Biaryl hydroxythiophene group IV transition metal polymerization with chain transfer capability

Patent metadata

Field	Value
Publication number	US-12297311-B2
Application number	US-202017437271-A
Country	US
Kind code	B2
Filing date	Mar 5, 2020
Priority date	Mar 8, 2019
Publication date	May 13, 2025
Grant date	May 13, 2025

Abstract

Embodiments of this disclosure include polymerization processes that include contacting propylene and/or one or more (C4-C12)α-olefins in a reactor including a catalyst system. The catalyst system comprises a metal-ligand complex according to formula (I).

First claim

The invention claimed is:

1. A polymerization process comprising:
contacting propylene and one or more (C 4 -C 12 )α-olefins in a reactor including a catalyst system, the catalyst system comprising a chain transfer or chain shuttling agent and a metal-ligand complex according to formula (I):

where:
M is a metal chosen from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4;
each X is a monodentate or bidentate ligand independently chosen from unsaturated (C 2 -C 20 )hydrocarbon, unsaturated (C 2 -C 50 )heterohydrocarbon, (C 1 -C 50 )hydrocarbyl, (C 6 -C 50 )aryl, (C 6 -C 50 )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C 4 -C 12 )diene, halogen, —OR C , —N(R N ) 2 , and —NCOR C ;
n is 1 or 2;
each Y is —O—;
each R 1 is independently selected from the group consisting of —H, (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, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):

where each of R 31-35 , R 41-48 , and R 51-59 is independently chosen from (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 , halogen, or —H,
provided at least one R 1 in formula (I) is a radical having formula (II), a radical having formula (III), or a radical having formula (IV);

Q is (C 1 -C 12 )alkylene, or (C 1 -C 12 )heteroalkylene;
each z 1 is sulfur, oxygen, —N(R Z )—, and each z 2 is —C(R Z )—, where R Z is (C 1 -C 8 )alkyl or —H;
R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b , and R 7b are independently chosen from (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, —Si(R C ) 3 , —OR C , —CN, —CF 3 , halogen, and —H, in which optionally R 4a and R 5a , or R 5a and R 6a , or R 6a and R 7a , or R 4b and R 5b , or R 5b and R 6b , or R 6b and R 76 may be covalently connected to form an aromatic ring or a non-aromatic ring;
each R C , R N , R Z and R P in formula (I) is independently selected from the group consisting of (C 1 -C 20 )hydrocarbyl, (C 1 -C 20 )heterohydrocarbyl, and —H.

2. The polymerization process of claim 1 , wherein the catalyst system further comprises one or more cocatalysts.

3. The polymerization process of claim 1 , wherein each R 1 is a radical having formula (III), in which:
(1) R 42 and R 47 are independently chosen from (C 1 -C 20 )alkyl, —Si(R C ) 3 , —CF 3 , or halogen, and R 43 and R 46 are —H; or
(2) R 43 and R 46 are independently chosen from (C 1 -C 20 )alkyl, (C 6 -C 40 )aryl, (C 5 -C 40 )heteroaryl, —Si(R C ) 3 , —CF 3 , or halogen, and R 42 and R 47 are —H.

4. The polymerization process of claim 1 , wherein each R 1 is a radical having formula (IV), in which at least one of R 51-59 is chosen from (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , or halogen.

5. The polymerization process of claim 1 wherein each R 1 is a radical having formula (IV), in which at least one of R 53 , R 55 , and R 57 is (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , or halogen.

6. The polymerization process of claim 1 , wherein each R 1 is a radical having formula (II).

7. The polymerization process of claim 1 , wherein each R 1 is a radical having formula (II), and wherein R 32 and R 34 are independently (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , or halogen.

8. The polymerization process of claim 1 , wherein each R 1 is a radical having formula (II), and wherein R 32 and R 34 are independently (C 1 -C 20 )alkyl, substituted (C 6 -C 20 )aryl, or unsubstituted (C 6 -C 20 )aryl.

9. The polymerization process of claim 1 , wherein each R 1 is a radical having formula (II), and wherein R 32 and R 34 are independently tert-butyl, phenyl, 3,5-di(tert-butyl)phenyl, 2,4,6-trimethylphenyl, or 2,4,6-tri(iso-propyl)phenyl.

10. The polymerization process of claim 1 , wherein the reactor has a reactor temperature of 140° C. or greater.

11. The polymerization process of claim 1 , wherein the polymer process further comprises a solution polymerization, and the solution polymerization takes place at a pressure from 10 psi to 2000 psi.

12. The polymerization process of claim 1 , wherein the chain transfer or chain shuttling agent is diethyl zinc.

Assignees

• Dow Global Technologies Llc

Inventors

• Camelio Andrew M
• Bailey Brad C
• Christianson Matthew D
• Froese Robert Dj
• Devore David D

Classifications

• C08F210/16

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

• C08F210/06

  Propene · CPC title

• C08F2/04

  Polymerisation in solution (C08F2/32 takes precedence) · CPC title

• C08F4/65908

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

• C08F4/64193

  OOOO · CPC title