[미국특허]
Polymerization catalysts for producing polymers with low melt elasticity
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
B01J-031/38
B01J-031/00
출원번호
US-0904735
(2007-09-28)
등록번호
US-8119553
(2012-02-21)
발명자
/ 주소
Yang, Qing
McDaniel, Max P.
Martin, Joel L.
Yu, Youlu
Rohlfing, David C.
Jensen, Michael D.
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Fletcher Yoder
인용정보
피인용 횟수 :
11인용 특허 :
98
초록▼
The present techniques relate to catalyst compositions, methods, and polymers encompassing a Group 4 metallocene compound comprising bridging η5-cyclopentadienyl-type ligands, typically in combination with a cocatalyst, and a activator. The compositions and methods presented herein include ethylene
The present techniques relate to catalyst compositions, methods, and polymers encompassing a Group 4 metallocene compound comprising bridging η5-cyclopentadienyl-type ligands, typically in combination with a cocatalyst, and a activator. The compositions and methods presented herein include ethylene polymers with low melt elasticity.
대표청구항▼
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: M1 is zirconium or hafnium;X′ and X″ are independently F, Cl, Br, or I;E is C or Si;R1 and R2 are independently an alkyl group, an
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: M1 is zirconium or hafnium;X′ and X″ are independently F, Cl, Br, or I;E is C or Si;R1 and R2 are independently an alkyl group, an aryl group, or hydrogen;R3A and R3B are independently a hydrocarbyl group, a trihydrocarbylsilyl group, or hydrogen;n is an integer from 0 to 10, inclusive; R4A and R4B are independently a hydrocarbyl group; andthe activator comprises: an activator-support comprising a solid oxide treated with an electron-withdrawing anion. 2. The catalyst composition of claim 1, wherein the activator comprises 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; andn is a number from 1 to 3, inclusive. 3. The catalyst composition of claim 1, wherein the solid oxide of the activator-support is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any combination thereof and the electron-withdrawing anion used to treat the solid oxide 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. 4. The catalyst composition of claim 1, wherein R3A and R3B are independently H, methyl, allyl, ethyl, propyl, benzyl, butyl, pentyl, hexyl, or trimethylsilyl. 5. The catalyst composition of claim 1, wherein: R1 and R2 are independently methyl or phenyl;R3A and R3B are independently H or methyl;n is 1 or 2; andR4A and R4B are t-butyl. 6. The catalyst composition of claim 1, wherein the activator comprises an organoboron compound, an organoborate compound, an organoaluminoxane compound, or any combination thereof, 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 R5m+αtRm−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; andnO(4) is the number of 4 coordinate oxygen atoms;Rt represents a linear or branched terminal alkyl group; andRb represents a linear or branched bridging alkyl group; orany combination thereof. 7. The catalyst composition of claim 2, wherein: the ansa-metallocene comprises or any combination thereof; the activator comprises a sulfated solid oxide; andthe organoaluminum compound comprises triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof. 8. The catalyst composition of claim 2, wherein: the ansa-metallocene has the formula: or any combination thereof; the activator comprises sulfated alumina; andthe organoaluminum compound comprises triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof. 9. A catalyst composition comprising the contact product of an ansa-metallocene and an activator, wherein: the ansa-metallocene comprises a compound having the formula: or any combination thereof and the activator comprises: an activator-support comprising a solid oxide treated with an electron-withdrawing anion. 10. The catalyst composition of claim 9, wherein the activator-support is wherein the solid oxide of the activator-support is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof. 11. The catalyst composition of claim 9, wherein 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. The catalyst composition of claim 9, wherein the activator is substantially free of an organoaluminum compound. 13. The catalyst composition of claim 9, wherein the activator comprises an organoaluminum compound. 14. The catalyst composition of claim 13, wherein the organoaluminum compound comprises trialkylaluminum compounds, dialkylaluminium halide compounds, dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds, or any combination thereof. 15. A catalyst composition comprising the contact product of an ansa-metallocene and an activator, 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;R1 and R2 are independently an alkyl group, an aryl group, or hydrogen;R3A and R3B are independently a hydrocarbyl group, a trihydrocarbylsilyl group, or hydrogen;n is an integer from 0 to 10, inclusive; R4A and R4B are independently a hydrocarbyl group; andthe activator comprises an activator-support comprising a solid oxide treated with an electron-withdrawing anion. 16. The catalyst composition of claim 15, wherein the solid oxide of the activator-support 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 used to treat the solid oxide 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.
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상세보기
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