Water soluble norbornene-type polymers and photoimageable compositions thereof

Patent metadata

Field	Value
Publication number	US-9328179-B2
Application number	US-201414285806-A
Country	US
Kind code	B2
Filing date	May 23, 2014
Priority date	May 23, 2013
Publication date	May 3, 2016
Grant date	May 3, 2016

Abstract

Embodiments in accordance with the present invention encompass water soluble polycyclic vinyl addition polymers having a norbornene type repeat unit derived from a norbornene type of monomer that encompasses a saccharide functional moiety. Embodiments in accordance with the present invention also encompass low and high molecular weight polymers with low catalyst loading.

First claim

What is claimed is:

1. A method for making a water soluble vinyl addition norbornene-type polymer comprising:
charging a reaction vessel with a first type of norbornene-type monomer represented by Formula A1:

where m is 0 or 1, at least one of R 1 , R 2 , R 3 , and R 4 is a saccharide functional moiety selected from monosaccharide, disaccharide, trisaccharide, oligosaccharide or a polysaccharide, and the remaining R 1 , R 2 , R 3 , and R 4 are hydrogen;
further charging the reaction vessel with water, a catalyst, formic acid as a chain transfer activating agent, and an optional co-catalyst where the monomer to catalyst ratio is at least 500/1;
providing agitation to the reaction vessel contents to promote dissolution of the first type of norbornene-type monomer, catalyst, chain transfer activating agent and optional co-catalyst in the solvent; and
providing heat and continued agitation to the contents for 18 to 120 hours to facilitate polymerization of the first type of norbornene-type monomer to obtain a polymer having a weight average molecular weight (M w ) of at least 18,000.

2. The method of claim 1 , further comprising:
charging the reaction vessel with a second type of norbornene-type monomer represented by Formula A2 distinct from said first type of norbornene-type monomer:

where p is 0 or 1, at least one of R 5 , R 6 , R 7 , and R 8 is a hydrocarbyl group, halohydrocarbyl group or a heterohydrocarbyl group and the remaining R 5 , R 6 , R 7 , and R 8 are hydrogen.

3. The method of claim 1 where the catalyst is selected from: allyl palladium chloride dimer,
(acetonitrile)bis(triisopropylphosphine)palladium(acetate) tetrakis(pentafluoro-phenyl)borate,
nonasodium hydrido tris (tri(metasulfonatophenyl)phosphine)palladium methanesulfonate,
(acetonitrile)bis(t-butyldicyclohexylphosphine)palladium (acetate) tetrakis(perfluorophenyl)borate,
and mixtures in any combination thereof.

4. The method of claim 1 where the co-catalyst is selected from one or more of the following:
Li tetrakis(pentafluorophenyl)borate etherate (LiFABA), and
N-dimethylanilinium tetrakis-(pentafluorophenyl)borate (DANFABA).

5. The method of claim 1 where the formic acid is present in an amount of from 0.1 to 30 mol % of the total monomer loading to the reaction mixture.

6. The method of claim 1 , where the formic acid is present in an amount of from 1 to 10 mol % of the total monomer loading to the reaction mixture.

7. A water soluble vinyl addition norbornene-type polymer comprising a first type of norbornene-type repeating unit represented by Formula B1 which is derived from a monomer of formula A1:

where m is 0 or 1, at least one of R 1 , R 2 , R 3 , and R 4 is a saccharide functional moiety selected from monosaccharide, disaccharide, trisaccharide, oligosaccharide or a polysaccharide, and the remainingR 1 , R 2 , R 3 , and R 4 are hydrogen; and
said polymer has a weight average molecular weight (M w ) of at least 18,000.

8. The polymer of claim 7 , further comprising the second type of norbornene-type repeating unit represented by Formula B2 derived from a second norbornene-type monomer represented by Formula A2:

where p is 0 or 1, at least one of R 5 , R 6 , R 7 , and R 8 is a hydrocarbyl group, halohydrocarbyl group, or a heterohydrocarbyl group, and the remaining R 5 , R 6 , R 7 , and R 8 are hydrogen.

9. The polymer of claim 7 , where said saccharide functional moiety is a monosaccharide, a disaccharide, or an oligosaccharide selected from a derivative of an aldose, a ketose, L isomers thereof, D isomers thereof, cyclic isomers thereof, and combinations thereof.

10. The polymer of claim 9 , where said aldose is selected from erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, or talose, and combinations thereof; and where said ketose is selected from erythrulose, xylulose, ribulose, tagatose, sorbose, or fructose, and combinations thereof.

11. The polymer of claim 7 , which is poly(N-norbornene methyl gluconamide) having a weight average molecular weight (M w ) from 18,000 to 130,000.

12. An aqueous based crosslinkable composition comprising:
a water soluble vinyl addition norbornene-type polymer comprising a first type of norbornene-type repeating unit represented by Formula B1 which is derived from a monomer of formula A1:

where m is 0 or 1, at least one of R 1 , R 2 , R 3 , and R 4 is a saccharide functional moiety selected from monosaccharide, disaccharide, trisaccharide, oligosaccharide or a polysaccharide, and the remaining R 1 , R 2 , R 3 , and R 4 are hydrogen; and said polymer has a weight average molecular weight (M w ) of at least 18,000;
a casting solvent; and
a crosslinking agent.

13. The composition of claim 12 where the crosslinking agent is glutaraldehyde.

14. The composition of claim 13 which is capable of thermally curing at a temperature below 200° C.

15. A method of forming a crosslinking composition comprising combining
a water soluble vinyl addition norbornene-type polymer of claim 12 ;
a casting solvent; and
a crosslinking agent.

16. The method of claim 15 where a crosslinking additive is glutaraldehyde.

17. A method of forming a patterned image comprising:
forming a layer of a crosslinking composition of claim 12 ;
imagewise exposing the layer to appropriate actinic radiation;
causing exposed portions of the layer to undergo crosslinking; and
removing unexposed portions of the layer to form said patterned image.

18. An aqueous based photoimageable composition comprising:
a water soluble vinyl addition norbornene-type polymer of claim 12 ;
a photoactive compound; and
a solvent.

Assignees

• Promerus Llc
• Sumitomo Bakelite Co

Inventors

• Rhodes Larry F
• Burgoon Hugh
• Smith Steven J
• Fujita Kazuyoshi

Classifications

• G03F7/0395

  the macromolecular compound having a backbone with alicyclic moieties · CPC title

• G03C1/73

  containing organic compounds · CPC title

• C08F232/08

  having condensed rings (coumarone-indene polymers C08F244/00) · CPC title

• C08F132/04

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

• C08F32/04 Primary

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