[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
US-0096077
(2011-04-28)
등록번호
US-8222174
(2012-07-17)
발명자
/ 주소
Yang, Qing
Crain, Tony R.
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Fletcher Yoder P.C.
인용정보
피인용 횟수 :
6인용 특허 :
100
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 an activator. The bridged η5-cyclopentadienyl-type ligands are connected by a
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 an activator. The bridged η5-cyclopentadienyl-type ligands are connected by a cyclic substituent.
대표청구항▼
1. An ansa-metallocene, comprising: 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;a first substituent on X1 and X2 comprises a
1. An ansa-metallocene, comprising: 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;a first 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 of the substituted or unsubstituted carbon chain connected to E to form a ring structure;a second substituent on X1 or X2 comprises a substituted or an unsubstituted alkenyl group; andX3 and X4 independently comprise a halide, a hydrocarbyl group, H, BH4, a hydrocarbyloxide group, a hydrocarbylamino group, a trihydrocarbylsilyl group, an amido group, a phosphido group, OBRA2, or SO3RA, wherein RA is an alkyl group or an aryl group. 2. The ansa-metallocene of claim 1, wherein an additional substituent on X1 or X2 comprises 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, or a boron group, or any combination thereof, and the additional substituent comprises between 1 and 20 carbons. 3. The ansa-metallocene of claim 1, wherein an additional substituent on X1 or X2 comprises F, Cl, Br, I, or H. 4. The ansa-metallocene of claim 1, wherein the second substituent comprises up to 20 carbons. 5. The ansa-metallocene of claim 1, wherein the second substituent on X1 or X2 comprises up to 12 carbons. 6. The ansa-metallocene of claim 1, wherein X1 comprises substituted cyclopentadienyl and X2 comprises substituted fluorenyl. 7. The ansa-metallocene of claim 1, wherein the second substituent on X1 or X2 is a substituted alkenyl group substituted with 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, or a boron group, or any combination thereof. 8. The ansa-metallocene of claim 1, wherein X3 and X4 independently comprise a hydrocarbyloxide group comprising up to 20 carbons or a hydrocarbylamino group comprising up to 20 carbons, OBRA2, or SO3RA, wherein RA is an alkyl group or an aryl group having up to 12 carbons. 9. The ansa-metallocene of claim 1, wherein Cyc is a substituted carbon chain substituted with 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, or a boron group. 10. The ansa-metallocene of claim 1, wherein E(Cyc) has the formula C(CH2CH2CH2CH2), C(CH2CH2CH2CH2CH2), Si(CH2CH2CH2CH2), Si(CH2CH2CH2CH2CH2), Ge(CH2CH2CH2CH2), Ge(CH2CH2CH2CH2CH2), Sn(CH2CH2CH2CH2), or Sn(CH2CH2CH2CH2CH2). 11. An ansa-metallocene, comprising: a compound having the formula: wherein:M1 is zirconium, hafnium, or titanium;X3 and X4 are independently a halide, a hydrocarbyl, a trihydrocarbyl silyl, or a boron-containing group;E is C, Si, Ge, or Sn;n is an integer from 1 to 3, inclusive;R3A and R3B are independently a hydrocarbyl group, a trihydrocarbylsilyl group, or hydrogen;m is an integer from 0 to 10, inclusive; andR4A and R4B are independently a hydrocarbyl group or hydrogen. 12. The ansa-metallocene of claim 11, wherein R3A and R3B independently comprise a hydrocarbyl group comprising up to 20 carbon atoms or a trihydrocarbylsilyl group comprising up to 20 carbon atoms. 13. The ansa-metallocene of claim 11, wherein R4A and R4B are independently a hydrocarbyl group group having up to 12 carbon atoms, or hydrogen. 14. The ansa-metallocene of claim 11, wherein: M1 is zirconium or hafnium;X3 and X4 are independently F, Cl, Br, or I;E is C or Si;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; andR4A and R4B are independently a hydrocarbyl group having up to 6 carbon atoms, or hydrogen. 15. The ansa-metallocene of claim 11, wherein: M1 is zirconium or hafnium;E is C or Si;X3 and X4 are independently H, BH4, methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH2CMe2Ph, CH2SiMe2Ph, CH2CMe2CH2Ph, or CH2SiMe2CH2Ph;R3A and R3B are independently a hydrocarbyl group having up to 20 carbon atoms or a trihydrocarbylsilyl group having up to 20 carbon atoms, or hydrogen; andR4A and R4B are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen. 16. The ansa-metallocene of claim 11, wherein: M1 is zirconium or hafnium;E is C or Si;X3 and X4 are independently F, Cl, Br, or I;n is 1 or 2;R3A and R3B are independently H or methyl;m is 1 or 2; andR4A and R4B are independently H or t-butyl. 17. A ligand for a metallocene polymerization catalyst, comprising: a compound having the formula: (X1)(X2), wherein:X1 and X2 independently comprise a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;X1 and X2 are connected via a cyclic bridging moiety 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 of the carbon chain connected to E to form a ring structure; andone substituent on X1 or X2 comprises a substituted or an unsubstituted alkenyl group. 18. The ligand of claim 17, wherein the compound has the formula: wherein: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;m is an integer from 0 to 10, inclusive; andR4A and R4B are independently a hydrocarbyl group or hydrogen. 19. The ligand of claim 17, wherein the compound has the formula: wherein: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; andR4A and R4B are independently a hydrocarbyl group having up to 6 carbon atoms, or hydrogen. 20. The ligand of claim 17, wherein the compound has the formula:
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