Process for manufacturing single-site polyolefins
A dual olefin polymerization process is disclosed. The process uses a bridged indenoindolyl ligand-containing Group 4 transition metal complex and an activator. It is carried out in multiple stages or in multiple reactors. The same complex and the same activator are used in all stages or reactors. Different polyolefins are made in different stages or reactors by varying the monomer compositions, hydrogen concentrations, or both. The process of the invention produces polyolefins which have broad molecular weight distributions, composition distributions, or both.
1. A dual process comprising two or more sequential stages:
(1) polymerizing, in the presence of a bridged indenoindolyl ligand-containing group 4 transition metal complex and an activator, ethylene or a mixture of ethylene and a C 3 to C 10 α-olefin in a reactor in the presence of hydrogen at an ethylene/α-olefin weight ratio greater than 95/5 and a hydrogen/ethylene molar ratio within the range of about 0.001/1 to about 10/1 to produce a high density polyethylene (HDPE); and
(2) continuing the polymerization, in the presence of the same complex and the same activator as in stage (1), by adding a mixture of ethylene and a C 3 to C 10 α-olefin to the reactor at an ethylene/α-olefin weight ratio less than 95/5 and a hydrogen/ethylene molar ratio less than 1/1 to produce a linear low density polyethylene (LLDPE).
2. The process of claim 1 wherein from about 30 to about 70 wt % of the product is produced in stage (1).
3. The process of claim 1 wherein the complex has the general structure:
wherein M is a Group 4 transition metal; B is a bridging group; L 1 is an indenoindolyl ligand; L 2 is a ligand selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, boraarys, pyrrolyls, azaborolinyls, quinolinyls, indenoindolyls, and phosphinimines; L 3 and L 4 , the same or different, are independently selected from the group consisting of hydrogen, halogens, alkyls, aryls, alkoxys, aryloxys, siloxys, alkyl aminos, and aryl aminos.
4. The process of claim 3 wherein M is selected from the group consisting of Zr and Ti.
5. The process of claim 3 wherein M is Zr.
6. The process of claim 3 wherein B is selected from the group consisting of CR 2 , C 2 R 4 , SiR 2 , Si 2 R 4 , GeR 2 , Ge 2 R 4 , R 2 SiCR 2 , NR, and PR wherein the substituents R, the same or different from each other, are selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkylaryl, and arylalkyl groups.
7. The process of claim 3 wherein B is selected from the group consisting of methylene, dimethylene, isopropylidene, and dimethylsilyl.
8. The process of claim 3 wherein L 1 is selected from the group consisting of
wherein R 1 is selected from the group consisting of alkyl, aryl, aralkyl, and silyl groups; R 2 through R 10 are the same or different and selected from the group consisting of hydrogen, alkyl, aryl, aralkyl, alkylaryl, silyl, halogen, alkoxy, aryloxy, siloxy, nitro, dialkyl amino, and diaryl amino groups.
9. The process of claim 3 wherein L 3 and L 4 , the same or different, are independently selected from halogens.
10. The process of claim 3 wherein both L 3 and L 4 are chlorine.
11. The process of claim 1 wherein the complex is selected from the group consisting of Me 2 Si(indeno[1,2-b]indolyl)(Cp)ZrCl 2 , Me 2 Si(indeno[1,2-b]indolyl) 2 ZrCl 2 , Me 2 Si(indeno[2,1-b]indolyl)(Cp)ZrCl 2 , Me 2 Si(indeno[2,1-b]indolyl) 2 ZrCl 2 , Me 2 C(indeno[1,2-b]indolyl)(Cp)ZrCl 2 , Me 2 C(indeno[1,2-b]indolyl) 2 ZrCl 2 , Me 2 C(indeno[2,1-b]indolyl)(Cp)ZrCl 2 , Me 2 C(indeno[2,1-b]indolyl) 2 ZrCl 2 , Ph 2 C(indeno[1,2-b]indolyl)(Cp)ZrCl 2 , Ph 2 C(indeno[1,2-b]indolyl) 2 ZrCl 2 , Ph 2 C(indeno[2,1-b]indolyl)(Cp)ZrCl 2 , Ph 2 C(indeno[2,1-b]indolyl) 2 ZrCl 2 , Me 2 Si(indeno[1,2-b]indolyl)(Flu)ZrCl 2 , Me 2 Si(indeno[2,1-b]indolyl)(Flu)ZrCl 2 , Me 2 C(indeno[1,2-b]indolyl)(Flu)ZrCl 2 , Me 2 C(indeno[2,1-b]indolyl)(Flu)ZrCl 2 , Ph 2 C(indeno[1,2-b]indolyl)(Flu)ZrCl 2 , Ph 2 C(indeno[2,1-b]indolyl)(Flu)ZrCl 2 , (CH 2 —CH 2 )(indeno[1,2-b]indolyl)(Cp)ZrCl 2 , (CH 2 —CH 2 )(indeno[1,2-b]indolyl) 2 ZrCl 2 , (CH 2 —CH 2 )(indeno[2,1-b]indolyl)(Cp)ZrCl 2 , (CH 2 —CH 2 )(indeno[2,1-b]indolyl) 2 ZrCl 2 , ((CH 3 ) 2 Si—Si(CH 3 ) 2 ))(indeno[1,2-b]indolyl)(Cp)ZrCl 2 , ((CH 3 ) 2 Si—Si(CH 3 ) 2 ))(indeno[1,2-b]indolyl) 2 ZrCl 2 , ((CH 3 ) 2 Si—Si(CH 3 ) 2 ))(indeno[2,1-b]indolyl)(Cp)ZrCl 2 , ((CH 3 ) 2 Si—Si(CH 3 ) 2 ))(indeno[2,1-b]indolyl) 2 ZrCl 2 , and mixtures thereof.
12. The process of claim 1 wherein the complex is supported.
13. The process of claim 1 wherein the activator is selected from the group consisting of alumoxanes, alkyl aluminums, alkyl aluminum halides, anionic compounds of boron or aluminum, trialkylboron and triarylboron compounds, and mixtures thereof.
14. The process of claim 1 wherein the activator is methylalumoxane (MAO) or polymeric MAO.
15. The process of claim 1 wherein the activator is tris-(pentafluorophenyl)borane.
16. The process of claim 1 wherein the α-olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and mixtures thereof.
17. The process of claim 1 wherein the α-olefin is 1-hexene.
18. The process of claim 1 wherein the olefin is 1-butene.
19. A dual process comprising two or more sequential reactors:
(1) in a first reactor, polymerizing, in the presence of a bridged indenoindolyl ligand-containing group 4 transition metal complex and an activator, ethylene or a mixture of ethylene and a C 3 to C 10 α-olefin in the presence of hydrogen at an ethylene/α-olefin weight ratio greater than 95/5 and a hydrogen/ethylene molar ratio within the range of about 0.001/1 to about 10/1 to produce an HDPE; and
(2) transferring the product of (1) into a second reactor and continuing the polymerization in the presence of the same complex and the same activator as in stage (1) by adding a mixture of ethylene and a C 3 to C 10 α-olefin to the second reactor at an ethylene/α-olefin weight ratio less than 95/5 and a hydrogen/ethylene molar ratio less than 1/1 to produce an LLDPE.
20. The process of claim 19 wherein about 30 to about 70 wt % of the product is produced in the first reactor.
21. The process of claim 19 wherein the complex has the general structure:
wherein M is a Group 4 transition metal; B is a bridging group; L 1 is an indenoindolyl ligand; L 2 is a ligand selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, boraarys, pyrrolyls, azaborolinyls, quinolinyls, indenoindolyls, and phosphinimines; L 3 and L 4 , the same or different, are independently selected from the group consisting of hydrogen, halogens, alkyls, aryls, alkoxys, aryloxys, siloxys, alkyl aminos, and aryl aminos.
22. The process of claim 21 wherein M is selected from the group consisting of Zr and Ti.
23. The process of claim 21 wherein M is Zr.
24. The process of claim 21 wherein B is selected from the group consisting of CR 2 , C 2 R 4 , SiR 2 , Si 2 R 4 , GeR 2 , Ge 2 R 4 , R 2 SiCR 2 , NR, and PR wherein the substituents R, the same or different from each other, are selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkylaryl, and arylalkyl groups.
25. The process of claim 21 wherein B is selected from the group consisting of methylene, dimethylene, isopropylidene, and dimethylsilyl.
26. The process of claim 21 wherein L 1 is selected from the group consisting of
wherein R 1 is selected from the group consisting of alkyl, aryl, aralkyl, and silyl groups; R 2 through R 10 are the same or different and selected from the group consisting of hydrogen, alkyl, aryl, aralkyl, alkylaryl, silyl, halogen, alkoxy, aryloxy, siloxy, nitro, dialkyl amino, and diaryl amino groups.
27. The process of claim 21 wherein L 3 and L 4 , the same or different, are independently selected from halogens.
28. The process of claim 21 wherein both L 3 and L 4 are chlorine.
29. A dual process comprising two or more parallel reactors:
(1) in a first reactor, polymerizing in the presence of a bridged indenoindolyl ligand-containing group 4 transition metal complex and an activator, ethylene or a mixture of ethylene and a C 3 to C 10 α-olefin in the presence of hydrogen at an ethylene/α-olefin weight ratio greater than 95/5 and hydrogen/ethylene molar ratio within the range of about 0.001/1 to about 10/1 to produce an HOPE; and
(2) in a second reactor, polymerizing, in the presence of the same complex and the same activator as in stage (1), a mixture of ethylene and a C 3 to C 10 α-olefin to the second reactor at an ethylene/α-olefin weight ratio less than 95/5 and hydrogen/ethylene molar ratio less than 1/1 to produce an LLDPE; wherein the products from the reactors are mixed.
30. The process of claim 29 wherein about 30 to about 70 wt % of the product is produced in the first reactor.
31. The process of claim 29 wherein the complex has the general structure:
wherein M is a Group 4 transition metal; B is a bridging group; L 1 is an indenoindolyl ligand; L 2 is a ligand selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, boraarys, pyrrolyls, azaborolinyls, quinolinyls, indenoindolyls, and phosphinimines; L 3 and L 4 , the same or different, are independently selected from the group consisting of hydrogen, halogens, alkyls, aryls, alkoxys, aryloxys, siloxys, alkyl aminos, and aryl aminos.
32. The process of claim 31 wherein M is selected from the group consisting of Zr and Ti.
33. The process of claim 31 wherein M is Zr.
34. The process of claim 31 wherein B is selected from the group consisting of CR 2 , C 2 R 4 , SiR 2 , Si 2 R 4 , GeR 2 , Ge 2 R 4 , R 2 SiCR 2 , NR, and PR wherein the substituents R, the same or different from each other, are selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkylaryl, and arylalkyl groups.
35. The process of claim 31 wherein B is selected from the group consisting of methylene, dimethylene, isopropylidene, and dimethylsilyl.
36. The process of claim 31 wherein L 1 is selected from the group consisting of
wherein R 1 is selected from the group consisting of alkyl, aryl, aralkyl, and silyl groups; R 2 through R 10 are the same or different and selected from the group consisting of hydrogen, alkyl, aryl, aralkyl, alkylaryl, silyl, halogen, alkoxy, aryloxy, siloxy, nitro, dialkyl amino, and diaryl amino groups.
37. The process of claim 31 wherein L 3 and L 4 , the same or different, are independently selected from halogens.
38. The process of claim 31 wherein both L 3 and L 4 are chlorine.