[미국특허]
Polymerization catalysts for producing polymers with high comonomer incorporation
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
B01J-031/00
C08F-004/44
출원번호
UP-0904728
(2007-09-28)
등록번호
US-7799721
(2010-10-11)
발명자
/ 주소
Yang, Qing
Crain, Tony R.
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Yoder, Fletcher
인용정보
피인용 횟수 :
7인용 특허 :
91
초록▼
The present techniques relate to catalyst compositions, methods, and polymers encompassing a Group 4 metallocene compound comprising bridged η5-cyclopentadienyl-type ligands, typically in combination with a cocatalyst, and a activator. The bridged η5-cyclopentadienyl-type ligands are con
The present techniques relate to catalyst compositions, methods, and polymers encompassing a Group 4 metallocene compound comprising bridged η5-cyclopentadienyl-type ligands, typically in combination with a cocatalyst, and a activator. The bridged η5-cyclopentadienyl-type ligands are connected by a cyclic substituent. The catalysts of the present techniques may be more effective at the incorporation of comonomers into the backbone of a polyolefin polymer.
대표청구항▼
What is claimed is: 1. A catalyst composition comprising the contact product of an ansa-metallocene and an activator, wherein: the ansa-metallocene comprises a compound having the formula: (X1)(X2)(X3)(X4)M1, wherein: M1 comprises titanium, zirconium, or hafnium; X1 and X2 independently comprise
What is claimed is: 1. A catalyst composition comprising the contact product of an ansa-metallocene and an activator, wherein: the ansa-metallocene comprises a compound having the formula: (X1)(X2)(X3)(X4)M1, wherein: M1 comprises titanium, zirconium, or hafnium; X1 and X2 independently comprise a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; one substituent on X1 and X2 comprises a bridging group having the formula E(Cyc), wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both X1 and X2, and wherein Cyc is a substituted or an unsubstituted carbon chain of from 4 to 6 carbon atoms in length with each end connected to E to form a ring structure; one substituent on X1 or X2 comprises a substituted or an unsubstituted alkenyl group; X3 and X4 independently comprise: F, Cl, Br, or I; a hydrocarbyl group, H, or BH4; a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group; OBRA2 or SO3RA, wherein RA is an alkyl group or an aryl group; and the activator comprises: an activator-support comprising a solid oxide treated with an electron-withdrawing anion, a layered mineral, an ion-exchangeable activator-support, or any combination thereof; an organoaluminoxane compound; an organoboron compound or an organoborate compound; or any combination thereof. 2. The catalyst composition of claim 1, wherein any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, a boron group, a halide, or hydrogen. 3. The catalyst composition of claim 1, wherein if neither X3 nor X4 is a hydrocarbyl group, H, or BH4, and the activator does not comprise an organoaluminoxane compound, then the catalyst composition comprises the contact product of the ansa-metallocene, the activator, and an organoaluminum compound having the formula: Al(X5)n(X6)3-n, wherein: X5 is a hydrocarbyl; X6 is a halide, a hydride, an alkoxide or an aryloxide; and n is a number from 1 to 3, inclusive. 4. The catalyst composition of claim 1, wherein: the ansa-metallocene comprises a compound having the formula: M1 is zirconium or hafnium; X3 and X4 are independently F, Cl, Br, or I; E is C or Si; n is an integer from 1 to 3, inclusive; R3A and R3B are independently a hydrocarbyl group, a trihydrocarbylsilyl group, or hydrogen; bond ‘a’ is a single or a double bond; m is an integer from 0 to 10, inclusive; and R4A and R4B are independently a hydrocarbyl group, or hydrogen; and the activator is an activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein: the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, or any combination thereof. 5. The catalyst composition of claim 1, wherein the ansa-metallocene comprises a compound having the formula: M1 is zirconium or hafnium; X3 and X4 are independently F, Cl, Br, or I; E is C or Si; n is an integer from 1 to 3, inclusive; bond ‘a’ is a single or a double bond; R3A and R3B are independently H, methyl, ethyl, propyl, allyl, benzyl, butyl, pentyl, hexyl, or trimethylsilyl; m is an integer from 1 to 6, inclusive; and R4A and R4B are independently a hydrocarbyl group or hydrogen. 6. The catalyst composition of claim 1, wherein the ansa-metallocene comprises a compound having the formula: M1 is zirconium or hafnium; X3 and X4 are independently Cl, Br, or I; E is C or Si; R3A and R3B are independently H or methyl; n is 1 or 2; bond ‘a’ is a single bond or a double bond; m is 1 or 2; and R4A and R4B are independently H or t-butyl. 7. The catalyst composition of claim 1, wherein the ansa-metallocene is or any combination thereof. 8. The catalyst composition of claim 1, wherein the organoaluminoxane compound comprises: a cyclic aluminoxane having the formula: wherein R is a linear or branched alkyl and n is an integer from 3 to about 10; a linear aluminoxane having the formula: wherein R is a linear or branched alkyl and n is an integer from 1 to about 50; or a cage aluminoxane having the formula Rt5m+αRbm−αAl4mO3m, wherein: m is 3 or 4; α is equal to nAl(3)−nO(2)+nO(4), wherein: nAl(3) is the number of three coordinate aluminum atoms; nO(2) is the number of two coordinate oxygen atoms; and nO(4) is the number of 4 coordinate oxygen atoms; Rt represents a linear or branched terminal alkyl group; and Rb represents a linear or branched bridging alkyl group; or any combination thereof. 9. The catalyst composition of claim 3, wherein: the ansa-metallocene comprises combination thereof; the activator comprises a sulfated solid oxide; and the organoaluminum compound comprises triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof. 10. The catalyst composition of claim 3, wherein: the ansa-metallocene comprises combination thereof; the activator comprises sulfated alumina; and the organoaluminum compound comprises triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof. 11. The catalyst composition according to claim 1, wherein: the ansa-metallocene comprises a compound having the formula: M1 is zirconium or hafnium; X′ and X″ are independently H, BH4, methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH2CMe2Ph; CH2SiMe2Ph; CH2CMe2CH2Ph; or CH2SiMe2CH2Ph; E is C or Si; n is an integer from 1 to 3, inclusive; R3A and R3B are independently a hydrocarbyl group, a trihydrocarbylsilyl group, or hydrogen; bond ‘a’ is a single or a double bond; m is an integer from 0 to 10, inclusive; and R4A and R4B are independently a hydrocarbyl group or hydrogen; and the activator comprises an activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein: the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, or any combination thereof. 12. An ansa-metallocene having a general formula of
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