Polymerization process for producing ethylene based polymers

Patent metadata

Field	Value
Publication number	US-10059787-B2
Application number	US-201615357901-A
Country	US
Kind code	B2
Filing date	Nov 21, 2016
Priority date	Dec 27, 2012
Publication date	Aug 28, 2018
Grant date	Aug 28, 2018

Abstract

The instant invention provides a polymerization process for producing ethylene based polymers.
In one embodiment, the instant invention provides a polymerization process for producing ethylene based polymers comprising: polymerizing ethylene with optionally one or more α-olefins in the presence of one or more first catalyst systems and optionally one or more second catalyst systems in a dual reactor system or a multiple reactor system, wherein first catalyst system comprises;
(a) one ore more procatalysts comprising a metal-ligand complex of formula (I):

First claim

We claim:

1. A polymerization process for producing ethylene based polymers comprising:
polymerizing ethylene and optionally one or more α-olefins in the presence of one or more first catalyst systems and optionally one or more second catalyst systems in a dual reactor system or a multiple reactor system, wherein first catalyst system comprises;
(a) one or more procatalysts comprising a metal-ligand complex of formula (I):

wherein:
M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; and n is an integer of from 0 to 3, and wherein when n is 0, X is absent; and 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; and 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 oxygen 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 oxygen 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 ), 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 or absent;
R 1a and R 1b independently are (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 )2NC(O)— or halogen atom;
R 3 , R 6 , R 8 , R 9 , R 11 , and R 14 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 )2NC(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 )2NC(O)—, or halogen atom;
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 )2NC(O)—, or halogen atom;

optionally two or more the R 3 , R 6 , R 8 , R 9 , R 11 , and R 14 groups can combine together into ring structures, with such ring structures having from 3 to 50 atoms in the ring excluding any hydrogen atoms;
each 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 )2NC(O)—, hydrocarbylene, and heterohydrocarbylene groups is independently unsubstituted or substituted with one or more R S substituents;
wherein each R S independently is a halogen atom, polyfluoro substitution, perfluoro substitution, 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; and

(b) 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.

2. The polymerization process according to claim 1 , wherein R 3 and R 14 are independently chosen from tert-octyl or tert-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 1a and each R 1b is independently chosen tert-butyl, n-propyl, 2-propyl, SiMe 3 , —Si(Me) 2 tBu, 3,5-di-tert-butylphenyl, 3,5-di-methylphenyl, or phenyl.

6. The polymerization process according to claim 1 , wherein each R 1a and each R 1b is tert-butyl.

7. The polymerization process according to claim 1 , wherein each R 1a and each R 1b is tert-butyl; R 3 and R 14 is 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 1a and each R 1b is tert-butyl; R 3 and R 14 is 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 1a and each R 1b is tert-butyl; R 3 and R 14 is 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 1a and each R 1b is tert-butyl; R 3 and R 14 is 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—.

Assignees

• Dow Global Technologies Llc

Inventors

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

Classifications

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F2/001

  Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer (C08F295/00, C08F297/00 take precedence) · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C08F4/60193

  OOOO · CPC title

• C08F4/64193

  OOOO · CPC title