Catalyst systems for olefin polymerization

Patent metadata

Field	Value
Publication number	US-10214622-B2
Application number	US-201715652606-A
Country	US
Kind code	B2
Filing date	Jul 18, 2017
Priority date	Dec 27, 2012
Publication date	Feb 26, 2019
Grant date	Feb 26, 2019

Abstract

The instant invention provides procatalysts and catalyst systems for olefin polymerization, olefin based polymers polymerized therewith, and process for producing the same. In one embodiment, the instant invention provides a procatalyst comprising a metal-ligand complex of formula (I):

First claim

We claim:

1. A procatalyst comprising a metal-ligand complex of formula (I):

where:
M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; and n is an integer from 0 to 3, and wherein when n is 0, X is absent;
each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic; or two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; and X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral;
each Z is O;
L is (C 3 -C 40 )hydrocarbylene or (C 3 -C 40 )heterohydrocarbylene, wherein the (C 3 -C 40 )hydrocarbylene has a portion that comprises a 3-carbon atom to 10-carbon atom linker backbone linking the Z atoms in formula (I) and the (C 3 -C 40 )heterohydrocarbylene has a portion that comprises a 3-atom to 10-atom linker backbone linking the Z atoms in formula (I), wherein each of the 3 to 10 atoms of the 3-atom to 10-atom linker backbone of the (C 3 -C 40 )heterohydrocarbylene independently is a carbon atom or heteroatom, wherein each heteroatom independently is O, S, S(O), S(O) 2 , Si(R c ) 2 , Ge(R c) 2 , P(R P ), —N═, or N(R n ), wherein independently each R C is (C 1 -C 30 )hydrocarbyl, each R P is (C 1 -C 30 )hydrocarbyl; and each R N is (C 1 -C 30 )hydrocarbyl;
R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are independently selected from the group consisting of a (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, Si(R c ) 3 , Ge(R c ) 3 , P(R P ) 2 , N(R N ) 2 , OR c , SR c , NO 2 , CN, CF 3 , R c S(O)—, R c S(O) 2 -, (R c ) 2 C=N—, R c C(O)O—, R c OC(O)—, R c C(O)N(R)—, (R c ) 2 NC(O)—, halogen atom, and hydrogen atom
when R 8 is H, R 9 is a (C 1 -C 40 )hydrocarbyl; (C 1 -C 40 )heterohydrocarbyl; Si(R c ) 3 , Ge(R c ) 3 , P(R P ) 2 , N(R N ) 2 , OR c , SR c , NO 2 , CN, CF 3 , R c S(O)—, R c S(O) 2 -, (R c ) 2 C═N—, R c C(O)O—, R c OC(O)—, R c C(O)N(R)—, (R c ) 2 NC(O)—or halogen atom; or
when R 9 is H, R 8 is a (C 1 -C 40 )hydrocarbyl; (C 1 -C 40 )heterohydrocarbyl; Si(R c ) 3 , Ge(R c ) 3 , P(R P ) 2 , N(R N ) 2 , OR c , SR c , NO 2 , CN, CF 3 , R c S(O)—, R c S(O) 2 -, (R c ) 2 C=N—, R c C(O)O—, R c OC(O)—, R c C(O)N(R)—, (R c ) 2 NC(O)—or halogen atom; and
R 1 and R 16 are independently selected from radicals having formula (II)

 where each R 22 and R 19 is independently chosen from (C 1 -C 20 )alkyl, (C 3 -C 40 )cycloalkyl, ( C6-C40 )aryl, (C 1 -C 40 )heterohydrocarbyl, -Si(R C ) 3 , -Ge(R C ) 3 , -N(R N ) 2 , -N═R C , -OR C ;
optionally two or more of R 2 , R 3 , and R 4 , or two or more of R 5 , R 6 , R 7 , and R 8 , or two or more of R 9 , R 10 , R 11 , and R 12 , or two or more of R 13 , R 14 and R 15 can be covalently connect in ring structures, with such ring structures having from 3 to 50 atoms in the ring excluding any hydrogen atoms;
each of the aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl, Si(R C ) 3 , Ge(R C ) 3 , P(R P ) 2 , N(R N ) 2 , OR C , SR C , R C S(O)—, R c S(O) 2 -, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, hydrocarbylene, and heterohydrocarbylene groups independently is unsubstituted or substituted with one or more R s substituents; and
each R s independently is a halogen atom, unsubstituted (C 1 -C 18 )alkyl, F 3 C—, FCH 2 O—, F 2 HCO—, F 3 CO—, R 3 Si—, R 3 Ge—, RO—, RS—, RS(O)—, RS(O) 2 —, R 2 P—, R 2 N—, R 2 C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R 2 NC(O)—, or two of the R s are taken together to form an unsubstituted (C 1 -C 18 )alkylene, wherein each R independently is an unsubstituted (C 1 -C 18 )alkyl.

2. The polymerization process according to claim 1 , wherein R 3 and R 14 are independently chosen from tert-octyl or tent-butyl.

3. The polymerization process according to claim 1 , wherein R 8 and R 9 are independently chosen from methyl, ethyl, 2-propyl, chloro, fluoro, or —NMe 2 .

4. The polymerization process according to claim 1 , wherein R 6 and R 11 are independently chosen from methyl, chloro, or fluoro.

5. The polymerization process according to claim 1 , wherein each R 19 and each R 22 is independently chosen tent-butyl, n-propyl, 2 -propyl, cyclohexyl, —SiMe 3 , —Si(Me) 2 (tBu), —CH 2 Si(Me) 3 , 3,5-di-tert-butylphenyl, 3,5-di-methylphenyl, or phenyl.

6. The polymerization process according to claim 1 , wherein each R 19 and each R 22 are tert-butyl.

7. The polymerization process according to claim 1 , wherein each R 19 and each R 22 are tert-butyl; R 3 and R 14 are tert-octyl; R 6 and R 11 are fluoro; R 8 is hydrogen; and R 9 is methyl.

8. The polymerization process according to claim 1 , wherein each R 19 and each R 22 are tert-butyl; R 3 and R 14 are tert-octyl; R 6 and R 11 are fluoro; and R 8 and R 9 are methyl.

9. The polymerization process according to claim 1 , wherein each R 19 and each R 22 are tert-butyl; R 3 and R 14 are tert-octyl; R 6 and R 11 are fluoro; R 8 and R 9 are methyl; and L is —CH 2 Si(Et) 2 CH—.

10. The polymerization process according to claim 1 , wherein each R 19 and each R 22 are tert-butyl; R 3 and R 14 are tert-octyl; R 6 and R 11 are fluoro; R 8 is hydrogen; R 9 is methyl; and L is —CH 2 Si(Et) 2 CH—.

11. A catalyst system comprising the reaction product of:
one or more procatalysts of claim 1 ; and
one or more cocatalysts; wherein the ratio of total number of moles of the one or more metal-ligand complexes of formula (I) to total number of moles of the one or more cocatalysts is from 1:10,000 to 100:1.

12. A polymerization process comprising the:
polymerizing ethylene one or more a-olefins in the presence of one or more catalyst systems of claim 1 under olefin polymerizing conditions; and thereby forming an olefin based polymer.

Assignees

• Dow Global Technologies Llc

Inventors

• Klosin Jerzy
• Figueroa Ruth
• Thomas Pulikkottil J
• Demirors Mehmet
• Desjardins Sylvie
• Kapur Mridula
• Fontaine Philip P

Classifications

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title

• C08L2205/02

  containing two or more polymers of the same C08L -group · CPC title

• C08L23/0815

  with aliphatic 1-olefins containing one carbon-to-carbon double bond · CPC title

• C08L23/08

  Copolymers of ethene (C08L23/16 takes precedence) · CPC title

• C08L23/06

  Polyethylene · CPC title