High glass transition temperature photoimageable polycarbonate polymers with pendent polycyclic functional groups

Patent metadata

Field	Value
Publication number	US-9527957-B2
Application number	US-201414759708-A
Country	US
Kind code	B2
Filing date	Feb 28, 2014
Priority date	Feb 28, 2013
Publication date	Dec 27, 2016
Grant date	Dec 27, 2016

Abstract

Embodiments in accordance with the present invention relate generally to polycarbonate polymers having repeat units derived from polycyclic-epoxide monomers and methods of using such polymers and compositions containing them, and more specifically to polymers and compositions of polycarbonates that encompass repeat units derived from norbornane and tetracyclododecane, and methods of using such compositions.

First claim

What is claimed is:

1. A compound of the formula (I):

wherein:
m is an integer from 0 to 2, inclusive;
X is —CH 2 — or —CH 2 —CH 2 —;
each occurrence of R 1 , R 2 , R 3 and R 4 independently represents hydrogen, ethyl, linear or branched C 3 -C 12 -alkyl, C 3 -C 12 -cycloalkyl, C 6 -C 12 -bicycloalkyl, C 7 -C 14 -tricycloalkyl, C 10 -C 14 -tetracycloalkyl, C 6 -C 10 -aryl, C 6 -C 10 -aryl-C 1 -C 3 -alkyl, C 5 -C 10 -heteroaryl, C 5 -C 10 -heteroaryl-C 1 -C 3 -alkyl, C 1 -C 12 -alkoxy, C 3 -C 12 -cycloalkoxy, C 6 -C 12 -bicycloalkoxy, C 7 -C 14 -tricycloalkoxy, C 10 -C 14 -tetracycloalkoxy, C 6 -C 10 -aryloxy-C 1 -C 3 -alkyl, C 5 -C 10 -heteroaryloxy-C 1 -C 3 -alkyl, C 6 -C 10 -aryloxy, C 5 -C 10 -heteroaryloxy, C 1 -C 6 -acyloxy and halogen; or
R 1 and R 2 or R 2 and R 3 or R 3 and R 4 taken together with the carbon atom to which they are attached form a C 3 -C 12 -cycloalkyl ring optionally containing one or more hetero atoms selected from nitrogen, oxygen and sulfur;
each occurrence of R 5 and R 6 independently represents hydrogen, methyl, ethyl, linear or branched C 3 -C 12 -alkyl; or
R 5 and R 6 taken together with the carbon atom to which they are attached form a C 3 -C 12 -cycloalkyl ring optionally containing one or more hetero atoms selected from nitrogen, oxygen and sulfur;
R 7 represents hydrogen, methyl, ethyl, linear or branched C 3 -C 12 -alkyl and phenyl;
or an enantiomer, stereoisomer or a racemic mixture thereof; and
with the exception of following compounds:
2-(bicyclo[2.2.1]heptan-2-yl)oxirane;
2-(6-phenylbicyclo[2.2.1]heptan-2-yl)oxirane; and
2-(5-phenylbicyclo[2.2.1]heptan-2-yl)oxirane.

2. The compound according to claim 1 , wherein:
m is 0 or 1;
X is CH 2 ;
each occurrence of R 1 , R 2 , R 3 and R 4 independently represents hydrogen, cyclohexyl, bicyclo[2.2.1]heptanyl and decahydro-1,4:5,8-dimethanonaphthalenyl; and
each occurrence of R 5 and R 6 independently represents hydrogen, methyl and ethyl; and
R 7 is hydrogen.

3. The compound according to claim 1 , which is selected from:
(S)-2-((1S,2S,4R)-bicyclo[2.2.1]heptan-2-yl)oxirane;
(R)-2-((1S,2S,4R)-bicyclo[2.2.1]heptan-2-yl)oxirane;
(S)-2-((1R,2R,4S)-bicyclo[2.2.1]heptan-2-yl)oxirane;
(R)-2-((1R,2R,4S)-bicyclo[2.2.1]heptan-2-yl)oxirane;
2-(6-cyclohexylbicyclo[2.2.1]heptan-2-yl)oxirane;
2-(5-cyclohexylbicyclo[2.2.1]heptan-2-yl)oxirane;
2-([2,2′-bi(bicyclo[2.2.1]heptan)]-6-yl)oxirane;
2-([2,2′-bi(bicyclo[2.2.1]heptan)]-5-yl)oxirane;
2-(6-(decahydro-1,4:5,8-dimethanonaphthalen-2-yl)bicyclo[2.2.1]heptan-2-yl)oxirane;
2-(5-(decahydro-1,4:5,8-dim ethanonaphthalen-2-yl)bicyclo[2.2.1]heptan-2-yl)oxirane; and
2-(decahydro-1,4:5,8-dimethanonaphthalen-2-yl)oxirane.

4. A polymer comprising the repeat units of formula (III), said repeat unit is derived from a compound of formula (I):

wherein:
in is an integer from 0 to 2, inclusive;
X is —CH 2 — or —CH 2 —CH 2 —;
each occurrence of R 1 , R 2 , R 3 and R 4 independently represents hydrogen, ethyl, linear or branched C 3 -C 12 -alkyl, C 3 -C 12 -cycloalkyl, C 6 -C 12 -bicycloalkyl, C 7 -C 14 -tricycloalkyl, C 10 -C 14 -tetracycloalkyl, C 6 -C 10 -aryl, C 6 -C 10 -aryl-C 1 -C 3 -alkyl, C 5 -C 10 -heteroaryl, C 5 -C 10 -heteroaryl-C 1 -C 3 -alkyl, C 1 -C 12 -alkoxy, C 3 -C 12 -cycloalkoxy, C 6 -C 12 -bicycloalkoxy, C 7 -C 14 -tricycloalkoxy, C 10 -C 14 -tetracycloalkoxy, C 6 -C 10 -aryloxy-C 1 -C 3 -alkyl, C 5 -C 10 -heteroaryloxy-C 1 -C 3 -alkyl, C 6 -C 10 -aryloxy, C 5 -C 10 -heteroaryloxy, C 1 -C 6 -acyloxy and halogen; or
R 1 and R 2 or R 2 and R 3 or R 3 and R 4 taken together with the carbon atom to which they are attached form a C 3 -C 12 -cycloalkyl ring optionally containing one or more hetero atoms selected from nitrogen, oxygen and sulfur; and
each occurrence of R 5 and R 6 independently represents hydrogen, methyl, ethyl, linear or branched C 3 -C 12 -alkyl; or
R 5 and R 6 taken together with the carbon atom to which they are attached form a C 3 -C 12 -cycloalkyl ring optionally containing one or more hetero atoms selected from nitrogen, oxygen and sulfur.

5. The polymer according to claim 4 , wherein:
m is 0 or 1;
X is CH 2 ;
each occurrence of R 1 , R 2 , R 3 and R 4 independently represents hydrogen, phenyl, cyclohexyl, bicyclo[2.2.1]heptanyl and decahydro-1,4:5,8-dimethanonaphthalenyl; and
each occurrence of R 5 and R 6 independently represents hydrogen, methyl and ethyl.

6. The polymer according to claim 4 , wherein said repeat unit is derived from a compound selected from one or more of the following:
2-(bicyclo[2.2.1]heptan-2-yl)oxirane;
2-(bicyclo[2.2.1]heptan-2-yl)oxirane;
2-(6-phenylbicyclo[2.2.1]heptan-2-yl)oxirane;
2-(5-phenylbicyclo[2.2.1]heptan-2-yl)oxirane;
(S)-2-((1S,2S,4R)-bicyclo[2.2.1]heptan-2-yl)oxirane;
(R)-2-((1S,2S,4R)-bicyclo[2.2.1]heptan-2-yl)oxirane;
(S)-2-((1R,2R,4S)-bicyclo[2.2.1]heptan-2-yl)oxirane;
(R)-2-((1R,2R,4S)-bicyclo[2.2.1]heptan-2-yl)oxirane;
2-(6-cyclohexylbicyclo[2.2.1]heptan-2-yl)oxirane;
2-(5-cyclohexylbicyclo[2.2.1]heptan-2-yl)oxirane;
2-([2,2′-bi(bicyclo[2.2.1]heptan)]-6-yl)oxirane;
2-([2,2′-bi(bicyclo[2.2.1]heptan)]-5-yl)oxirane;
2-(6-(decahydro-1,4:5,8-dimethanonaphthalen-2-yl)bicyclo[2.2.1]heptan-2-yl)oxirane;
2-(5-(decahydro-1,4:5,8-dimethanonaphthalen-2-yl)bicyclo[2.2.1]heptan-2-yl)oxirane; and
2-(decahydro-1,4:5,8-dimethanonaphthalen-2-yl)oxirane.

7. The polymer according to claim 4 , wherein the weight average molecular weight of said polymer is from about 1,000 to about 300,000.

8. The polymer according to claim 4 , wherein said polymer exhibits a glass transition temperature of at least about 60° C.

9. The polymer according to claim 4 , wherein said polymer exhibits a glass transition temperature of at least about 100° C.

10. A process for making a polymer of formula (III) according to claim 4 comprising:
reacting a compound of formula (I) with carbon dioxide in the presence of a ligand-supported metal catalyst:

wherein:
m is an integer from 0 to 2, inclusive;
X is —CH 2 — or —CH 2 —CH 2 —;
each occurrence of R 1 , R 2 , R 3 and R 4 independently represents hydrogen, ethyl, linear or branched C 3 -C 12 -alkyl, C 3 -C 12 -cycloalkyl, C 6 -C 12 -bicycloalkyl, C 7 -C 14 -tricycloalkyl, C 10 -C 14 -tetracycloalkyl, C 6 -C 10 -aryl, C 6 -C 10 -aryl-C 1 -C 3 -alkyl, C 5 -C 10 -heteroaryl, C 5 -C 10 -heteroaryl-C 1 -C 3 -alkyl, C 1 -C 12 -alkoxy, C 3 -C 12 -cycloalkoxy, C 6 -C 12 -bicycloalkoxy, C 7 -C 14 -tricycloalkoxy, C 10 -C 14 -tetracycloalkoxy, C 6 -C 10 -aryloxy-C 1 -C 3 -alkyl, C 5 -C 10 -heteroaryloxy-C 1 -C 3 -alkyl, C 6 -C 10 -aryloxy, C 5 -C 10 -heteroaryloxy, C 1 -C 6 -acyloxy and halogen;
R 1 and R 2 or R 2 and R 3 or R 3 and R 4 taken together with the carbon atom to which they are attached form a C 3 -C 12 -cycloalkyl ring optionally containing one or more hetero atoms selected from nitrogen, oxygen and sulfur; and
each occurrence of R 5 and R 6 independently represents hydrogen, methyl, ethyl, linear or branched C 3 -C 12 -alkyl; or
R 5 and R 6 taken together with the carbon atom to which they are attached form a C 3 -C 12 -cycloalkyl ring optionally containing one or more hetero atoms selected from nitrogen, oxygen and sulfur.

11. The process according to claim 10 which includes a halogenated solvent.

12. The process according

Assignees

• Promerus Llc

Inventors

• Tsang W C Peter
• Bell Andrew
• Seto Keitaro

Classifications

• G03F7/0045

  with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors · CPC title

• G03F7/0392

  the macromolecular compound being present in a chemically amplified positive photoresist composition · CPC title

• C09D169/00

  Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates · CPC title

• C08G64/06 Primary

  not containing aliphatic unsaturation · CPC title

• C07D303/04 Primary

  containing only hydrogen and carbon atoms in addition to the ring oxygen atoms · CPC title