Dynamic modulation of metallocene catalysts

Patent metadata

Field	Value
Publication number	US-8969482-B2
Application number	US-201213623263-A
Country	US
Kind code	B2
Filing date	Sep 20, 2012
Priority date	Sep 30, 2011
Publication date	Mar 3, 2015
Grant date	Mar 3, 2015

Abstract

This invention relates to a process to alter comonomer distribution in a copolymer (as compared to a copolymer made absent the Lewis base modifier) comprising contacting ethylene and one or more C 3 to C 40 comonomers; with a catalyst system comprising: 1) a Lewis base modifier; 2) an activator; and 3) a bridged bisindenyl group 4 transition metal metallocene catalyst compound having a hydrogen atom at least one 2 position.

First claim

The invention claimed is:

1. A process to alter comonomer distribution in a copolymer (as compared to a copolymer made under the same conditions absent the Lewis base modifier) comprising contacting ethylene and one or more C 3 to C 40 comonomers; with a catalyst system consisting essentially of:
1) Lewis base modifier present at greater than 1:1 molar ratio of Lewis base modifier to activator, where the Lewis base modifier is represented by the formula:
(R 1 ) z (R 2 )X n (R 3 )(R 4 ) y or (R 1 ) z (R 4 ) y X n ═R 2 or Z═C—R 5

where, z is 0 or 1, y is 0 or 1, a is the valence of X and is 2 or 3, and z y 2 n, X is a group 15 atom, Z is N or P, R 1 , R 4 , and R 5 each, independently, are hydrogen, a heteroatom, a substituted heteroatom, or a substituted or unsubstituted alkyl or substituted gar unsubstituted aryl,
R 2 and R 3 each, independently, are a heteroatom, a substituted heteroatom, or a substituted or unsubstituted alkyl or substituted or unsubstituted aryl, and R 1 and R 2 can form a single ring, R 1 and R 4 can form a single ring, R 2 and R 3 can form a single ring, and R 3 and R 4 can form a single ring;
2) activator and optional co-activator; and
3) metallocene catalyst compound represented by the formula:

where;
M is a Group transition 4 metal; z is 1 indicating the presence of a bridging group T, each X′ is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two X′ groups may form a part of a fused ring or a ring system), each R is, independently, hydrogen, or a C 1 to C 10 alkyl group, provided that at least one R 1 group is H; each R 2 is, independently, hydrogen, or a C 1 to C 10 alkyl group; each R 3 , R 4 , R 5 , and R 6 is, independently, hydrogen, a substituted hydrocarbyl group, an unsubstituted hydrocarbyl group, or a heteroatom, provided that any of adjacent R 3 , R 4 , R 5 , and R 6 groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated, wherein the process occurs at a temperature of from about 0° C. to about 120° C.

2. The process of claim 1 , further comprising obtaining copolymer having an average r 1 r 2 of at least 10% greater than the copolymer made under the same conditions without the Lewis base modifier present.

3. The process of claim 1 , further comprising obtaining copolymer having a DSC peak melting temperature, Tm, of Y or more, where Y=134−(6.25*X″), where X is the mol % comonomer.

4. The process of claim 1 , wherein no more than one metallocene catalyst compound is present in the catalyst system.

5. The process of claim 1 , wherein the Lewis base modifier is represented by the formula:
(R 1 ) z (R 2 )X n (R 3 )

where, z is 0 or 1, n is the valence of X and is 2 or 3, X is N, air P, R 1 is hydrogen, a heteroatom, a substituted heteroatom, or a substituted or unsubstituted alkyl or substituted or unsubstituted aryl, R 2 and R 3 each, independently, are a heteroatom, a substituted heteroatom, or a substituted or unsubstituted alkyl or substituted or unsubstituted aryl, and R 1 and R 2 can form a single ring, and R 2 and R 3 can form a single ring.

6. The process of claim 1 , wherein the Lewis base modifier is represented by the formula:
(R 1 ) z (R 4 ) y X n ═R 2

where, z is 0 or 1, y is 0 or 1, n is the valence of X and is 2or 3, and z+y+2=n, X is N, S, or P, R 1 , R 2 , and R 4 each, independently, are hydrogen, a heteroatom, a substituted heteroatom, or a substituted or unsubstituted alkyl or substituted or unsubstituted aryl, and R 1 and R 2 can form a single ring, and R 1 and R 4 can form a single ring.

7. The process of claim 6 , where, R 1 , R 2 , and R 4 each, independently, are hydrogen, a heteroatom, a substituted heteroatom, or a substituted or unsubstituted alkyl or substituted or unsubstituted aryl.

8. The process of claim 6 , where, R 1 , R 2 , and R 4 each, independently, are hydrogen, methyl, ethyl propyl, butyl, pentyl, hexyl, heptyl, acetyl, decyl, undecyl, dodecyl, phenyl, substituted phenyl (such as tolyl), or isomers thereof.

9. The process of claim 1 , wherein the Lewis base modifier comprises one or more of trimethylamine, ethyldimethylamine, diethylmethylamine, triethylamine, tripropylamine (including n-propyl, and isopropyl, and combinations thereof), dimethylpropylamine (including n-propyl, and isopropyl), diethylpropylamine (including n-propyl, and isopropyl), methyldipropylamine (including n-propyl, and isopropyl), ethyldipropylamine (including n-propyl, and isopropyl), tributylamine (including n-butyl, sec-butyl, and isobutyl), dimethylbutylamine (including n-butyl, sec-butyl, and isobutyl), dimethylphenylamine, diethylbutylamine (including n-butyl, sec-butyl, and isobutyl), butyldipropylamine (including n-propyl, isopropyl, n-butyl, sec-butyl, and isobutyl), dibutylpropylamine (including n-propyl, isopropyl, n-butyl, sec-butyl, and isobutyl), methyldiphenylamine, triphenylamine, pyridine, and 4-(dimethylamino)pyridine, quinoline, isoquinoline, 1,2,3,4-tetrahydroquinoline, or acridine.

10. The process of claim 1 , wherein the Lewis base modifier is present at a molar ratio of X in the Lewis base modifier, as described in the formulae in claim 1 , to transition metal in the catalyst compound of from 0.5:1 to 1000:1.

11. The process of claim 1 , wherein M is Hf, Ti, and/or Zr.

12. The process of claim 1 , wherein each X′ is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms and halides.

13. The process of claim 1 , wherein all R 1 groups in the metallocene formula are hydrogen.

14. The process of claim 1 , wherein all R 1 groups in the metallocene formula are hydrogen and all R 2 groups are hydrogen.

15. The process of claim 1 , wherein all R 1 groups in the metallocene formula are hydrogen and all R 2 groups are, independently, hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.

16. The process of claim 1 , wherein T is represented by one or more of the formulae: R′ 2 C, R′ 2 Si, R′ 2 Ge, R′ 2 CCR′ 2 , R′ 2 CCR′ 2 CR′ 2 , R′ 2 CCR′ 2 CR′ 2 CR′ 2 , R′C═CR′, R′C═CR′CR′ 2 , R′ 2 CCR′═CR′CR′ 2 , R′C═CR′CR′═CR′, R′C═CR′CR′ 2 CR′ 2 , R′ 2 CSiR′ 2 , R′ 2 SiSiR′ 2 , R 2 CSiR′ 2 CR′ 2 , R′ 2 SiCR′ 2 SiR′ 2 , R′C═CR′SiR′ 2 , R′ 2 CGeR′ 2 , R′ 2 GeGeR′ 2 , R′ 2 CGeR′ 2 CR′ 2 , R′ 2 GeCR′ 2 GeR′ 2 , R′ 2 SiGeR′ 2 , R′C═CR′GeR′ 2 , R′B, R′ 2 C—BR′, R′ 2 C—BR′—CR′ 2 , R′ 2 C—O—CR′ 2 , R′ 2 CR′ 2 C—O—CR′ 2 CR′ 2 , R′ 2 C—O—CR′ 2 CR′ 2 , R′ 2 C—O—CR′═CR′, R′ 2 C—S—CR′ 2 , R′ 2 CR′ 2 C—S—CR′ 2 CR′ 2 , R′ 2 C—S—CR′ 2 CR′ 2 , R′ 2 C—S—CR′═CR′, R′ 2 C—Se—CR′ 2 , R′ 2 CR′ 2 C—Se—CR′ 2 CR′ 2 , R′ 2 C—Se—CR 2 CR′ 2 , R′ 2 C—Se—CR′═CR′, R′ 2 C—N═CR′, R′ 2 C—NR′—CR′ 2 , R′ 2 C—NR′—CR′ 2 CR′ 2 , R′ 2 C—NR′—CR′═CR′, R′ 2 CR′ 2 C—NR′—CR′ 2 CR′ 2 , R′ 2 C—P═CR′, and R′ 2 C—PR′—CR′ 2 where R′ is hydrogen or a C 1 to C 20 containing hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituent and optionally two or more adjacent R′ may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent.

17. The process of claim 1 , wherein T is selected from CH 2 , CH 2 CH 2 , C(CH 3 ) 2 , SiMe 2 , SiPh 2 , SiMePh

Assignees

• Exxonmobil Chem Patents Inc

Inventors

• Stewart Ian C

Classifications

• C08F4/65927 Primary

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F10/00 Primary

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F2410/01

  Additive used together with the catalyst, excluding compounds containing Al or B · CPC title

• C08F297/083

  the monomers being ethylene or propylene · CPC title