Metal-ligand complex, olefin polymerization catalyst derived therefrom, and olefin polymerization method utilizing the catalyst

Patent metadata

Field	Value
Publication number	US-9862734-B2
Application number	US-201415032150-A
Country	US
Kind code	B2
Filing date	Nov 11, 2014
Priority date	Dec 19, 2013
Publication date	Jan 9, 2018
Grant date	Jan 9, 2018

Abstract

A metal-ligand complex has formula (I): wherein J, L, M, R 1 , R 2 , R 3 , R 4 , X, p, q, and r are defined herein. The metal-ligand complex is useful as a catalyst or catalyst precursor for olefin polymerization.

First claim

The invention claimed is:

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

wherein
J is a monoanionic moiety selected from (R K )(R L )(R X )P═N—, (R K )(R L )C═N—, (R K )((R L )(R X )N)C═N—, (R K )(R L )B—O—, R K O—, R K S—, R K S(O)—, (R K )(R L )N—, (R K N═C(R L )—N(R X ))—, (R K )(R L )NO—, R K C(O)O—, R K C(O)NH—, and (R K )(R L )P—, wherein each R K , R L , and R X is independently is hydrogen, (C 1 -C 40 )hydrocarbyl-, ((C 1 -C 15 )hydrocarbyl) 3 Si—, ((C 1 -C 15 )hydrocarbyl) 2 N—, or (C 1 -C 40 )heterohydrocarbyl-; provided that wne J is (R K )(R L )P— or (R K )(R L )N—, R K and R L are optionally taken together to form (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene, or R K and R L are optionally taken together to form a group double bonded to P—, or one of R K and R L is optionally taken together with one of R 1 , R 2 , R 3 , R 4 , or L to form a (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene, or one of R K and R L is optionally covalently bonded to X; and provided that when J is R K O— or R K S—, R K is optionally taken together with one of R 1 , R 2 , R 3 , R 4 , or L to form a (C 1 -C 40 )heterohydrocarbylene, or R K is optionally covalently bonded to X;
L is independently at each occurrence halogen, hydrogen, ((C 1 -C 40 )hydrocarbyl)C(O)N(H)—, ((C 1 -C 40 )hydrocarbyl)C(O)N(H)(C 1 -C 20 )hydrocarbyl-, ((C 1 -C 40 )hydrocarbyl)C(O)O—, (C 1 -C 40 )hydrocarbyl-, (C 1 -C 40 )heterohydrocarbyl-, R K (R L )N—, R L O—, R L S—, or R K (R L )P—, wherein each of R K and R L independently is as defined above; and each occurrence of L is a monoanionic moiety that is bonded to M;
M is a metal of any one of Groups 3, 4, 5, and 6 of a Periodic Table of the Elements, the metal being in a formal oxidation state of +2, +3, +4, +5, or +6;
R 1 , R 2 , R 3 , and R 4 are independently at each occurrence hydrogen, (C 1 -C 40 )hydrocarbyl-, ((C 1 -C 40 )hydrocarbyl)O—, ((C 1 -C 40 )hydrocarbyl)S—, ((C 1 -C 40 )hydrocarbyl) 3 Si—, or (C 1 -C 40 )heterohydrocarbyl-;
X is a neutral Lewis base group selected from R X N(R K )(R L ), R X ═N(R K ), R K O(R L ), R K S(R L ), and R X P(R K )(R L ), wherein each of R K , R L , and R X independently is as defined above;
p is 0, 1, 2, or 3, and q is 0 or 1, provided that the sum of p and q is at least 1;
r is 2 or 3;
two occurrences of L are optionally taken together to form a (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene, or (R D ) 2 C═C(R D )—C(R D )═C(R D ) 2 , wherein each R D independently is H, unsubstituted (C 1 -C 6 )alkyl, phenyl, or naphthyl;
J and one of R 1 , R 2 , R 3 , and R 4 are optionally taken together to form (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene;
one occurrence of L and one of R 1 , R 2 , R 3 , and R 4 are optionally taken together to form (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene;
one occurrence of X and one of R 1 , R 2 , R 3 , and R 4 are optionally taken together to form (C 1 -C 40 )heterohydrocarbylene;
any two of R 1 , R 2 , R 3 , and R 4 are optionally taken together to form a (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene;
X and J are optionally taken together to form a monoanionic bidentate moiety X-J, provided that when X-J is bound to M to form a fragment having the structure

then R 5 , R 6 , and R 7 are each independently hydrogen, (C 1 -C 40 )hydrocarbyl-, ((C 1 -C 40 )hydrocarbyl)O—, ((C 1 -C 40 )hydrocarbyl)S—, ((C 1 -C 40 )hydrocarbyl) 3 Si—, or (C 1 -C 40 )heterohydrocarbyl-; one of R 5 , R 6 , or R 7 is optionally taken together with one of R 1 , R 2 , R 3 , R 4 , or L to form a (C 2 -C 40 )hydrocarbylene or (C1-C40)heteohydrocarbylene; and provided that when X-J is bound to M via an anionic nitrogen and a Lewis base nitrogen, X-J and M form a four-membered metallocycle or a six-membered metallocycle; and
each of the above-mentioned (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, (C 2 -C 40 )hydrocarbylene, and (C 1 -C 40 )heterohydrocarbylene independently is the same or different and is unsubstituted or substituted with one or more substituents R S selected from halogen, unsubstituted (C 1 -C 18 )hydrocarbyl, F 3 C—, FCH 2 O—, F 2 HCO—, F 3 CO—, oxo, R 3 Si—, 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)—, wherein each R independently is an unsubstituted (C 1 -C 18 )hydrocarbyl.

2. The metal-ligand complex of claim 1 , wherein M is Ti, Zr, or Hf.

3. The metal-ligand complex of claim 1 , wherein one of R 1 and R 2 and one of R 3 and R 4 are taken together to form

4. The metal-ligand complex of claim 1 , having formula (II)

wherein
L, M, R 1 , R 2 , R 3 , and R 4 are as defined in claim 1 ;
R 5 , R 6 , and R 7 are each independently hydrogen, (C 1 -C 40 )hydrocarbyl-, ((C 1 -C 40 )hydrocarbyl)O—, ((C 1 -C 40 )hydrocarbyl)S—, ((C 1 -C 40 )hydrocarbyl) 3 Si—, or (C 1 -C 40 )heterohydrocarbyl-;
one occurrence of L and any one of R 1 , R 2 , R 3 , or R 4 are optionally taken together to form (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene;
any two of R 1 , R 2 , R 3 , or R 4 are optionally taken together to form a (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene;
one of R 5 , R 6 , or R 7 is optionally taken together with one of R 1 , R 2 , R 3 , R 4 , or L to form a (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene; and
the two occurrences of L are optionally taken together to form a (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene, or (R D ) 2 C═C(R D )—C(R D )═C(R D ) 2 , wherein each R D independently is H, unsubstituted (C 1 -C 6 )alkyl, phenyl, or naphthyl.

5. The metal-ligand complex of claim 4 , selected from the group consisting of

and combinations thereof.

6. The metal-ligand complex of claim 1 , having formula (III)

wherein
L, M, p, R 1 , R 2 , R 3 , R 4 , and X are as defined in claim 1 ;
J 1 is N or P;
R 8 and R 9 are each independently hydrogen, (C 1 -C 40 )hydrocarbyl-, ((C 1 -C 40 )hydrocarbyl)O—, ((C 1 -C 40 )hydrocarbyl)S—, ((C 1 -C 15 )hydrocarbyl) 3 Si—, or (C 1 -C 40 )heterohydrocarbyl-;
one occurrence of L and any one of R 1 , R 2 , R 3 , or R 4 are optionally taken together to form (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene;
the two occurrences of L are optionally taken together to form a (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene, or (R D ) 2 C═C(R D )—C(R D )═C(R D ) 2 , wherein each R D independently is H, unsubstituted (C 1 -C 6 )alkyl, phenyl, or naphthyl;
any two of R 1 , R 2 , R 3 , or R 4 optionally are taken together to form a (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene;
R 8 and R 9 are optionally taken together to form (C 2 -C 40 )hydrocarbylene or (C 1 -C 40 )

Assignees

• Dow Global Technologies Llc

Inventors

• Klosin Jerzy
• Fontaine Philip P
• Figueroa Ruth
• Pearson David M
• Senecal Todd D

Classifications

• C08F210/02

  Ethene · CPC title

• C08F4/659

  Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F4/64072

  NN · CPC title

• C08F4/64044

  NN · CPC title

• C07F7/28

  Titanium compounds · CPC title