Production of polyolefins with internal unsaturation structures using a metallocene catalyst system
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IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/6592
C08F-210/16
C07F-007/08
C08F-210/02
출원번호
US-0249021
(2016-08-26)
등록번호
US-9926396
(2018-03-27)
발명자
/ 주소
Holtcamp, Matthew W.
Bedoya, Matthew S.
Ye, Xuan
Sanders, David F.
Day, Gregory S.
Mattler, Sarah J.
출원인 / 주소
ExxonMobil Chemical Patents Inc.
인용정보
피인용 횟수 :
0인용 특허 :
11
초록
This invention relates to a process to polymerize olefins, particularly to produce ethylene polymers with internal unsaturation structures.
대표청구항▼
1. A process to polymerize olefins comprising: 1) contacting olefin monomers with a catalyst system comprising an activator and a bis-cyclopentadienyl metallocene compound represented by the formula: wherein:M is Hf;each X1 and X2 is, independently, a hydrocarbyl radical having from 1 to 20 carbon a
1. A process to polymerize olefins comprising: 1) contacting olefin monomers with a catalyst system comprising an activator and a bis-cyclopentadienyl metallocene compound represented by the formula: wherein:M is Hf;each X1 and X2 is, independently, a hydrocarbyl radical having from 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether, or X1 and X2 optionally form a part of a fused ring or a ring system;each of R1, R2, R3, R4, R6, R7, R8, and R9 is, independently, hydrogen, halide, alkoxide or a C1 to C40 substituted or unsubstituted hydrocarbyl group, provided that at least one of R1, R2, R3, R4, R6, R7, R8, and R9 is a linear C3 to C20 substituted or unsubstituted hydrocarbyl group;T is a group 14 atom;each Ra and Rb is, independently, a C1 to C40 substituted or unsubstituted hydrocarbyl;andwherein the bis-cyclopentadienyl metallocene compound generates hydrogen and the polymerization occurs in the presence of hydrogen;2) obtaining a polymer having:a) an internal unsaturation of 50% or more;b) a melt index of less than 20 g/10 min; andc) a g′vis of 0.95 or more. 2. The process of claim 1, wherein each X1 and X2 is, independently, a halide or a C1 to C5 alkyl group. 3. The process of claim 1, wherein each Ra and Rb is, independently, a C6 to C20 substituted or unsubstituted aryl. 4. The process of claim 1, wherein at least one of R6, R7, R8, and R9 and at least one of R1, R2, R3, R4, is a linear C3 to C20 substituted or unsubstituted hydrocarbyl group. 5. The process of claim 1, wherein each R2, R3, R4, R6, R7, R8, and R9 is, independently, a linear C3 to C20 alkyl group. 6. The process of claim 1, wherein at least one of R7 and R8 and at least one of R2 and R3 is, independently, a n-propyl, n-butyl, n-pentyl, or n-hexyl group. 7. The process of claim 1, wherein each Ra and Rb comprises a phenyl or substituted phenyl group. 8. The process of claim 1, wherein the metallocene compound comprises one or more of: diphenylsilylbis(n-propylcyclopentadienyl)hafnium X1X2, diphenylsilylbis(n-butylcyclopentadienyl)hafniumX1X2, diphenylsilylbis(n-pentylcyclopentadienyl)hafniumX1X2, diphenylsilyl(n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafniumX1X2, diphenylsilylbis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumX1X2, dimethylsilylbis(n-propylcyclopentadienyl)hafniumX1X2, dimethylsilylbis(n-butylcyclopentadienyl)hafniumX1X2, dimethylsilylbis(n-pentylcyclopentadienyl)hafniumX1X2, dimethylsilyl(n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafniumX1X2, dimethylsilylbis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumX1X2, wherein each X1 and X2 is, independently, selected from the group consisting of chlorides, fluorides, methyl, ethyl, propyl, and butyl groups. 9. The process of claim 1, wherein the activator comprises alumoxane and/or a non-coordinating anion activator. 10. The process of claim 9, wherein the activator comprises alumoxane present at a molar ratio of aluminum to transition metal of the metallocene compound of 100:1 or more. 11. The process of claim 1, wherein the activator is represented by the formula: (Z)d+(Ad−)wherein Z is (L-H) or a reducible Lewis Acid, L is a neutral Lewis base; H is hydrogen; (L-H)+ is a Bronsted acid; Ad− is a non-coordinating anion having the charge d−; and d is an integer from 1 to 3. 12. The process of claim 1, wherein the activator is one or more of: N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Me3NH+][B(C6F5)4-], 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate), trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N-dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di -(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, wherein alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl. 13. The process of claim 1, wherein the olefin monomer comprises ethylene. 14. The process of claim 1, wherein the catalyst system is supported on an inert support material. 15. The process of claim 1, wherein the catalyst system is supported on support material selected from the group consisting of talc, inorganic oxides, zeolites, clays, organoclays and mixtures thereof. 16. The process of claim 1, wherein step 1) occurs at a temperature of from about 0° C. to about 300° C., at a pressure in the range of from about 0.35 MPa to about 10 MPa, and at a time of up to 300 minutes. 17. The process of claim 1, wherein step 1) occurs at a temperature of from about 0° C. to about 300° C., at a pressure in the range of from about 0.35 MPa to about 10 MPa, and at a time of up to 300 minutes.
Turner Howard William ; Vaughan George Alan ; Fisher Richard Allen ; Walzer ; Jr. John Flexer ; Speed Charles Stanley ; Folie Bernard Jean ; Crowther Donna Jean, High temperature olefin polymerization process.
Dimeska, Anita; Maier, Ralph-Dieter; Paczkowski, Nicola S.; Thorn, Matthew Grant; Winter, Andreas; Schulte, Joerg; Sell, Thorsten, Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers.
Schottek,Joerg; Paczkowski,Nicola Stefanie; Winter,Andreas; Sell,Thorsten, Metallocene ligands, metallocene compounds and metallocene catalysts, their synthesis and their use for the polymerization of olefins.
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