Thermoset polymers having a triazine network obtained by reaction of cyanate esters with dicyanamide room temperature ionic liquids

Patent metadata

Field	Value
Publication number	US-10544265-B2
Application number	US-201615543550-A
Country	US
Kind code	B2
Filing date	Jan 29, 2016
Priority date	Jan 29, 2015
Publication date	Jan 28, 2020
Grant date	Jan 28, 2020

Abstract

The invention relates to the use of dicyanamide-containing ionic liquids which decrease the cure temperature of cyanate esters to form unique thermoset polymers having a triazine network. These thermoset polymers having the triazine network have an ionic character allowing for use in varied applications. The thermoset polymers described herein are useful in high temperature performance composites, and their high Tg makes them useful as a substitute for epoxies in the microelectronics industry. The thermoset polymers have good fracture toughness, excellent substrate adhesion, low shrinkage, and low moisture uptake.

First claim

The invention claimed is:

1. A curable composition for preparing a thermoset polymer having a triazine network, said curable composition comprising:
(a) a cyanate ester monomer; and
(b) at least one ionic liquid comprising a dicyanamide anion.

2. The curable composition of claim 1 , wherein said ionic liquid comprises the dicyanamide anion and at least one cation selected from the group consisting of imidazolium, phosphonium, pyridinium and pyrrolidinium.

3. The curable composition of claim 1 , wherein said cation is selected from the group consisting of 1-ethyl-3-methyl imidazolium, 1-(3-cyanopropyl)-3-methyl imidazolium, trihexyltetradecylphosphonium, 1-(2-hydroxyethyl)-3-methylimidazolium, 1-butyl-3-methyl pyridinium, and 1-butyl-1-methyl-pyrrolidinium.

4. The curable composition as claimed in claim 1 , wherein said cyanate ester monomer has two cyanate ester groups bonded to a core which is an optionally substituted aryl, alkyl or aralkyl group.

5. The curable composition as claimed in claim 1 , wherein said cyanate ester monomer has two cyanate ester groups bonded to a core which is an optionally substituted aralkyl group having 2 or more phenyl rings.

6. The curable composition of claim 1 , wherein said cyanate ester monomer has two cyanate ester groups bonded to phenyl rings of an alkylenebisphenyl group.

7. The curable composition of claim 6 , wherein the alkylene group of said alkylenebisphenyl group is an isopropylene or ethylidene.

8. The curable composition of claim 6 , wherein the two cyanate ester groups are bonded at para positions of the phenyl rings.

9. The curable composition of claim 1 , wherein a hydroxyl donor is present in the curable composition and is at least one selected from the group consisting of water, an optionally substituted aryl, alkyl or aralkyl group having a hydroxyl, or phenol.

10. The curable composition of claim 1 , wherein metals which can catalyze trimerization of cyanate ester monomer under curing conditions are not added to the curable composition.

11. A method of preparing a thermoset polymer having a triazine network comprising combining, in any order, the following:
(a) a cyanate ester monomer; and
(b) at least one ionic liquid comprising a dicyanamide anion, to form a mixture, and heating the mixture to a temperature sufficient to cause a curing reaction to thereby form the thermoset polymer having a triazine network.

12. The method according to claim 11 , wherein the cyanate ester monomer to dicyanamide ratio of 2:1 to 400:1.

13. The method according to claim 11 , wherein the temperature of the curing reaction is 80 to 350C.

14. The method according to claim 11 , wherein said ionic liquid comprises the dicyanamide anion and at least one cation selected from the group consisting of imidazolium, phosphonium, pyridinium and pyrrolidinium.

15. The method according to claim 11 , wherein said cyanate ester monomer has two cyanate ester groups bonded to a core which is an optionally substituted aryl, alkyl or aralkyl group.

16. The method according to claim 11 , wherein a hydroxyl donor is present in the mixture and is at least one selected from the group consisting of water, an optionally substituted aryl, alkyl or aralkyl group having a hydroxyl, or phenol.

17. The method according to claim 11 , wherein the majority of triazine rings formed during the curing reaction have a residue of the dicyanamide anion making up part of the triazine ring structure.

Assignees

• Palmese Giuseppe R
• Throckmorton James
• Univ Drexel

Inventors

• Palmese Giuseppe R
• Throckmorton James

Classifications

• C08G73/0655

  from polycyanurates · CPC title

• C08G73/0661 Primary

  characterised by the catalyst used · CPC title

• C08L79/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title

• C08G73/0644

  Poly(1,3,5)triazines · CPC title