Group transfer polymerization for the production of functional monomers

Patent metadata

Field	Value
Publication number	US-11286340-B2
Application number	US-202016775755-A
Country	US
Kind code	B2
Filing date	Jan 29, 2020
Priority date	Jan 29, 2019
Publication date	Mar 29, 2022
Grant date	Mar 29, 2022

Abstract

The present invention provides efficient processes for preparing brush polymers. In general, the process comprises three distinct reaction steps utilizing two separate catalysts. In the first step, the initiating compound comprising norbornene is contacted with a silane in the presence of a catalyst, thereby forming a silated intermediate. This silated intermediate is then contacted with a monomer in the presence of a catalyst via Group Transfer Polymerization (GTP). The resulting compound from GTP is contacted with a ring opening metathesis polymerization (ROMP) catalyst to prepare the brush polymer. Surprisingly, the brush polymers obtained from the above process are accessed in an efficient and rapid GTP methodology as compared to prior methods.

First claim

What is claimed is:

1. A method for preparing a compound comprising Formula (V)

the method comprising:
(a) contacting an initiating compound comprising Formula (I):

in the presence of a silane and a first catalyst to form a compound comprising Formula (II):

(b) contacting the compound comprising Formula (II) with a monomer comprising Formula (III), optionally in the presence of a second catalyst:

to prepare a compound comprising Formula (IV):

and
(c) contacting the compound comprising Formula (IV) with a ring opening metathesis polymerization (ROMP) catalyst to prepare the compound comprising Formula (V);

wherein
A and B are independently selected from CH 2 or C═O;
R is selected from substituted or unsubstituted C 1 -C 10 OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1 -C 10 COR 7 , substituted or unsubstituted arylCOR 7 , substituted or unsubstituted C 1 -C 10 OCOCH═CH 2 , substituted or unsubstituted arylOCOCH═CH 2 , substituted or unsubstituted C 1 -C 10 OCOC(CH 3 )═CH 2 , substituted or unsubstituted arylOCOC(CH 3 )═CH 2 , substituted or unsubstituted C 1 -C 10 NHCOCH═CH 2 , or substituted or unsubstituted arylNHCOCH═CH 2 ;
R 1 is the residue of a group selected from the group consisting of a substituted or unsubstituted C 1 -C 10 OH, a substituted or unsubstituted arylOH, a substituted or unsubstituted C 1 -C 10 COR 7 , a substituted or unsubstituted arylCOR 7 , a substituted or unsubstituted C 1 -C 10 OCOCH═CH 2 , a substituted or unsubstituted arylOCOCH═CH 2 , a substituted or unsubstituted C 1 -C 10 OCOC(CH 3 )═CH 2 , a substituted or unsubstituted arylOCOC(CH 3 )═CH 2 , a substituted or unsubstituted C 1 -C 10 NHCOCH═CH 2 , and a substituted or unsubstituted arylNHCOCH═CH 2 ;
R 3 is CHR 8 or O;
R 4 , R 5 , and R 6 are independently selected from a group consisting of H, C 1 -C 8 substituted or unsubstituted alkyl, or substituted or unsubstituted aryl;
R 7 is selected from a group consisting of hydrogen, or substituted or unsubstituted C 1 -C 10 alkyl; X is CN, COOR 8 or CONR 9 R 10 ;
R 8 , R 9 , and R 10 are independently selected from a group consisting of H, C 1 -C 10 substituted or unsubstituted alkyl optionally substituted with at least one heteroatom on the alkyl chain, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; and
R 11 and R 12 are independently selected from a group consisting of H, C 1 -C 10 substituted or unsubstituted alkyl optionally substituted with at least one heteroatom on the alkyl chain, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

2. The method of claim 1 , wherein A and B are independently selected from —CH 2 -or C═O; R 1 is selected from substituted or unsubstituted C 1 -C 6 OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1 -C 6 COR 7 , substituted or unsubstituted arylCOR 7 , substituted or unsubstituted C 1 -C 6 OCOCH═CH 2 , substituted or unsubstituted arylOCOCH═CH 2 , substituted or unsubstituted C 1 -C 6 OCOC(CH 3 )═CH 2 , substituted or unsubstituted arylOCOC(CH 3 )═CH 2 , substituted or unsubstituted C 1 -C 6 NHCOCH═CH 2 , or substituted or unsubstituted arylNHCOCH═CH 2 ; R 3 is a CH 2 or O; R 4 , R 5 , and R 6 are independently selected from a group consisting of H, C 1 -C 4 substituted or unsubstituted alkyl, or substituted or unsubstituted aryl; R 7 is selected from a group consisting of hydrogen, or substituted or unsubstituted C 1 -C 8 alkyl; X is COOR 8 or CONR 9 R 10 ; R 8 , R 9 , and R 10 are independently selected from a group consisting of H, C 1 -C 6 substituted or unsubstituted alkyl optionally substituted with at least one heteroatom on the alkyl chain, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; and R 11 and R 12 are independently selected from a group consisting of H, C 1 -C 6 substituted or unsubstituted alkyl optionally substituted with at least one heteroatom on the alkyl chain, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

3. The method of claim 1 , wherein A and B are independently selected from —CH 2 -or C═O; R 1 is a residue of a group selected from substituted or unsubstituted C 1 -C 4 OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1 -C 4 COR 4 , substituted or unsubstituted arylCOR 4 , substituted or unsubstituted C 1 -C 4 OCOCH═CH 2 , substituted or unsubstituted arylOCOCH═CH 2 , substituted or unsubstituted C 1 -C 4 OCOC(CH 3 )═CH 2 , substituted or unsubstituted arylOCOC(CH 3 )═CH 2 , substituted or unsubstituted C 1 -C 4 NHCOCH═CH 2 , or substituted or unsubstituted arylNHCOCH═CH 2 ; R 3 is a CH 2 or O; R 4 , R 5 , and R 6 are independently selected from a group consisting of C 1 -C 4 substituted or unsubstituted alkyl, or substituted or unsubstituted aryl; R 7 is selected from a group consisting of hydrogen, or substituted or unsubstituted C 1 -C 8 alkyl; X is COOR 8 or CONR 9 R 10 ; and R 8 , R 9 , and R 10 are independently selected from a group consisting of H, C 1 -C 4 substituted or unsubstituted alkyl optionally substituted with at least one heteroatom on the alkyl chain, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; and R 11 and R 12 are independently selected from a group consisting of H, C 1 -C 4 substituted or unsubstituted alkyl optionally substituted with at least one heteroatom on the alkyl chain, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

4. The method of claim 1 , wherein A and B are C═O; R 1 is selected from a group consisting of CH 2 CH 2 OCOCH═CH 2 , CH 2 CH 2 OCOC(CH 3 )═CH 2 , —CH 2 CH 2 NHCOCH═CH 2 ; R 3 is CH 2 ; R 4 , R 5 , and R 6 is selected from a group consisting of methyl, tert-butyl, or phenyl; R 7 is selected from a group consisting of hydrogen, methyl, or ethyl; X is COOR 8 ; R 8 is selected from a group consisting of hydrogen, methyl, ethyl, 2-methoxymethyl, n-butyl, iso-butyl, or 2-ethylhexyl; and R 11 and R 12 are H.

5. The method of claim 1 , wherein the mole ratio of the silane to the compound comprising Formula (I) in step (a) ranges from about 0.95:1.00 to about 1.50:1.00.

6. The method of claim 1 , wherein the first catalyst is a Lewis Acid catalyst, and the mole ratio of the first catalyst to the compound comprising Formula (I) in step (a) ranges from about 0.001:1.0 to about 0.1:1.0.

7. The method of claim 1 , wherein the reaction temperature of step (a) ranges from about −10° C. to about 80° C.

8. The method of claim 1 , wherein in step (b) the monomer comprising Formula (III) is present in an amount such that the mole-to-mole ratio of the monomer comprising Formula (III) present in step (b) to the compound comprising Formula (I) present in step (a) ranges from about 10.0:1.0 to about 100.0:1.0.

9. The method of claim 1 , wherein step (b) is performed in the presence of a second catalyst, which is the same or different from the first catalyst, and the second catalyst is present in an amount such that the mole-to-mole ratio of the second catalyst present in step (b) to the compound comprising Formula (I) present in step (a) ranges from about 0.001:1.0 to

Assignees

• Univ Colorado State Res Found

Inventors

• Miyake Garret
• Pearson Ryan M
• Ryan Matthew D

Classifications

• C08G61/125 Primary

  with a five-membered ring containing one oxygen atom in the ring · CPC title

• C08G2261/418

  Ring opening metathesis polymerisation [ROMP] · CPC title

• C08G2261/136

  Comb-like structures · CPC title

• C08G2261/3245

  containing nitrogen and oxygen as heteroatoms · CPC title

• C08G61/08 Primary

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title