[미국특허]
Catalyst system comprising a mixture of catalyst components for producing a polyolefin blend
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/6592
C08F-004/00
C08F-004/6392
출원번호
US-0491360
(2002-09-26)
등록번호
US-7396888
(2008-07-08)
우선권정보
EP-01203656(2001-09-27)
국제출원번호
PCT/EP02/010942
(2002-09-26)
§371/§102 date
20041223
(20041223)
국제공개번호
WO03/029303
(2003-04-10)
발명자
/ 주소
Razavi,Abbas
출원인 / 주소
TOTAL Petrochemicals Research Feluy
대리인 / 주소
Kilpatrick Lee,Diane L.
인용정보
피인용 횟수 :
11인용 특허 :
10
초록▼
Provided is a catalyst system for producing a polyolefin blend, which catalyst system comprises a mixture including the following catalyst components: i) a catalyst component A capable of producing an isotactic olefin polymer, and/or a catalyst component A' capable of producing a polymer comprising
Provided is a catalyst system for producing a polyolefin blend, which catalyst system comprises a mixture including the following catalyst components: i) a catalyst component A capable of producing an isotactic olefin polymer, and/or a catalyst component A' capable of producing a polymer comprising an isotactic polyolefin block; and ii) a catalyst component B capable of producing a syndiotactic polyolefin, and/or a catalyst component B' capable of producing a polymer comprising a syndiotactic polyolefin block; wherein each of the components in the catalyst system is distinct from the other components in the catalyst system.
대표청구항▼
The invention claimed is: 1. A catalyst system for producing a polyolefin blend, which catalyst system comprises a mixture of a first catalyst component supported on a first support and a second catalyst component supported on a second support, wherein the first catalyst component is at least one o
The invention claimed is: 1. A catalyst system for producing a polyolefin blend, which catalyst system comprises a mixture of a first catalyst component supported on a first support and a second catalyst component supported on a second support, wherein the first catalyst component is at least one of a catalyst component A capable of producing an isotactic olefin polymer, and a catalyst component A' capable of producing a polymer comprising an isotactic polyolefin block; and the second catalyst component is at least one of a catalyst component B capable of producing an syndiotactie polyolefin, and a catalyst component B' capable of producing a polymer comprising an syndiotactic polyolefin block; wherein each of the components in the catalyst system is distinct from the other components in the catalyst system, and wherein the catalyst component A comprises at least one metallocene having the formula: description="In-line Formulae" end="lead"R"(CpR1R2)(Cp'R'n)MQ2 (1)description="In-line Formulae" end="tail" wherein: (CpR1R2) is a substituted cyclopentadienyl ring; (Cp'R'n) is a substituted or unsubstituted fluorenyl ring; R" is a structural bridge imparting stereorigidity to the component; R1 is a substituent on the cyclopentadienyl ring which is distal to the bridge, which distal substituent comprises a bulky group of the formula XR*3 in which X is an atom from group IVA and each R* is the same or different and is chosen from a hydrogen or a hydrocarbyl group having from 1-20 carbon atoms, R2 is a substituent on the cyclopentadienyl ring which is proximal to the bridge and positioned non-vicinal to the distal substituent and is a hydrogen or is of the formula YR#3 in which Y is an atom from group IVA, and each R# is the same or different and is chosen from a hydrogen or a hydrocarbyl group having from 1-7 carbon atoms, each R' is the same or different and is a hydrocarbyl group having from 1-20 carbon atoms, and n is an integer of from 0-8; M is a metal atom from group IVB or is vanadium; and each Q is a hydrocarbon having from 1-20 carbon atoms or is a halogen; or the formula: description="In-line Formulae" end="lead"(Ind)2R'MQ2 (2)description="In-line Formulae" end="tail" or the formula: description="In-line Formulae" end="lead"(IndH4)2R"MQ2 (3)description="In-line Formulae" end="tail" wherein: each Ind is the same or different and is a substituted or unsubstituted indenyl group, wherein each IndH4 is the same or different and is a substituted or unsubstituted tetrahydroindenyl group, R' is a structural bridge imparting stereorigidity to the component, R" is a structural bridge imparting stereorigidity to the component; M is a metal atom from group IVB or is vanadium; and each Q is a hydrocarbon having from 1-20 carbon atoms or is a halogen, wherein the catalyst component B has the formula: description="In-line Formulae" end="lead"R"(CpRm)(Cp'R'r)MQ2 (4)description="In-line Formulae" end="tail" wherein: (CpRm) is a substituted or unsubstituted cyclopentadienyl ring; (Cp'R'r) is a substituted or unsubstituted fluorenyl ring; R" is a structural bridge imparting stereorigidity to the component, each R is the same or different and is a hydrocarbyl group having from 1-20 carbon atoms; each R' is the same or different and is a hydrocarbyl group having from 1-20 carbon atoms; m is an integer of from 0-4; r is an integer from 0-8; M is a metal atom from group IVB or is vanadium; and each Q is a hydrocarbon having from 1-20 carbon atoms or is a halogen, wherein the catalyst component A' has the formula: description="In-line Formulae" end="lead"R"(CpRx)(Cp'R'y)MQ2 (5)description="In-line Formulae" end="tail" wherein: (CpRx) is a substituted cyclopentadienyl ring; (Cp'R'y) is a substituted or unsubstituted fluorenyl ring; R" is a structural bridge imparting stereorigidity to the component; each R is the same or different and is a hydrocarbyl group having from 1-20 carbon atoms, each R' is the same or different and is a hydrocarbyl group having from 1-20 carbon atoms and x and y are independently an integer of from 1-4 and 0-8 respectively; M is a metal atom from group IVB or is vanadium; and each Q is a hydrocarbon having from 1-20 carbon atoms or is a halogen; wherein the CpRx group lack bilateral symmetry, and wherein the catalyst component B' has the formula: description="In-line Formulae" end="lead"R"(CpRq)XMQ2 (6)description="In-line Formulae" end="tail" wherein: CpRq is a substituted cyclopentadienyl ring or a substituted or unsubstituted fluorenyl ring; R" is a structural bridge between Cp and X imparting stereorigidity to the component; each R is the same or different and is selected from a hydrocarbyl group having from 1-20 carbon atoms, a halogen, an alkoxy group, and alkoxyalkyl group, an alkoxyalkyl group, an alkkylamino group or an alkylsilylo group when Cp is a cyclopentadienyl ring, q is an integer from 0-4; and when Cp is a fluorenyl ring q is an integer from 0-8; X is a heteroatom from group VA or group VIA; M is a metal atom from group IIIB, IVB, VB or VIB in any of its theoretical oxidation states; and each Q is a hydrocarbon having from 1-20 carbon atoms or is a halogen; wherein the bilateral symmetry of the CpRq group is maintained. 2. A catalyst system according to claim 1, wherein M is Ti, Zr, or Hf. 3. A catalyst system according to claim 2, wherein Q is Cl. 4. A catalyst system according to claim 1, wherein R" is substituted or unsubstituted and comprises an alkylene radical having from 1-20 carbon atoms, a dialkyl germanium group, a dialkyl silicon group, a dialkyl siloxane group, an alkyl phosphine radical or an amine radical. 5. A catalyst system according to claim 4, wherein R" comprises an isopropylidene, (Me2C), Ph2C, ethylenyl or Me2Si group. 6. A catalyst system according to claim 1, further comprising an aluminum-or boron-containing activating agent capable of activating at least one of said first catalyst component and said second catalyst component. 7. A catalyst system according to claim 1, wherein catalyst component A is capable of producing isotactie polypropylene and catalyst component B is capable of producing syndiotactie polypropylene. 8. A catalyst system according to claim 1 wherein the first catalyst component comprises a catalyst component A as defined by formula (1) wherein R1 is a substituent on the cyclopentadienyl ring Cp, at a position which is distal to the bridge R" and R2 is a substituent on the cyclopentadienyl ring Cp, at a position which is proximal to the bridge R" and is positioned non-vicinal to the distal substituent R1. 9. A catalyst system according to claim 1, wherein the first catalyst component is a metallocene according to formula (2) or (3), in which R" is a C1-C4 alkylene group. 10. A catalyst system according to claim 1, wherein the second catalyst component is a catalyst component B according to formula (4), in which the group CpRm has bilateral symmetry. 11. A catalyst system according to claim 10 in which the value of m is 0 to provide that the group CpRm is unsubstituted. 12. A catalyst system according to claim 1, wherein the first catalyst component comprises a catalyst component A' as characterized by formula (5) in which the group CpRx lacks bilateral symmetry. 13. A catalyst system according to claim 12 wherein the group CpRx is substituted at the 3 position. 14. A catalyst system according to claim 13 wherein the substituent K is a trimethylsilyl group. 15. A catalyst system according to claim 1, wherein the second catalyst component comprises a catalyst component B as characterized by formula (6), in which the group CpRq is a symmetrically substituted cyclopentadienyl group or fluorenyl group. 16. A process for producing a blend of an isotactic polyolefin and a syndiotactie polyolefin, which comprises: a. providing a catalyst system for producing a polyolefin blend, which catalyst system comprises a mixture of a first catalyst component supported on a first support and a second catalyst component supported on a second support, wherein the first catalyst component is s at least one of a catalyst component A capable of producing an isotactie olefin polymer, and a catalyst component A' capable of producing a polymer comprising an isotactic polyolefin block; and the second catalyst component is at least one of a catalyst component B capable of producing an syndiotactic polyolefin, and a catalyst component B' capable of producing a polymer comprising an syndiotactic polyolefin block; wherein each of the components in the catalyst system is distinct from the other components in the catalyst system, and wherein the catalyst component A comprises at least one metallocene having the formula: description="In-line Formulae" end="lead"R"(CpR'Rb(cp'R'n)MQ2 (1)description="In-line Formulae" end="tail" wherein: (CpR1R2) is a substituted cyclopentadienyl ring; (Cp'R'n) is a substituted or unsubstituted fluorenyl ring; R" is a structural bridge imparting stereorigidity to the component; R1 is a substituent on the cyclopentadienyl ring which is distal to the bridge, which distal substituent comprises a bulky group of the formula XR*3 in which X is an atom from group IVA and each R* is the same or different and is chosen from a hydrogen or a hydrocarbyl group having from 1-20 carbon atoms, R2 is a substituent on the cyclopentadienyl ring which is proximal to the bridge and positioned non-vicinal to the distal substituent and is a hydrogen or is of the formula YR#3 in which Y is an atom from group IVA, and each R# is the same or different and is chosen from a hydrogen or a hydrocarbyl group having from 1-7 carbon atoms, each R' is the same or different and is a hydrocarbyl group having from 1-20 carbon atoms, and n is an integer of from 0-8; M is a metal atom from group IVB or is vanadium; and each Q is a hydrocarbon having from 1-20 carbon atoms or is a halogen; or the formula: description="In-line Formulae" end="lead"(Ind)2R'MQ2 (2)description="In-line Formulae" end="tail" or the formula: description="In-line Formulae" end="lead"(IndH4)2R"MQ2 (3)description="In-line Formulae" end="tail" wherein: each md is the same or different and is a substituted or unsubstituted indenyl group, wherein each IndU4 is the same or different and is a substituted or unsubstituted tetrahydroindenyl group, R' is a structural bridge imparting stereorigidity to the component, R" is a structural bridge imparting stercorigidity to the component; M is a metal atom from group IVB or is vanadium; and each Q is a hydrocarbon having from 1-20 carbon atoms or is a halogen, wherein the catalyst component B has the formula: description="In-line Formulae" end="lead"R"(CPRm)(CP'R'r)MQ2 (4)description="In-line Formulae" end="tail" wherein: (CpRm) is a substituted or unsubstituted cyclopentadienyl ring; (Cp'R'r) is a substituted or unsubstituted fluorenyl ring; R" is a structural bridge imparting stereorigidity to the component, each R is the same or different and is a hydrocarbyl group having from 1-20 carbon atoms; each R' is the same or different and is a hydrocarbyl group having from 1-20 carbon atoms; m is an integer of from 0-4; r is an integer from 0-8; M is a metal atom from group IVB or is vanadium; and each Q is a hydrocarbon having from 1-20 carbon atoms or is a halogen, wherein the catalyst component A' has the formula: description="In-line Formulae" end="lead"R"(CpRx)(Cp'R'y)MQ2 (5)description="In-line Formulae" end="tail" wherein: (CpRx) is a substituted cyclopentadienyl ring; (Cp'R'y) is a substituted or unsubstituted fluorenyl ring; R" is a structural bridge imparting stereorigidity to the component; each R is the same or different and is a hydrocarbyl group having from 1-20 carbon atoms, each R' is the same or different and is a hydrocarbyl group having from 1-20 carbon atoms and x and y are independently an integer of from 1-4 and 0-8 respectively; M is a metal atom from group IVB or is vanadium; and each Q is a hydrocarbon having from 1-20 carbon atoms or is a halogen; wherein the CpRx group lack bilateral symmetry, and wherein the catalyst component B' has the formula: description="In-line Formulae" end="lead"R"(CpRq)XMQ2 (6)description="In-line Formulae" end="tail" wherein: CpRq is a substituted cyclopentadienyl ring or a substituted or unsubstituted fluorenyl ring; R" is a structural bridge between Cp and X imparting stercorigidity to the component; each R is the same or different and is selected from a hydrocarbyl group having from 1-20 carbon atoms, an alkoxyalkyl group, an alkylamino group or an alkylsilylo group; from 0-4; and when Cp is a fluorenyl ring q is an integer from 0-8; X is a heteroatom from group VA or group VJA; M is a metal atom from group IIIB, IVB, VB or VIB in any of its theoretical oxidation states; and each Q is a hydrocarbon having from 1-20 carbon atoms or is a halogen; wherein the bilateral symmetry of the CpRq group is maintained; and further comprising a co-catalyst of an aluminum-or boron-containing activating agent capable of activating at least one of said first catalyst component and said second catalyst component; b. contacting said catalyst system with an olefin monomer in a polymerization reaction zone under polymerization conditions to form a polyolefin product; and c. withdrawing said polyolefin product from said polymerization reaction zone. 17. The process of claim 16 wherein said olefin monomer is propylene. 18. The process of claim 17 wherein said first catalyst component is a catalyst component effective in the polymerization of propylene to produce isotactic polypropylene and said second catalyst component is a catalyst component effective in the polymerization of propylene to produce syndiotactic polypropylene, wherein the polyolcfm product withdrawn from said polymerization reaction zone is a mixture of isotactic polypropylene and syndiotactic polypropylene.
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