Organopalladium compounds as polymerization catalysts

Patent metadata

Field	Value
Publication number	US-9415354-B2
Application number	US-201514827571-A
Country	US
Kind code	B2
Filing date	Aug 17, 2015
Priority date	Aug 15, 2014
Publication date	Aug 16, 2016
Grant date	Aug 16, 2016

Abstract

A series of bicycloalkene-palladium compounds having utility as addition polymerization catalysts are disclosed. Also disclosed are the methods of making these compounds.

First claim

What is claimed is:

1. A compound of the formula (I):

wherein,

is (C 5 -C 10 )cycloalkene, (C 7 -C 12 )bicycloalkene or (C 8 -C 12 )tricycloalkene group;
M is nickel, palladium or platinum;
LB is a Lewis Base;
Z ⊖ is a weakly coordinating anion;
Y is PR 3 or O═PR 3 , where R is independently selected from methyl, ethyl, (C 3 -C 6 )alkyl, substituted or unsubstituted (C 3 -C 7 )cycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aralkyl, methoxy, ethoxy, (C 3 -C 6 )alkoxy, substituted or unsubstituted (C 3 -C 7 )cycloalkoxy, (C 6 -C 10 )aryloxy or (C 6 -C 10 )aralkyloxy; and
R 1 is methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aralkyl or R 2 CO, where R 2 is methyl, ethyl or (C 3 -C 6 )alkyl.

2. The compound of claim 1 , wherein:
LB is selected from acetonitrile, propionitrile, n-butyronitrile, tert-butyronitrile, C 6 H 5 CN, C 6 H 5 CH 2 CN, 2,4,6-trimethylbenzonitrile, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine, 2,6-di-t-butylpyridine, 2,4-di-t-butylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, pyrazine, 2,3,5,6-tetramethylpyrazine, diethyl ether, di-n-butyl ether, dibenzyl ether, tetrahydrofuran, tetrahydropyran, benzophenone, triphenylphosphine oxide, triphenyl phosphate or PR 3 , where R is independently selected from methyl, ethyl, (C 3 -C 6 )alkyl, substituted or unsubstituted (C 3 -C 7 )cycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aralkyl, methoxy, ethoxy, (C 3 -C 6 )alkoxy, substituted or unsubstituted (C 3 -C 7 )cycloalkoxy, (C 6 -C 10 )aryloxy or (C 5 -C 10 )aralkyloxy; and
Z ⊖ is selected from B(C 6 F 5 ) 4 ⊖ , B[C 6 H 3 (CF 3 ) 2 ] 4 ⊖ , B(C 6 H 5 ) 4 ⊖ , [Al(OC(CF 3 ) 2 C 6 F 5 ) 4 ] ⊖ , BF 4 ⊖ , PF 6 ⊖ , AsF 6 ⊖ , SbF 6 ⊖ , (CF 3 SO 2 )N ⊖ or CF 3 SO 3 ⊖ .

3. The compound of claim 1 , wherein

is cyclooctene, bicyclo[3,3,0]octene, bicyclo[2,2,1]hept-2-ene, bicyclo[2,2,2]oct-2-ene or tricyclo[5,2,1,0 2,6 ]dec-3-ene;
M is palladium;
LB is acetonitrile, tert-butyronitrile, C 6 H 5 CN, 2,4,6-trimethylbenzonitrile, pyridine, 4-methylpyridine, 3,5-dimethylpyridine, 4-methoxypyridine, benzophenone or triphenylphosphine oxide;
Z ⊖ is selected from B(C 6 F 5 ) 4 ⊖ , B[C 6 H 3 (CF 3 ) 2 ] 4 ⊖ , (CF 3 SO 2 )N ⊖ and CF 3 SO 3 ⊖ ;
Y is PR 3 or O═PR 3 , where R is independently selected from isopropyl, sec-butyl, tert-butyl, cyclohexyl, phenyl, benzyl, isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy, phenoxy or benzyloxy; and
R 1 is methyl, ethyl, isopropyl, sec-butyl, tert-butyl, phenyl, phenoxy or acetyl.

4. The compound of claim 1 , which is of the formula (II):

wherein,
LB is selected from pyridine, acetonitrile or C 6 H 5 CN;
Z ⊖ is selected from B(C 6 F 5 ) 4 ⊖ ), B(C 6 H 5 ) 4 ⊖ , BF 4 ⊖ or CF 3 SO 3 ⊖ ;
R is independently selected from methyl, ethyl, (C 3 -C 6 )alkyl, substituted or unsubstituted (C 3 -C 7 )cycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aralkyl, methoxy, ethoxy, (C 3 -C 6 )alkoxy, substituted or unsubstituted (C 3 -C 7 )cycloalkoxy, (C 6 -C 10 )aryloxy or (C 6 -C 10 )aralkyloxy; and
R 1 is methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, (C 6 -C 10 )aralkyl or R 2 CO, where R 2 is methyl, ethyl or (C 3 -C 6 )alkyl.

5. The compound of claim 4 , wherein:
LB is acetonitrile;
Z ⊖ is B(C 6 F 5 ) 4 ⊖ ;
R is n-propyl, isopropyl, tert-butyl or phenyl; and
R 1 is n-propyl, isopropyl, tert-butyl or —COCH 3 .

6. The compound of claim 4 , which is of the formula (IIA):

wherein:
LB is acetonitrile or pyridine;
Z ⊖ is selected from B(C 6 F 5 ) 4 ⊖ or BF 4 ⊖ ; and
R 1 is isopropyl or —COCH 3 .

7. The compound of claim 6 , wherein LB is acetonitrile.

8. The compound of claim 6 , wherein LB is pyridine.

9. The compound of claim 6 , wherein Z ⊖ is B(C 6 F 5 ) 4 ⊖ .

10. The compound of claim 6 , wherein Z ⊖ is BF 4 ⊖ .

11. The compound of claim 4 , which is selected from the group consisting of:

wherein Py is pyridine.

12. A compound of formula (III):

wherein,

is (C 5 -C 10 )cycloalkene, (C 7 -C 12 )bicycloalkene or (C 8 -C 12 )tricycloalkene group;
M is nickel, palladium or platinum;
X is halogen, triflate, mesylate or tosylate;
Y is PR 3 or O═PR 3 , where R is independently selected from methyl, ethyl, (C 3 -C 6 )alkyl, substituted or unsubstituted (C 3 -C 7 )cycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aralkyl, methoxy, ethoxy, (C 3 -C 6 )alkoxy, substituted or unsubstituted (C 3 -C 7 )cycloalkoxy, (C 6 -C 10 )aryloxy or (C 6 -C 10 )aralkyloxy; and
R 1 is methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aralkyl or R 2 CO, where R 2 is methyl, ethyl or (C 3 -C 6 )alkyl; and
with the proviso that when R is phenyl R 1 is not methyl.

13. The compound of claim 12 , wherein

is cyclooctene, bicyclo[3,3,0]octene, bicyclo[2,2,1]hept-2-ene, bicyclo[2,2,2]oct-2-ene or tricyclo[5,2,1,0 2.6 ]dec-3-ene;
M is palladium;
X is chlorine or triflate;
Y is PR 3 or O═PR 3 , where R is independently selected from isopropyl, sec-butyl, tert-butyl, cyclohexyl, phenyl, benzyl, isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy, phenoxy or benzyloxy; and
R 1 is methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl, phenyl, phenoxy or acetyl; and
with the proviso that when R is phenyl R 1 is not methyl.

14. The compound of claim 12 , which is of the formula (IIIA):

wherein:
X is chlorine or triflate; and
R 1 is n-propyl, isopropyl or —COCH 3 .

15. The compound of claim 14 , wherein R 1 is n-propyl, isopropyl or —COCH 3 .

16. The compound of claim 12 , which is selected from the group consisting of:

17. A polymerization composition comprising:
a compound of the formula (I):

wherein,

is (C 5 -C 10 )cycloalkene, (C 7 -C 12 )bicycloalkene or (C 8 -C 12 )tricycloalkene group;
M is nickel, palladium or platinum;
LB is a Lewis Base;
Z ⊖ is a weakly coordinating anion;
Y is PR 3 or O═PR 3 , where R is independently selected from methyl, ethyl, (C 3 -C 6 )alkyl, substituted or unsubstituted (C 3 -C 7 )cycloalkyl, (C

Assignees

• Promerus Llc

Inventors

• Bell Andrew

Classifications

• C07F15/006

  Palladium compounds · CPC title

• C08F299/02

  from unsaturated polycondensates · CPC title

• C08F32/04

  having one carbon-to-carbon double bond · CPC title

• B01D67/0002

  Organic membrane manufacture · CPC title

• B01D69/08

  Hollow fibre membranes (manufacture of hollow fibres D01D5/24, D01F1/08) · CPC title