB是由加入的共聚单体如己烯-1或丁烯-1形成的。最优选地是,最终聚合物为具有至少0.3至4个LCB/1000个CH2单元的LDPE(密度为0.91-0.93g/cc),此LDPE的结构接近树枝状构型。如此生产的聚合物可用市购的常规稳定剂如Irganox®1035进行稳定化后处理。聚合物分子量可通过用链转移剂如氢气控制。在众多的用途中,这些聚合物适用于在薄膜和模塑产品中使用。乙烯-烃互连化合物和乙烯-烃互连化合物-己烯制得透明,基本无凝胶的薄膜。
本文中引用的所有专利这里作为参考引入。
下列实施例进一步说明本发明。除非另有说明,所有份数和百分数可以重量计。
实施例术语表:
密度根据ASTM 1505,基于ASTM D-1928,规则C,板试样来测定。制备板并将其在100℃下处理1小时使其接近平衡结晶度,然后在密度梯度柱中测量密度。
MAO是甲基铝氧烷在甲苯中的溶液(其中铝约1.8mol),购自Etnyl Corporation(Baton Rougl,LA)。
在异戊烷中的MMAO是含异丁基基团的改性甲基铝氧烷在异戊烷中的溶液,购自Akzo Nobel(Chicago Illinois)。
TMA是三甲基铝
TEAL是乙基铝
TIBA是三异丁基铝
TNBAL是三(正丁基)铝
MFR表示熔体流动比,即流动指数与熔体指数的比例,它与聚合物的分子量分布有关。
MI表示熔体指数,单位g/10min,按照ASTM D-1238,规则E于190℃下测定。FI表示流动指数,g/10min,是根据ASTMD-1238,规则F测定的并在10倍于熔体指数测试中所用重量的重量下测试。步骤测量长链支化的SEC-粘度
具有长链支链的聚乙烯与相同摩尔质量的线型聚乙烯链相比在稀溶液中显示较少延伸的空间构象排列。因此,前者因其低流体动力尺寸,所以具有较低的特性粘度值。已经提出理论关系,该关系得以从支化聚合物的特性粘度值与其线型参照物的粘度值的比例计算长链支化统计值。例如,可参见Mirabella,F.M.Jr.和Wild L.发表在Polymer Characteriation,Amer.Chem.Soc.Symp.Ser.227,190,P.23中的题目为"Determination of Long-Chain Branching Distributions of Polyethylenes"的论文。因此,通过测量含长链支链的聚乙烯的作为分子量函数的特性粘度并将此结果与相同量的线型聚乙烯的相应测量值进行对比,提供了支化聚乙烯中的长链支链估计值。测定分子量、分子量分布和长链支化
使用装有用于测量分子量的和用于测量粘度的Viscotek 150R粘度计凝胶渗透色谱(GPC)柱的Waters 150-C液相色谱仪。凝胶渗透色谱仪提供聚乙烯样品的分子量分布,粘度计和GPC红外检测器相结合测量浓度并测定粘度。对于尺寸排阻色谱法,先使用具有50公称孔尺寸的25cm长的初始柱(购自Polymer Labs),接着使用具有80公称孔尺寸的25cm长Shodex A-80 M/S (Showa)柱,然后使用具有80公称孔尺寸的25cm长Shodex A-80 M/S (Showa)柱。两个柱都是苯乙烯-二乙烯基苯类材料。将1,2,4-三氯苯用作溶剂和色谱洗脱液。所有测量都在140±0.5℃下进行。对SEC-粘度测量工艺法和用于将GPC和粘度测量数据转化为长链支化和校准分子量的方程的详细讨论在上述Mirabella和Wild的论文中给出。差示扫描量热计和熔化热
通过测量放在波形铝盘中的样品与对照物之间的差示热流(使用升高温度梯度,用IA-2910 DSC控制器和A21W数据站)得到DSC热谱图。测定聚乙烯中的Al、Zr和Si
将聚乙烯样品称量放入铂坩埚中,然后放入隔焰炉(580℃)中直至所有碳完全烧掉。冷却后将盐酸加入残余物中并慢慢加热使其溶解。将坩埚冷却,并加入氢氟酸以确保硅烷完全溶解。然后将样品定量移出并用15ml去离子水稀释,用Inductively-Coupled Plasma(Atom Scan 25,ThermoJarrell Ash)进行分析。由温度升高洗脱分级进行的乙烯共聚物组成分布分析
已建立了温度升高洗脱分级或TREF作为测量乙烯/α-烯烃共聚物的组成(或短链支链)分布的主要方法。将在溶剂如1,2,4-三氯苯中的稀释共聚物溶液在高温下以0.1-0.5%w/v加到填充柱上。然后将柱子以控制方式冷却至室温,使聚合物在填料上结晶以便随温度降低增加支化(或减少结晶度)。接着将柱子又以控制方式加热至140℃以上同时使恒定的溶剂流过柱子。随着温度升高,洗脱出来的聚合物级分降低了支化度(或增加了结晶度)。绘制聚合物浓度与洗脱温度的函数图即得所谓的TREF差示热分析图。
Refevence:Wild,L.等人,J.Polym.Sci.,Polym.Phys.Ed.,20,P.441(1982)由碳-13 NMR分析支化
通过在NMR管中将聚烯烃溶于邻二氯苯(ODCB)中制备浓度为8%w/v的溶液。将密封的重水毛细管插入NMR管中作为场频锁定。在115℃下使用30°PW和5秒重复时间的NOE增强条件将数据收集在Bruker AC300上。对于要求更短示踪更高度支化的样品,碳原子扫描个数都常为1,000至10,000。沿总脂族区域的面积测量每个峰的面积。将共聚单体贡献的碳原子的面积平均并折合为骨架面积得到摩尔分数。然后将此数值转化为支化频率。由IR测定聚乙烯中不饱和度的方法
不饱和基团的CH平面外谱带对双键上的取代基性质敏感。因此,可以区别三种不同类的不饱和现象、乙烯基(910cm-1)、亚乙烯基(890cm-1)和反式1,2-亚乙烯基(965cm-1)吸收;然而,不能测定顺式1,2-亚乙烯基,原因是在720cm-1处的CH2左右摆动振动所致。总不饱度由上述三种之和测定。
此方法使用每1,000个CH2基团的支化频率(BF)方程测定:
BF=[A/te]*[14.0/2.54×10-3]其中:
A为峰高(吸收单位)、t为厚度(密耳)、e为消光系数(l/cm*mol),消光系数的值取自Anderson和Seyfreid的著作(1)。溴化方法(2)用于消除来自丁基支链的干扰。这涉及使用溴化薄膜作为参考。参考文献:
1.J.A.Anderson and W.D. Seyfreid,Anal.Chem.20,998(1948)。
2.D.R.Rueda,F.J.Balta-Calleeja,and A.Hidalgo,Spectrochim. Acta 30A,1545(1974)。
催化剂制备BIEZr(Oipr)3催化剂
将1,2-双(茚基)乙烷(BIE)溶于含等摩尔量的四(异丙醇)锆的甲苯中。将等分量的此溶液加入到MMAO的庚烷溶液中使所得混合物的Al/Zr比为1000(mol)。BIEZr(O2CHEt2)3催化剂
将1,2-双(茚基)乙烷(BIE)在125-/2hr下与等摩尔量的四(二乙基酰胺)锆反应并将所得二乙胺抽出。将残余物在0-和大气压下溶于所加入的甲苯和二氧化碳中(3CO2
/Zr)。将等分量的此溶液加入到MMAO的庚烷溶液中,使所得混合物的Al/Zr比为1000(mol)。茚基三(氨基甲酸二乙酯)锆[η5-IndZr(O2CNEt2)3]催化剂
将四(二乙基酰胺)锆在120-/大气压下在氮气气氛下与150%过量的茚反应2小时,同时蒸发二乙基酰胺(脱出1mol Et2NH/Zr)。这样得到定量的η5-茚基三(二乙基酰胺)锆。用甲苯将其稀释至5wt%浓度的溶液并使其与二氧化碳接触。每摩尔锆化合物约吸收3mol二氧化碳。将等分量的此溶液与MMAO反应,使最终聚合物的AC/Zr比为1000(mol)。BIEZr(O2CC6H5)3催化剂
按上述方法使双(茚基)乙烷与四(二乙基酰胺)锆反应制备BIEZr(NEt2)3。将其溶于甲苯中形成稀释溶液并在-78-下慢慢加入3摩尔苯甲酸/molBIEZr(NEt2)3,后者同样作为稀溶液。将所得的三(苯甲酸盐)溶液与MMAO反应,形成Al/Zr1000(mol)的活性催化剂。使用的二烯烃
OCTDN -1,7-辛二烯
VNB -5-乙烯基-1-降
冰片烯
NBD -降冰片烯二烯烃三元聚合物产品的稳定性
用熔体指数试验仪测聚合产品的反应后稳定性。在1p或10p挤出之前按常规程序将聚合物在仪器中加热5分钟。为测试熔体稳定性,在1P挤出前将聚合物预热5和15分钟。
熔体指数(1P)
预热时间
5min 15min
6.61 6.64
4.27 4.01
3.42 3.55
2.60 2.70
0.99 1.17
除最后一次外,MI都在“噪声度”数值范围内。严重的胶凝交联本应基本上经长时预热而降低。提取
此方法与ASTM-D-2765-84相似,制备120目SS筛网的小袋并将小心称量的聚合物加入此袋中。测定空袋和满袋的精确重量。然后将其悬挂入1500ml二甲苯和5g BHT的溶液中并在四流(~135-)下提取4hr。将袋干燥(110-/在空气烘箱中过夜)并重新称量。对于含二烯烃的聚合物重量损失为99.9-100.1%。在搅拌淤浆反应器中聚合(编号A至N)
用下列步骤在1.81搅拌反应器中进行这些聚合。在N2流下在~100-下烘烤后,将反应器冷却(在N2流下)。加入11已烷、100ml己烯-1(经CaH2蒸馏的)、给定量的二烯烃和1.14ml TIBA(1.0mmol Al)并将反应器密封。将温度调至85-,加入给定量的氢气(0-1000ml STP)并用乙烯(约1.8mol)将反应器压力升至200psi。然后将催化剂溶液经压力注射器注入,引发聚合反应,反应时间一般为30min,尽管对于非常活泼的催化剂仅用10min。通过在反应条件下注射入1ml异丙醇使反应终止。冷却和放空后,加入0.2gIrganox-1035在丙酮中的溶液作为稳定剂。将此聚合物在空气中干燥并贮存于聚乙烯袋中。在机械搅拌的气相反应器中的聚合(编号O至T)
在每次反应前的晚上,将31b预备床加入反应器中,然后用氮气三次加压清洗至100psig。调节夹套温度使物料保持在约80-C下过夜,同时在100psig反应器压力下用3-41b/hr氮气流清洗。每天早上在开始反应之前,将反应器一次加压至300psig并加入50ml助催化剂溶液进一步钝化反应器。然后将反应器加压清洗4次以上使压力接近100psig。加入原料建立乙烯、己烯-1和氮气的初始气相浓度;气相浓度通常在整批进料过程中保持接近这些初始值。
将催化剂淤浆或溶液在第一个2.5hr小时内连续加入反应器中(0.3-0.5mmol Zr),用烷基铝助催化剂溶液作为载体,氮气作为分散剂。
按需要将单体和氢气连续加入以保持整批进料过程中的气相组成。使用少量放空气流以防止与催化剂一起加入的氮气的积累。反应器按间歇方式操作,当床的重量接近25-301b时终止该批次的反应。反应终止时,关闭进料并将反应器迅速放空至大气压。然后将反应器用干燥氮气加压清洗5次使压力接近100psi。接着将树脂卸出并暴露于空气中。将双喷嘴清洗岐管很深地插入树脂内以清洗除去烃并用水饱和的氮气在室温下使催化剂失活过夜。
表1NBD己烯-1-乙烯的三元聚合结果,使用BIE·Zr(Oipr)3/MMAO催化剂
聚合物编号 A B C D E F催化剂类型 BIEZr(Oipr)3→ → → → →加入的氢气(ml.STP) 0 150 450 600 800 800催化剂用量(mmole) 0.33 0.65 0.65 0.55 0.63 0.49二烯烃(g) 0 0.81 0.80 1.25 1.29 1.77聚合物产量(g) 74.2 59.4 53.8 41.9 51.8 44.3活性(g PE/hr-mmole 225,000 183,000 165,000 152,700 82,200 90,400Zr-100 psi C2=)聚合物性质BBF(丁基个数/1000 CH2个数) 17.6 16.8 16.9 18.0 NA NA己烯-1(wt%) 9.9 9.5 9.5 10.1 -- --SEC(形状) 单峰式 NA → → → 单峰式Mn 31.900 -- 4680PDI 1.9 -- 38.3回复率(%) -- 92.6MI 6.63 0.8(MF) 0.43 0.39 1.79 0.57MFR 19.0 95 140 77.2 176.5TREF(形状) NA 窄 双峰式 双峰式 斜峰宽峰 宽峰LD(≤60_,%) -- 15.3 16.3 24.7 18.3 31.6HD(≥90_,%) -- 1.1 16.6 8.7 1.4 1.1提取(%溶液) -- 100.1 100.2 99.4 99.97 99.67红外(wt.%)NA反式 NA NA .004 .012 NA .004乙烯基 -- -- .72 1.50 -- .050=CH2 -- -- .029 .031 -- .020DSC(第二次加热)形状 尖峰 (比较宽) NA (比较尖) 宽峰 宽峰m.pt.(_) 110.8 109.5 -- 108.2 107.6 105.9晶体(%) 38.3 19.6 -- 36.4 43.9 37.9LCB(每1000C1s)) 0 1.4 2.0 4.7 4.6 11.8特性粘度 -- 1.15 0.86 0.77 0.72 0.69 |
表IIOCTDN-己烯-1-乙烯的三元聚合结果,使用BIEZr(O2CC6H5)3/MMAO催化剂
聚合物编号 G H I J催化剂(19170-) 36-1 → 36-2 36-3催化剂类型 BIEZr(O2CC6H5)3 → → →催化剂量(mmol) 0.72 0.81 0.67 0.69二烯烃(g) 0 0.8 1.5 3.0聚合物产量(g) 82.2 91.9 81.6 69.8活性(corr.for[Zr](g PE/hr-mmole 113,800 112,000 116,000 101,000Zr-100 psi C2)聚合物性质BBF(丁基个数/1000个CH2) 16.7 19.2 17.7 15.2己烯-1(wt%) 9.4 10.7 9.6 8.6SEC(形状) 单 → → →Mn 28,400 28,500 29,400 29,800PDI 2.1 2.0 2.0 2.1回复率(%)MI 6.61 4,27 3.42 2.60MFR 19.9 25.4 28.0 31.3TREF(形状) NA → → →LD(≤60_,%)HD(≥90_,%)JWN提取(%溶液.)(19457-113) 100 100 100 100红外(wt.%)反 .01 NA → →乙烯基 -- .077=CH2 -- .015DSC(第二次加热) 单 单 单 →形状 (比较尖) (稍宽) (比较尖)m.pt.(_) 111.6 109.8 110.4 112.0晶体(%) 38.8 41.9 40.0 42.0LCB(支链/1000个C原子) 0 0.8 0.7 1.0特性粘度 0.88 1.07 1.11 1.11 |
表III:VNB-己烯-1和乙烯的三元聚合结果,使用BIEZr(O3CNEt2)3/MMAO催化剂
αBHT稳定化产品:由延伸粘度测定法检测LCB正值的样品
聚合物编号 Ka La Mab Na催化剂类型 BIEZr(O2CNEt2)3 → → →120ml H2,No TIBA聚化剂量(mmole) 0.20 0.52 1.92 1.88二烯烃(g) 0 6.5 13.0 18.4聚合物产量(g) 89.5 52.4 87.5 44.0活性(g PE/hr-mmole 447,000 104,800 43,700 23,400Zr-100 psi C2=)聚合物性质BBF(丁基个数/1000CH2个数) 19.0 13.4 13.5 11.0己烯-1(wt%) 10.6 7.4 7.3 6.0SEC(形状) 单 双峰式 双峰式 双峰式Mn 26,100 25,400 20,000 19,000PDI 1.9 6.90 11.2 9.33回复率(%)MI 9.7 2.75 0.32 0.47MFR 21.2 33.6 59.7 59.5TREF(形状) 单no NA (非常宽) NALD(≤60_,%) 15.8 40.3HD(≥90_,%) 2.1 6.2JWN提取(%so1.)--红外(wt.%)反式 .003 .026 .029 .037乙烯基 .068 1.36 2.05 2.19=CH2 .015 .039 .065 .048DSC(第二次加热)形状 长尾峰 单峰 (非常宽) →V.Broad 双峰式m.pt.(_) 111.0 100.7 89.9/113.1 87.7/116.3晶体(%) 52 23.5 13.3/5.6 11.9/10.6LCB(每1000C1s)0 2.2 3.0 3.6特性粘度 -- 1.05 1.07 1.02 |
表IV气相反应器产品的一些基本物理性质
aV极低催化剂活性,原因未知b95±2%回复率为无凝胶分子的标准oBBF-13.4;7.6wt.%引入的己烯dBBF-12.7;7.2wt.%引入的己烯
编号 O Po Qd R Sa T在PR-1原料中的己烯 0 0.8 1.6 3.2 6.4 12.8-1中的NBD(wt.%)MI 2.96 4.04 2.71 1.29 0.31 0.47MFR 30.0 36.8 30.4 47.5 67.7 50.0挤出物外观 半光滑 光滑 粗糙 非常粗糙光滑TREF LD(%≤60_) 14.7 12.2 11.8 14.3 23.8 21.8HD(%≥90_) 10.7 14.2 11.3 11.6 12.3 14.2Lw/Ln 4.26 3.79 3.04 3.31 4.57 4.52外观 双峰式 双峰式宽 → → → 非常宽 →SEC Mw/Mn 2.88 3.10 3.02 3.42 3.05 2.73MN 24,200 22,600 23,800 20,000 20,500 21,000外观 对称 → → → → →回复率(%)b 96.2 97.4 97.4 94.9 93.6 87.2特性粘度 1.20 1.22 1.25 1.18 1.02 0.87LCB/1000CH2 1s 0.6 0.4 0.3 0.4 1.5 3.8红外(wt.%C=C)反 .024 .024 .029 .026 .032 .030乙烯基 .014 .012 .014 .012 .024 .031=CH2 .038 .033 .049 .039 .047 .047聚合物中的Zr 2.6 3.8 3.8 3.0 2.9 3.0 |
表V气相反应器聚合数数据总汇
+三磅来自标记的编号
编号 O P Q R S T己烯-1原料中的NBD(wt.%) 0 0.8 1.6 3.2 6.4 12.8反应条件压力(psig) 350 → → → → →温度(_C) 80 → → → → →比例(C6/C2) .022-.029 .020-.03 .020-.025 .025-.03 .026-.029 .023-.030乙烯压力(psig) 200 → → → → →最大产率(lb/hr) 3.6 4.5 3.4 3.0 1.5 3.3最低夹套温度(_C) 68 67 70 68 79 70最大Dew Pt(_C) 44 44 40 44 45 45(BWR Equ.)催化剂催化剂类型 P-24-U → → → → →(19170-95-) H E F G G I催化剂进料(mmole) 350 449 481 404 302 431催化剂进料时间(hr) 2.0 2.5 2.5 2.0 1.5 3.0催化剂载体和助催化剂 15% MMAO/iC5 → → → →助催化剂进料速度(ml/hr) 150 → → → → →Al/Zr比例(mole) 1000 → → → → →加料方式初始床+ S 5 MILLDPE P Q R O初始床的钝化(ml TIBA) 50 → → → → →产品重量(初始床的wt) 27.0 23.7 24.7 27.0 20.5 26.2(wt.of pre-bed)(lb) |
Claims (10)
1.一种生产具有长链支化的聚乙烯均聚物、共聚物或三元聚合物的方法,包括在聚合条件下在用量足以提供链缠结或长链支化的烃互连化合物存在下,在含金属茂聚合催化剂的反应区中提供乙烯和非必要的具有3至18个碳原子的α-烯烃。
2.权利要求1的方法,其中烃互连化合物自二烯烃、三烯烃、环烷化合物及其混合物,其中催化剂包括:
(i)选自如下通式的化合物及其混合物的催化剂前体:
其中:
M为Zr或Hf;
L为取代或未取代的1-键合配位体;
Q可以是相同或不同的,并独立地选自-O-、-NR-、-CR2-和-S-;
Y为C或S;
Z选自-OR、-NR2、-CR3、-SR、-SiR3、-PR2和-H,条件是当Q为-NR-时,Z选自-OR、-NR2、-SR、SiR3、-PR2和-H;
n为1或2;
当n为2时A为一价阴离子基团,或当n为1时A为二价阴离子基团。
R可为相同或不同的,并独立地为含有碳、硅、氮、氧和/或磷的基团,且一个或多个R基团可非必要性地与L取代基连接;
T为选自含1至10个碳原子的亚烷基、亚芳基、锗、有机硅和烷基膦的基团;m为1至7;和
(ii)助催化剂
3.权利要求2的方法,其中烃互连化合物选自1,6-庚二烯、1,7-辛二烯、1,8-壬二烯、1,9-癸二烯、1,11-十二碳二烯,5-乙烯基-2-降冰片烯、5-(2-丙烯基)-2-降冰片烯、降冰片二烯、二环戊二烯、1,4,4a,5,8,8a-六氢-1,4,5,8-二甲桥萘及其混合物。
4.权利要求2的方法,其中Q为氧,y为碳,Z选自-OR、-CR3和-NR2,R为具有1至20个碳原子的烃基,L为取代的环戊二烯配位体,T为亚乙基基团或有机硅基团;m为2或3;和其中助催化剂选自(a)含有通式-(Al(R′)O)-的重复单元的支化或环状低聚聚(烃基氧化铝),其中R′为含有1至约12个碳原子的烷基或芳基如取代或未取代苯基或萘基和(b)硼酸盐。
5.权利要求4的方法,其中将催化剂前体用胺预活化。
6.权利要求1的方法,其中烃互连化合物的用量按总单体进料量计为约0.001至约5%(重量)。
7.权利要求1的方法,其中方法在气相中进行,并且催化剂喷雾干燥或以液态形式。
8.权利要求1的方法,其中方法以冷凝方式进行。
9.一种根据权利要求1的方法获得的聚乙烯组合物。
10.一种包括权利要求9的组合物的薄膜或注塑制品。
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1996
- 1996-12-13 HU HU9603449A patent/HUP9603449A3/hu unknown
- 1996-12-13 CA CA002192862A patent/CA2192862A1/en not_active Abandoned
- 1996-12-13 EP EP96309147A patent/EP0784062A3/en not_active Withdrawn
- 1996-12-13 TR TR96/01005A patent/TR199601005A2/xx unknown
- 1996-12-13 AR ARP960105663A patent/AR005066A1/es unknown
- 1996-12-14 CN CN96121362A patent/CN1165151A/zh active Pending
- 1996-12-15 BR BR9606020A patent/BR9606020A/pt not_active Application Discontinuation
- 1996-12-16 CZ CZ963699A patent/CZ369996A3/cs unknown
- 1996-12-16 JP JP8352526A patent/JPH09227626A/ja active Pending
- 1996-12-16 SK SK1612-96A patent/SK161296A3/sk unknown
- 1996-12-16 AU AU75389/96A patent/AU7538996A/en not_active Abandoned
- 1996-12-16 PL PL96317509A patent/PL317509A1/xx unknown
Cited By (4)
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CN102762267A (zh) * | 2009-12-21 | 2012-10-31 | 陶氏环球技术有限责任公司 | 使用石墨碳固定相的聚烯烃聚合物的色谱分析 |
CN102762267B (zh) * | 2009-12-21 | 2015-06-10 | 陶氏环球技术有限责任公司 | 使用石墨碳固定相的聚烯烃聚合物的色谱分析 |
CN106478854A (zh) * | 2016-10-11 | 2017-03-08 | 浙江大学 | 聚(1,9‑癸二烯)及其制备方法 |
CN106478854B (zh) * | 2016-10-11 | 2019-04-02 | 浙江大学 | 聚(1,9-癸二烯)及其制备方法 |
Also Published As
Publication number | Publication date |
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SK161296A3 (en) | 1998-04-08 |
JPH09227626A (ja) | 1997-09-02 |
PL317509A1 (en) | 1997-06-23 |
HUP9603449A2 (hu) | 1998-03-02 |
AR005066A1 (es) | 1999-04-07 |
EP0784062A2 (en) | 1997-07-16 |
CZ369996A3 (en) | 1997-07-16 |
BR9606020A (pt) | 1998-09-01 |
EP0784062A3 (en) | 1998-04-22 |
HUP9603449A3 (en) | 2000-03-28 |
AU7538996A (en) | 1997-06-19 |
CA2192862A1 (en) | 1997-06-16 |
HU9603449D0 (en) | 1997-02-28 |
TR199601005A2 (tr) | 1997-07-21 |
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