Process for making macromolecular networks

Patent metadata

Field	Value
Publication number	US-11518828-B1
Application number	US-201916710123-A
Country	US
Kind code	B1
Filing date	Dec 11, 2019
Priority date	Jan 29, 2019
Publication date	Dec 6, 2022
Grant date	Dec 6, 2022

Abstract

The present invention relates to processes for making macromolecular networks, macromolecular networks made by such processes, and methods of using such macromolecular networks. Such process employs a low amount of amine compound as a reaction accelerant. The rates of chemical reaction are thereby easily controlled over several orders of magnitude, permitting efficient catalysis and control of reaction conditions needed to produce thermochemically stable macromolecular networks.

First claim

What is claimed is:

1. A process of making a macromolecular network said process comprising curing, via heating, a curative composition selected from the group consisting of:
a) Curative Composition 1, said Curative Composition 1 comprising:
(i) a telechelic oligomer comprising a backbone, chain ends and at least two reactive groups, each of said reactive groups being independently selected from carbon-carbon double bonds or carbon-carbon triple bonds;
(ii) a thiol tri- or tetrafunctionalized crosslinking agent;
(iii) an optional dithiol chain extender;
(iv) a free radical initiator; and
(v) based on total Curative Composition 1's weight, from about 0.1 wt % to about 10 wt % of an accelerator comprising an amine moiety;

b) Curative Composition 2, said Curative Composition 2 comprising:
(i) a telechelic oligomer comprising at least 2 reactive groups, each of said reactive groups being thiol functionalized;
(ii) a tri- or tetrafunctionalized crosslinking agent comprising one or more carbon-carbon double bonds and/or carbon-carbon triple bonds that provide said functionalization;
(iii) an optional difunctional chain extender comprising one or more carbon-carbon double bonds and/or carbon-carbon triple bonds that provide said functionalization;
(iv) a free radical initiator; and
(v) based on total Curative Composition 2's weight, from about 0.0110 wt % to about 10 wt % of an accelerator comprising an amine moiety; and

c) mixtures thereof.

2. A process of making a macromolecular network according to claim 1 , said process comprising curing, via heating, a curative composition selected from the group consisting of:
a) Curative Composition 1, said Curative Composition 1 comprising:
(i) a telechelic oligomer comprising a backbone, chain ends and from 2 to 4 reactive groups, each of said reactive groups being independently selected from carbon-carbon double bonds or carbon-carbon triple bonds;
(ii) a thiol tri- or tetrafunctionalized crosslinking agent;
(iii) an optional dithiol chain extender;
(iv) a free radical initiator; and
(v) based on total Curative Composition 1's weight, from about 0.1 wt % to about 1 wt % of an accelerator comprising an amine moiety;

b) Curative Composition 2, said Curative Composition 2 comprising:
(i) a telechelic oligomer comprising from 2 to 4 reactive groups, each of said reactive groups being thiol functionalized;
(ii) a tri- or tetrafunctionalized crosslinking agent comprising one or more carbon-carbon double bonds and/or carbon-carbon triple bonds that provide said functionalization;
(iii) an optional difunctional chain extender comprising one or more carbon-carbon double bonds and/or carbon-carbon triple bonds that provide said functionalization;
(iv) a free radical initiator; and
(v) based on total Curative Composition 2's weight, from about 0.02 wt % to about 1 wt % of an accelerator comprising an amine moiety; and

c) mixtures thereof.

3. A process of making a macromolecular according to claim 1 said process comprising curing, via heating, a curative composition selected from the group consisting of:
a) Curative Composition 1, said Curative Composition 1 comprising:
(i) a telechelic oligomer comprising a backbone, chain ends and two reactive groups, each of said reactive groups being independently selected from carbon-carbon double bonds or carbon-carbon triple bonds;
(ii) a thiol tri- or tetrafunctionalized crosslinking agent;
(iii) an optional dithiol chain extender;
(iv) a free radical initiator; and
(v) based on total Curative Composition 1's weight from about 0.1 wt % to about 0.5 wt % of an accelerator comprising an amine moiety;

b) Curative Composition 2, said Curative Composition 2 comprising:
(i) a telechelic oligomer comprising 2 reactive groups, each of said reactive groups being thiol functionalized;
(ii) a tri- or tetrafunctionalized crosslinking agent comprising one or more carbon-carbon double bonds and/or carbon-carbon triple bonds that provide said functionalization;
(iii) an optional difunctional chain extender comprising one or more carbon-carbon double bonds and/or carbon-carbon triple bonds that provide said functionalization;
(iv) a free radical initiator; and
(v) based on total Curative Composition 2's weight from about 0.03 wt % to about 0.2 wt % of an accelerator comprising an amine moiety; and

c) mixtures thereof.

4. A process of making a macromolecular network according to claim 1 , said process comprising curing, via heating, a curative composition selected from the group consisting of:
a) Curative Composition 1, said Curative Composition 1 comprising:
(i) a telechelic oligomer comprising a backbone, chain ends and two reactive groups, each of said reactive groups being independently selected from carbon-carbon double bonds or carbon-carbon triple bonds, said reactive groups being on said chain ends;
(ii) a thiol tri- or tetrafunctionalized crosslinking agent;
(iii) an optional dithiol chain extender;
(iv) a free radical initiator; and
(v) based on total Curative Composition 1's weight, from about 0.3 wt % to about 0.5 wt % of an accelerator comprising an amine moiety;

b) Curative Composition 2, said Curative Composition 2 comprising:
(i) a telechelic oligomer comprising 2 reactive groups, each of said reactive groups being thiol functionalized, said reactive groups being on the chain ends;
(ii) a tri- or tetrafunctionalized crosslinking agent comprising one or more carbon-carbon double bonds and/or carbon-carbon triple bonds that provide said functionalization;
(iii) an optional difunctional chain extender comprising one or more carbon-carbon double bonds and/or carbon-carbon triple bonds that provide said functionalization;
(iv) a free radical initiator; and
(v) based on total Curative Composition 2's weight, from about 0.05 wt % to about 0.1 wt % of an accelerator comprising an amine moiety; and

c) mixtures thereof.

5. A process of making a macromolecular network according to claim 4 , wherein for Curative Composition 1's telechelic oligomer, said reactive groups are vinylethers.

6. A process according to claim 1 , wherein:
a) for Curative Composition 1,
(i) said telechelic oligomer's backbone is selected from the group consisting of hydrogenated polybutadiene, polybutadiene, polyethylene glycol, polytetrahydrofuran, polycaprolactam, polycaprolactone and mixtures thereof;
(ii) said thiol tri- or tetrafunctionalized crosslinking agent is selected from the group consisting of cyclohexanetriethylthiols, pentaerythrityl tetrathiol, 1,1,1-tris(mercaptomethyl)ethane and mixtures thereof;
(iii) said dithiol chain extender is selected from the group consisting of alkyldithiols, 3,6-dioxa-1,8-octanedithiol and mixtures thereof;
(iv) said accelerator comprising an amine moiety is selected from the group consisting of N-phenyl-2-naphthylamine, aniline, p-anisidine, 1,2,3,4-tetrahydroquinoline, p-aminophenol, N,N-dimethylaniline, p-bromoaniline, p-nitroaniline, diphenylamine, 4-aminopyridine, anisole, 1,4-phenylenediamine and mixtures thereof; and
(v) said free radical initiator is selected from the group consisting of t-butylperoxy 2-ethylhexyl carbonate are lauroyl peroxide, t-butyl peroxybenzoate, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide or azobisisobutyronitrile and mixtures thereof;

b) for Curative Composition 2,
(i) said telechelic oligomer's backbone is selected from the group consisting of hydrogenated polybutadiene, polybutadiene, polyethylene glycol, polytetrahydrofuran, polycaprolactam, polycaprolactone, mixtures thereof;
(ii) said tri- or tetrafunctionalized crosslinking agent comprises one or more hydrocarbons comprising three or four unsaturated terminal sites;
(iii) said difunctional chain extender comprises alpha-omeg

Assignees

• Us Gov Air Force
• Us Air Force

Inventors

• Reams Josiah T
• Guenthner Andrew J
• Haddad Timothy S
• Marcischak Jacob C
• Ghiassi Kamran B
• Moore Levi Michael Joseph

Classifications

• C08K5/37 Primary

  Thiols · CPC title

• C08K5/14

  Peroxides · CPC title

• C08K5/18

  with aromatically bound amino groups · CPC title

• C08K5/01

  Hydrocarbons {(C08K5/0091 takes precedence)} · CPC title

• C08G65/20

  Tetrahydrofuran · CPC title