[미국특허]
Catalyst systems for production of alpha olefin oligomers and polymers
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/64
C08F-004/76
C08F-004/659
C08F-004/60
B01J-031/22
C08F-110/14
출원번호
US-0307517
(2014-06-18)
등록번호
US-9115225
(2015-08-25)
발명자
/ 주소
Hlavinka, Mark L.
Yang, Qing
Small, Brooke L.
Yu, Youlu
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Merchant & Gould
인용정보
피인용 횟수 :
0인용 특허 :
45
초록
Catalyst compositions containing N,N-bis2-hydroxidebenzylamine transition metal compounds are disclosed. Methods for making these transition metal compounds and for using such compounds in catalyst compositions for the polymerization or oligomerization of alpha olefins also are provided.
대표청구항▼
1. A process for producing a product, the process comprising: contacting a catalyst composition and an alpha olefin monomer comprising a C4 to C60 alpha olefin to produce the product, the catalyst composition comprising:(i) an N,N-bis[2-hydroxidebenzyl]amine compound having formula (Ia): wherein: M
1. A process for producing a product, the process comprising: contacting a catalyst composition and an alpha olefin monomer comprising a C4 to C60 alpha olefin to produce the product, the catalyst composition comprising:(i) an N,N-bis[2-hydroxidebenzyl]amine compound having formula (Ia): wherein: M is Ti, Zr, or Hf;X1 and X2 independently are a monoanionic ligand;each RB and RC independently is a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbylsilyl group, wherein p and q independently are 0, 1, 2, 3, or 4; andRA is a C1 to C36 hydrocarbyl group or C1 to C36 halogenated hydrocarbyl group;(ii) an activator-support comprising a solid oxide treated with an electron-withdrawing anion; and(iii) optionally, a co-catalyst. 2. The process of claim 1, wherein RA is a C1 to C12 hydrocarbyl group. 3. The process of claim 2, wherein: M is Zr or Hf;X1 and X2 independently are H, BH4, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 hydrocarboxy group, a C1 to C36 hydrocarbylaminyl group, a C1 to C36 hydrocarbylsilyl group, a C1 to C36 hydrocarbylaminylsilyl group, OBR12, or OSO2R1, wherein R1 is a C1 to C36 hydrocarbyl group; andeach RB and RC independently is Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or an allyldimethylsilyl group. 4. The process of claim 1, wherein the N,N-bis[2-hydroxidebenzyl]amine compound has formula (Ib): wherein, in formula (Ib): M is Ti, Zr, or Hf;X1 and X2 independently are a monoanionic ligand;RB1, RB2, RC1, and RC2 independently are a halide, C1 to C36 hydrocarbyl group, C1 to C36 halogenated hydrocarbyl group, C1 to C36 hydrocarboxy group, or C1 to C36 hydrocarbylsilyl group; andRA is a C1 to C18 hydrocarbyl group or C1 to C18 halogenated hydrocarbyl group. 5. The process of claim 4, wherein: RB1, RB2, RC1, and RC2 independently are a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, phenyl group, tolyl group, benzyl group, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, allyldimethylsilyl group, CF3, or Cl; andRA is a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, phenyl group, benzyl group, or phenylethyl group. 6. The process of claim 1, wherein the N,N-bis[2-hydroxidebenzyl]amine compound is: or a combination thereof. 7. The process of claim 1, wherein the catalyst composition comprises: an organoaluminum compound comprising trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof; andan activator-support comprising fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof. 8. The process of claim 1, wherein the alpha olefin monomer comprises 1-hexene, 1-octene, 1-decene, 1-tetradecene, or a mixture thereof. 9. The process of claim 1, wherein the process is conducted at a temperature in a range from −20° C. to 150° C. 10. The process of claim 1, wherein the product has a Mw of at least about 250,000 g/mol. 11. The process of claim 1, wherein: X1 and X2 independently are a halide or a C1 to C18 hydrocarbyl group;each RB and RC independently is a halide, a C1 to C18 hydrocarbyl group, or a C1 to C18 hydrocarbylsilyl group, wherein p and q independently are 0, 1, or 2;RA is a C1 to C18 hydrocarbyl group;the activator-support comprises a fluorided solid oxide, a sulfated solid oxide, or a combination thereof; andthe alpha olefin monomer comprises a C4 to C20 alpha olefin. 12. The process of claim 11, wherein: the catalyst composition comprises a co-catalyst;the process is conducted at a temperature in a range from 10° C. to 60° C.; andthe product has a Mw in a range from 750,000 to 7,500,000 g/mol. 13. The process of claim 11, wherein: M is Zr or Hf;X1 and X2 independently are a halide, methyl, benzyl, or phenyl;each RB and RC independently is a C1 to C5 alkyl group; andthe alpha olefin monomer comprises a C6 to C14 normal alpha olefin. 14. The process of claim 13, wherein: RA is a C1 to C8 alkyl group or a C3 to C8 terminal alkenyl group;the catalyst composition comprises an organoaluminum co-catalyst; andthe alpha olefin monomer comprises 1-hexene, 1-octene, 1-decene, 1-tetradecene, or a mixture thereof. 15. The process of claim 4, wherein the catalyst composition comprises a co-catalyst, and wherein, in formula (Ib): M is Zr or Hf;X1 and X2 independently are a halide or a C1 to C18 hydrocarbyl group;RB1, RB2, RC1, and RC2 independently are a halide, a C1 to C18 hydrocarbyl group, or a C1 to C18 hydrocarbylsilyl group; andRA is a C1 to C18 hydrocarbyl group. 16. The process of claim 15, wherein: the alpha olefin monomer comprises a C4 to C20 alpha olefin;the activator-support comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof; andRB1, RB2, RC1, and RC2 independently are a C1 to C5 alkyl group. 17. The process of claim 16, wherein: the alpha olefin monomer comprises a C6 to C14 normal alpha olefin;the product has a Mw in a range from 750,000 to 7,500,000 g/mol;the activator-support comprises fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, or any combination thereof;the catalyst composition comprises an organoaluminum co-catalyst; andin formula (Ib): X1 and X2 independently are a halide, methyl, benzyl, or phenyl; andRA is a C1 to C8 alkyl group or a C3 to C8 terminal alkenyl group. 18. The process of claim 4, wherein: the alpha olefin monomer comprises a C6 to C14 normal alpha olefin;the catalyst composition comprises a co-catalyst;the process is conducted at a temperature in a range from −20° C. to 150° C.; andthe product has a Mw in a range from 750,000 to 7,500,000 g/mol. 19. The process of claim 18, wherein, in formula (Ib): M is Zr or Hf;X1 and X2 independently are a halide or a C1 to C18 hydrocarbyl group;RB1, RB2, RC1, and RC2 independently are a halide, a C1 to C18 hydrocarbyl group, or a C1 to C18 hydrocarbylsilyl group; andRA is a C1 to C18 hydrocarbyl group. 20. The process of claim 19, wherein: the catalyst composition comprises an organoaluminum co-catalyst;the activator-support comprises a fluorided solid oxide, a sulfated solid oxide, or a combination thereof;the process is conducted at a temperature in a range from 10° C. to 60° C.;the alpha olefin monomer comprises 1-hexene, 1-octene, 1-decene, 1-tetradecene, or a mixture thereof; andin formula (Ib):X1 and X2 independently are a halide, methyl, benzyl, or phenyl;RB1, RB2, RC1, and RC2 independently are a C1 to C5 alkyl group; andRA is a C1 to C8 alkyl group or a C3 to C8 terminal alkenyl group.
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