US4129554A
Expired / Lapsed
US
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Thermosettable, polymerizable resin composition comprising a polyepoxide and a polyisocyanate stabilized by incorporating an organic electron acceptor
Assignee: Hitachi Ltd
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Filing: 1977-05-16
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Granted: 1978-12-12
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Expires: 1997-05-16
Abstract
Abstract A thermosettable, polymerizable resin composition comprising a polyepoxide and a polyisocyanate which is normally catalyzed by a basic curing catalyst for forming oxazolidone rings and isocyanurate rings or uredione rings is remarkably stabilized at low temperatures by incorporating a small amount of an organic electron acceptor, such as, picric acid, quinone, chloranil, or cyanoacetate ester into the composition. Since the specific electron acceptors effectively inhibit the polymerization of the reactive components in the composition at low temperatures, a shelf life of the composition is remarkably prolonged.
Inventors
- 👤 Yoshiharu Karasawa
- 👤 Tohru Koyama
- 👤 Toshikazu Narahara
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 05:52
CPC Classifications
C; C08; C08G; C08G18/00; C08G18/003; C08G18/06; C08G18/08; C08G18/089; C08G18/09
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
172 words
In the stabilizing of thermosettable, polymerizable compositions comprising polyepoxides having more than one epoxy group and polyisocyanates having more than one free-isocyanate group, on the average, which are normally catalyzed by a basic curing catalyst for forming in the cured product oxazolidone rings and isocyanurate rings or uretdione rings, or both, the improvement that comprises inhibiting at temperatures of about 60° C. or lower the polymerization of the reactive components in the compositions in the absence of the basic curing catalyst by incorporating into the compositions an electron acceptor selected from the group consisting of: (1) Compounds having an active methylene or methine group connected to an electron attractive group from the class consisting of group of --CN, --NO 2 , --COOR, --COR, and --CHO, where R is a lower alkyl group having one to 8 carbon atoms; and (2) Compounds of π-type electron acceptor, wherein the amount of the electron acceptor is of 1 × 10 -5 to 1% by weight based on the total weight of the polyepoxides and polyisocyanates.
Claim 2
Dependent Claim
172 words
In the stabilizing of thermosettable, polymerizable compositions comprising polyepoxides having more than one epoxy group and polyisocyanates having more than one free-isocyanate group, on the average, which are normally catalyzed by a basic curing catalyst for forming in the cured product oxazolidone rings and isocyanurate rings or uretdione rings, or both, the improvement that comprises inhibiting at temperatures of about 60° C. or lower the polymerization of the reactive components in the compositions in the absence of the basic curing catalyst by incorporating into the compositions an electron acceptor selected from the group consisting of: (1) Compounds having an active methylene or methine group connected to an electron attractive group from the class consisting of group of --CN, --NO 2 , --COOR, --COR, and --CHO, where R is a lower alkyl group having one to 8 carbon atoms; and (2) Compounds of π-type electron acceptor, wherein the amount of the electron acceptor is of 1 × 10 -5 to 1% by weight based on the total weight of the polyepoxides and polyisocyanates.
Claim 3
Dependent Claim
27 words
The improvement as defined in claim 1 wherein the equivalent ratio of polyepoxide to polyisocyanate in the composition is from more than 1 to about 40, respectively.
Claim 4
Dependent Claim
51 words
The improvement as defined in claim 1, wherein the electron acceptor is cyanoacetic acid, cyanoacetate lower alkyl esters, α-cyanoacetamide, α-cyanoacetanilide, malononitrile, nitroacetic acid, nitroacetate lower alkyl esters, dinitromethane, nitroacetone, nitrochloromethane, formyl acetic acid, formyl acetate lower alkyl esters, formyl acetone, acetyl acetone, malonate lower alkyl diesters, or acetoacetate lower alkyl esters.
Claim 5
Dependent Claim
13 words
The improvement as defined in claim 3, wherein the electron acceptor is malononitrile.
Claim 6
Dependent Claim
14 words
The improvement is defined in claim 3, wherein the electron acceptor is cyanoacetic acid.
Claim 7
Dependent Claim
24 words
The improvement as defined in claim 1, wherein the amount of the electron acceptor is of 1 × 10 -4 to 0.1% by weight.
Claim 8
Dependent Claim
28 words
The improvement as defined in claim 1, wherein the electron acceptor is trinitromethane, tricyanomethane, 1, 1-dicyanoethane, 1, 1-dinitroethane, triacetoxymethane, α-dinitroacetate lower alkyl esters, or α-nitropropionate lower alkyl esters.
Claim 9
Dependent Claim
38 words
The improvement as defined in claim 1, wherein the electron acceptor is tetracyanoethylene, tetracyanoquinodimethane, benzoquinone, dichlorodicyanobenzoquinone, tetrachlorobenzoquinone, tetrafluorobenzoquinone, tetracyanobenzoquinone, tetracyanobenzene, hexacyanobenzene, picric acid, picryl chloride, trinitrobenzoic acid, trinitrobenzoate lower alkyl esters trinitroanisole, tri-nitrofluorenone, tetra-nitrofluorenone, tetranitrocarbazole, anthraquinone, or nitrobenzaldehyde.
Claim 10
Dependent Claim
13 words
The improvement as defined in claim 8, wherein the electron acceptor is tetracyanoethylene.
Claim 11
Dependent Claim
30 words
The improvement as defined in claim 1, wherein the equivalent ratio of the polyepoxides to the polyisocyanates is from 1.5 to 30 when the polyisocyanates are liquid at room temperature.
Claim 12
Dependent Claim
30 words
The improvement as defined in claim 8, wherein the equivalant ratio of the polyepoxides to the polyisocyanates is from 1.5 to 5 when the polyisocyanates are solid at room temperature.
Claim 13
Dependent Claim
168 words
A composition of matter stabilized at temperatures of about 60° C. or lower, but polymerizable and curable by heating in the presence of a curing catalyst, which comprises a polyepoxide having more than one epoxy group and polyisocyanate having more than one free isocyanate group, on the average, in the equivalent ratio of the poylepoxide to the polyisocyanate of from more than one to about 40, which is free of a basic curing catalyst for forming in the cured product oxazolidone rings and isocyanurate rings and further contains in an amount from 1 × 10 -5 to 1% by weight based on the total weight of the polyepoxide and polyisocyanate an electron acceptor selected from the group consisting of: (1) Compounds having an active methylene or methine group connected to an electron attractive group selected from the group consisting of --CN, --NO 2 , --COOR, --COR and --CHO, where R is a lower alkyl group having one to 8 carbon atoms; and (2) Compounds of π-type electron acceptor.
Claim 14
Dependent Claim
168 words
A composition of matter stabilized at temperatures of about 60° C. or lower, but polymerizable and curable by heating in the presence of a curing catalyst, which comprises a polyepoxide having more than one epoxy group and polyisocyanate having more than one free isocyanate group, on the average, in the equivalent ratio of the poylepoxide to the polyisocyanate of from more than one to about 40, which is free of a basic curing catalyst for forming in the cured product oxazolidone rings and isocyanurate rings and further contains in an amount from 1 × 10 -5 to 1% by weight based on the total weight of the polyepoxide and polyisocyanate an electron acceptor selected from the group consisting of: (1) Compounds having an active methylene or methine group connected to an electron attractive group selected from the group consisting of --CN, --NO 2 , --COOR, --COR and --CHO, where R is a lower alkyl group having one to 8 carbon atoms; and (2) Compounds of π-type electron acceptor.
Claim 15
Dependent Claim
53 words
A stabilized composition of matter as defined in claim 12, wherein the electron acceptor is cyanoacetic acid, cyanoacetate lower alkyl esters, α-cyanoacetamide, α-cyanoacetanilide, malononitrile, nitroacetic acid, nitroacetate lower alkyl esters, dinitromethane, nitracetone, formyl acetic acid, formyl acetate lower alkyl esters, formyl acetone, acetyl acetone, malonate lower alkyl diesters, or acetoacetate lower alkyl esters.
Claim 16
Dependent Claim
31 words
A stabilized composition of matter as defined in claim 12, wherein the electron acceptor is trinitromethane, tricyanomethane, 1, 1-dicyanoethane, 1, 1-dinitroethane, triacetoxymethane, α-dinitroacetate lower alkyl esters or α-nitropropionate lower alkyl esters.
Claim 17
Dependent Claim
42 words
A stabilized composition of matter as defined in claim 12, wherein the electron acceptor is tetracyanoethylene, tetracyanoquinodimethane, benzoquinone, dichlorodicyanobenzoquinone, tetrachlorobenzoquinone, tetrafluorobenzoquinone, tetracyanobenzoquinone, tricyanobenzoquinone, tetracyanobenzene, hexacyanobenzene, picric acid, picryl chloride, trinitrobenzoic acid, trinitrobenzoate lower alkyl esters, trinitroanisole, trinitrofluorenone, tetranitrofluorenone, tetranitrocarbazole, anthraquinone or nitrobenzaldehyde.
Claim 18
Dependent Claim
27 words
A stabilized composition of matter as defined in claim 12, wherein the amount of the electron acceptor is of 1 × 10 -4 to 0.1% by weight.
Claim 19
Dependent Claim
17 words
A stabilized composition of matter as defined in claim 12, wherein the electron acceptor is cyanoacetic acid.
Claim 20
Dependent Claim
16 words
A stabilized composition of matter as defined in claim 12, wherein the electron acceptor is malononitrile.
Claim 21
Dependent Claim
76 words
A method of curing the stabilized composition of matter as defined in claim 35, which comprises incorporating into the stabilized composition of matter a basic curing catalyst for forming oxazolidone rings and isocyanurate rings in an amount of 0.01 to 10% by weight based on the total weight of the polyepoxide and polyisocyanate; and heating the composition of matter at a temperature of about 80 to about 250° C. for about 1 to about 50 hours.
Claim 22
Dependent Claim
96 words
A method of curing the stabilized composition of matter as defined in claim 12, which comprises applying a basic catalyst for forming oxazolidone rings and isocyanurate rings in the cured product to a material to be impregnated, cast or molded, in an amount from 0.01 to 10% by weight based on the total weight of the polyepoxide and polyisocyanate; impregnating, casting or molding the material with the composition of matter as defined in claim 34; and heating the composition of matter at a temperature of about 80 to 250° C. for about 1 to 50 hours.
Claim 23
Dependent Claim
24 words
A stabilized composition of matter as defined in claim 12, wherein the polyisocyanate is a mixture of diphenylmethane diisocyanate and carbodiimide of diphenylmethane diisocyanate.
Claim 24
Dependent Claim
16 words
A stabilized composition of matter as defined in claim 12, wherein the electron acceptor is α-cyanoacetamide.
Claim 25
Dependent Claim
17 words
A stabilized composition of matter as defined in claim 12, wherein the electron acceptor is picryl chloride.
Claim 26
Dependent Claim
17 words
A stabilized composition of matter as defined in claim 12, wherein the electron acceptor is picric acid.
Claim 27
Dependent Claim
21 words
A stabilized composition of matter as defined in claim 12, wherein the electron acceptor is 2, 4, 6-trinitrobenzoate lower alkyl esters.
Claim 28
Dependent Claim
18 words
A stabilized composition of matter as defined in claim 12, wherein the electron acceptor is 2, 4, 6-trinitroanisole.
Claim 29
Dependent Claim
18 words
A stabilized composition of matter as defined in claim 12, wherein the electron acceptor is 2, 3-dichloro-5, 6-dicyanobenzoquinone.
Claim 30
Dependent Claim
19 words
A stabilized composition of matter as defined in claim 12, wherein the electron acceptor is 1, 3, 6, 8-tetranitrocarbozole.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-12-11 | 1982-06-12 | 1982-12-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-12-11 | 1986-06-12 | 1986-12-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-12-11 | 1990-06-12 | 1990-12-12 | $7700.00 | Window Closed / Lapsed |