Amine glyoxal resins

Patent metadata

Field	Value
Publication number	US-10344115-B2
Application number	US-201715604755-A
Country	US
Kind code	B2
Filing date	May 25, 2017
Priority date	May 25, 2017
Publication date	Jul 9, 2019
Grant date	Jul 9, 2019

Abstract

Condensation polymers are prepared by agitating a mixture comprising glyoxal, a monomer comprising two or three primary aromatic amine groups, an organic solvent, and water at a temperature between 20° C. and 100° C. The resulting solution can be applied to a surface of a substrate, forming an initial film. Curing the initial film layer using two or more heating steps, wherein one of the heat steps is performed at a temperature of 150° C. to 250° C., produces a cured film layer. Depending on the relative amounts of glyoxal and monomer used, the film layer can contain predominantly high Tg imine-containing units or predominantly lower Tg aminal-containing units. All film layers were highly resistant to the solvent used to prepare the polymer. The Tg of the polymer can be about 190° C. to greater than 300° C.

First claim

What is claimed is:

1. A polymer, comprising:
i) a nitrogen-containing unit selected from the group consisting of:
divalent bis-imine units of structure (A):

trivalent imine-aminal units of structure (B):

tetravalent bis-aminal units of structure (C):

and
combinations thereof;
ii) divalent and/or trivalent bridging groups of formula (1):
K′ *) y′   (1),

wherein y′ is 2 or 3, and K′ is a radical comprising at least one 6-carbon aromatic ring; and
iii) polymer chain-terminating monovalent end groups;
wherein
each nitrogen of a given one of the nitrogen-containing units is covalently linked to an aromatic carbon of a different one of the bridging groups, and
the end groups are covalently linked to respective bridging groups.

2. The polymer of claim 1 , wherein the polymer comprises divalent bridging units of formula (8):

wherein
carbons para to L′ are labeled 4,
L′ is a divalent group selected from the group consisting of *—O—*, *—S—*, *—N(R′)—*, *—N(H)—*, and *—R″—*, wherein R′ and *—R″—* are independent hydrocarbyl groups comprising at least 1 carbon,
each nitrogen of a given glyoxal residue, when present, is covalently linked to a carbon para to L′ of a different one of the bridging units, and
the end groups are covalently linked to respective carbons para to L′ of respective bridging groups.

3. The polymer of claim 2 , wherein L′ is *—O—*.

4. The polymer of claim 2 , wherein L′ is *—S—*.

5. The polymer of claim 2 , wherein R′ is selected from the group consisting of methyl, ethyl, propyl, isopropyl, and phenyl, and *—R″—* is selected from the group consisting of methylene (*—CH 2 —*), ethan-1,2-diyl (*—CH 2 CH 2 —*), ethen-1,2-diyl (*—CH═CH—*), isopropylidenyl, and fluorenylidenyl:

6. The polymer of claim 5 , wherein L′ is *—R″—*, and *—R″—* is *—CH 2 —*.

7. The polymer of claim 2 , wherein L′ is *—R″—*, and *—R″—* is *—C(Me) 2 -*.

8. The polymer of claim 1 , wherein the polymer has a glass transition temperature greater than 190° C.

9. The polymer of claim 1 , wherein the polymer is crosslinked.

10. The polymer of claim 1 , wherein the polymer is a product of a reaction of glyoxal and a diamine monomer of formula (14):

wherein
carbons para to L′ are labeled 4, and
L′ is a divalent group selected from the group consisting of *—O—*, *—S—*, *—N(R′)—*, *—N(H)—*, and *—R″—*, wherein R′ and *—R″—* are independent hydrocarbyl groups comprising at least 1 carbon.

11. A method of forming the polymer of claim 1 , comprising:
agitating a reaction mixture comprising i) a monomer selected from the group consisting of diamine monomers comprising two primary aromatic amine groups, triamine monomers comprising three primary aromatic amine groups, and combinations thereof, ii) an optional diluent monomer comprising one aromatic primary amine group, iii) glyoxal, iv) a water-miscible organic solvent, and v) water, thereby forming a solution comprising an initial polymer; and
heating the solution using one or more independent heating steps that includes a last heating step, wherein the last heating step is performed at a temperature of 150° C. to 250° C., thereby producing the polymer.

12. The method of claim 11 , wherein the monomer is a diamine monomer of formula (14):

wherein
carbons para to L′ are labeled 4, and
L′ is a divalent group selected from the group consisting of *—O—*, *—S—*, *—N(R′)—*, *—N(H)—*, and *—R″—*, wherein R′ and *—R″—* are independent hydrocarbyl groups comprising at least 1 carbon.

13. The method of claim 12 , wherein L′ of the diamine is *—O—*.

14. The method of claim 12 , wherein the organic solvent is N-methyl pyrrolidone (NMP).

15. The method of claim 12 , wherein the glyoxal/diamine monomer mole ratio has a value in the range of 0.90 to 1.1.

16. The method of claim 15 , wherein the polymer has a Tg greater than 300° C. as measured by differential scanning calorimetry.

17. The method of claim 12 , wherein the glyoxal/diamine mole ratio of the mixture has a value in the range of 0.50 to less than 0.90.

18. The method of claim 17 , wherein the film has a Tg in the range of 194° C. to about 250° C. as measured by differential scanning calorimetry.

19. A film layer comprising the polymer of claim 1 .

20. A method of forming the film layer of claim 19 , comprising:
agitating a reaction mixture comprising i) a monomer selected from the group consisting of diamine monomers comprising two primary aromatic amine groups, triamine monomers comprising three primary aromatic amine groups, and combinations thereof, ii) an optional diluent monomer comprising one aromatic primary amine group, iii) glyoxal, iv) a water-miscible organic solvent, and v) water, thereby forming a solution comprising an initial polymer;
applying the solution to a surface of a substrate, thereby forming an initial film layer disposed on the surface; and
curing the initial film layer using one or more sequential heating steps that includes a last heating step, wherein the last heating step is performed at a temperature of 150° C. to 250° C., thereby forming the film layer.

21. The method of claim 20 , wherein the film layer has a glass transition temperature (Tg) greater than 190° C. as measured by differential scanning calorimetry.

22. A polymer comprising a plurality of units selected from the group consisting of divalent bis-imine units, trivalent imine-aminal units, tetravalent bis-aminal units, and combinations thereof, wherein the units are covalently linked to divalent or trivalent bridging groups;
wherein
the bridging groups comprise at least one 6-carbon aromatic ring,
aminal groups of the imine-aminal units and bis-aminal units comprise respective secondary nitrogens, and
nitrogens of the bis-imine units, imine-aminal units, and bis-aminal units are linked to respective aromatic carbons of the bridging groups.

Assignees

• IBM

Inventors

• Boday Dylan J
• Fevre Mareva B
• Hedrick James L
• Jones Gavin O
• Wojtecki Rudy J

Classifications

• C08G12/08 Primary

  aromatic · CPC title

• C08J5/18

  Manufacture of films or sheets · CPC title

• C08J2361/22

  of aldehydes with acyclic or carbocyclic compounds · CPC title

• C09D161/22

  of aldehydes with acyclic or carbocyclic compounds · CPC title