US4180640A
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Accelerator for curable acrylic ester compositions
Assignee: Henkel Loctite Corp
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Filing: 1977-10-31
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Granted: 1979-12-25
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Expires: 1997-10-31
Abstract
Abstract Curable acrylate ester compositions having as an accelerator for the polymerization a hydrazine derivative of the formula R 1 --HN--NH--CO--R 2 and as a co-accelerator, an acid having a pK a of less than about 6. The compositions may optionally be formulated as two-part compositions with the non-ester-containing part being applied as a primer. Typical of the monomers are the polyalkylene glycol dimethacrylates and the so-called urethane acrylates. Polymerization is preferably initiated by a peroxy compound such as cumene hydroperoxide, such a composition having anaerobic curing characteristics.
Inventors
- 👤 David P. Melody
- 👤 Daniel A. Doherty
- 👤 John F. O'Grady
- 👤 Richard D. Rich
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 22:17
CPC Classifications
C; C09; C09J; C09J5/00; C09J5/04; C09J4/00
Claims Analysis
Total Claims: 64
Claim 1
Independent Claim
166 words
A curable adhesive and sealant composition comprising: (a) a room temperature polymerizable acrylate ester; (b) a peroxy free radical initiator in an amount sufficient to initiate polymerization of said ester; (c) as a polymerization accelerator, a compound having the formula ##STR16## wherein R 1 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl and R 2 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkoxy, aryloxy, carbonyl group connected to an unreactive lower alkyl group of 1 to 4 carbons, amino, and the following groups: ##STR17## wherein R 10 is selected from the group consisting of alkyl groups containing one to about 10 carbon atoms, alkenyl groups containing two to about 10 carbon atoms, and aryl groups containing up to about 10 carbon atoms, said accelerator being present in an amount sufficient to accelerate the polymerization at room temperature; and (d) as co-accelerator, an acid having a pK a at room temperature of about 1 to about 6.
Claim 2
Dependent Claim
166 words
A curable adhesive and sealant composition comprising: (a) a room temperature polymerizable acrylate ester; (b) a peroxy free radical initiator in an amount sufficient to initiate polymerization of said ester; (c) as a polymerization accelerator, a compound having the formula ##STR16## wherein R 1 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl and R 2 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkoxy, aryloxy, carbonyl group connected to an unreactive lower alkyl group of 1 to 4 carbons, amino, and the following groups: ##STR17## wherein R 10 is selected from the group consisting of alkyl groups containing one to about 10 carbon atoms, alkenyl groups containing two to about 10 carbon atoms, and aryl groups containing up to about 10 carbon atoms, said accelerator being present in an amount sufficient to accelerate the polymerization at room temperature; and (d) as co-accelerator, an acid having a pK a at room temperature of about 1 to about 6.
Claim 3
Dependent Claim
19 words
A composition of claim 1 wherein R 1 is selected from the group consisting of alkyl, aryl and aralkyl.
Claim 4
Dependent Claim
19 words
A composition of claim 1 wherein R 1 is phenyl substituted with a C 1 -C 4 alkyl group.
Claim 5
Dependent Claim
20 words
A composition of claim 1 wherein R 2 is selected from the group consisting of hydrogen, alkyl, aryl and alkoxy.
Claim 6
Dependent Claim
18 words
A composition of claim 4 wherein R 2 is selected from the group consisting of hydrogen and alkyl.
Claim 7
Dependent Claim
11 words
A composition of claim 1 wherein the accelerator is 1-acetyl-2-phenyl hydrazine.
Claim 8
Dependent Claim
11 words
A composition of claim 1 wherein the accelerator is 1-acetyl-2(p-tolyl) hydrazine.
Claim 9
Dependent Claim
11 words
A composition of claim 1 wherein the accelerator is 1-formyl-2-phenyl hydrazine.
Claim 10
Dependent Claim
11 words
A composition of claim 1 wherein the initiator is a hydroperoxide.
Claim 11
Dependent Claim
11 words
A composition of claim 9 wherein the hydroperoxide is cumene hydroperoxide.
Claim 12
Dependent Claim
11 words
A composition of claim 1 wherein the initiator is hydrogen peroxide.
Claim 13
Dependent Claim
11 words
A composition of claim 1 wherein the initiator is a perester.
Claim 14
Dependent Claim
12 words
A composition of claim 1 wherein the initiator is a diacyl peroxide.
Claim 15
Dependent Claim
17 words
A composition of claim 1 wherein the acid has a pK a of less than about 3.
Claim 16
Dependent Claim
11 words
A composition of claim 14 wherein the acid is maleic acid.
Claim 17
Dependent Claim
35 words
A composition of claim 1 wherein the acid has a pK a between about 3 and about 6 and the concentration of the co-accelerator is at least about 5% by weight of the total composition.
Claim 18
Dependent Claim
10 words
A composition of claim 1 which has anaerobic curing properties.
Claim 19
Dependent Claim
14 words
A composition of claim 1 containing in addition an accelerating amount of a sulfimide.
Claim 20
Dependent Claim
11 words
A composition of claim 18 wherein the sulfimide is benzoic sulfimide.
Claim 21
Dependent Claim
168 words
A two-part, curable adhesive and sealant composition comprising a first part comprising a room temperature polymerizable acrylate ester and an acid having a pK a at room temperature of about 1 to about 6; and a second part comprising a peroxy free radical initiator in an amount sufficient to initiate polymerization of said ester and a polymerization accelerator having the formula ##STR18## wherein R 1 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl and R 2 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkoxy, aryloxy, carbonyl group connected to an unreactive lower alkyl group of 1 to 4 carbons, amino, and the following groups: ##STR19## wherein R 10 is selected from the group consisting of alkyl groups containing one to about 10 carbon atoms, alkenyl groups containing two to about 10 carbon atoms, and aryl groups containing up to about 10 carbon atoms, said accelerator being present in an amount sufficient to accelerate the polymerization at room temperature.
Claim 22
Dependent Claim
168 words
A two-part, curable adhesive and sealant composition comprising a first part comprising a room temperature polymerizable acrylate ester and an acid having a pK a at room temperature of about 1 to about 6; and a second part comprising a peroxy free radical initiator in an amount sufficient to initiate polymerization of said ester and a polymerization accelerator having the formula ##STR18## wherein R 1 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl and R 2 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkoxy, aryloxy, carbonyl group connected to an unreactive lower alkyl group of 1 to 4 carbons, amino, and the following groups: ##STR19## wherein R 10 is selected from the group consisting of alkyl groups containing one to about 10 carbon atoms, alkenyl groups containing two to about 10 carbon atoms, and aryl groups containing up to about 10 carbon atoms, said accelerator being present in an amount sufficient to accelerate the polymerization at room temperature.
Claim 23
Dependent Claim
19 words
A composition of claim 20 wherein R 1 is selected from the group consisting of alkyl, aryl and aralkyl.
Claim 24
Dependent Claim
19 words
A composition of claim 20 wherein R 1 is phenyl substituted with a C 1 -C 4 alkyl group.
Claim 25
Dependent Claim
20 words
A composition of claim 20 wherein R 2 is selected from the group consisting of hydrogen, alkyl, aryl and alkoxy.
Claim 26
Dependent Claim
18 words
A composition of claim 23 wherein R 2 is selected from the group consisting of hydrogen and alkyl.
Claim 27
Dependent Claim
11 words
A composition of claim 20 wherein the accelerator is 1-acetyl-2-phenyl hydrazine.
Claim 28
Dependent Claim
11 words
A composition of claim 20 wherein the accelerator is 1-acetyl-2(p-tolyl) hydrazine.
Claim 29
Dependent Claim
11 words
A composition of claim 20 wherein the accelerator is 1-formyl-2-phenyl hydrazine.
Claim 30
Dependent Claim
12 words
A composition of claim 20 wherein the initiator is a hydro peroxide.
Claim 31
Dependent Claim
11 words
A composition of claim 28 wherein the hydroperoxide is cumene hydroperoxide.
Claim 32
Dependent Claim
11 words
A composition of claim 20 wherein the initiator is hydrogen peroxide.
Claim 33
Dependent Claim
11 words
A composition of claim 20 wherein the initiator is a perester.
Claim 34
Dependent Claim
12 words
A composition of claim 20 wherein the initiator is a diacyl peroxide.
Claim 35
Dependent Claim
17 words
A composition of claim 20 wherein the acid has a pK a of less than about 3.
Claim 36
Dependent Claim
11 words
A composition of claim 33 wherein the acid is maleic acid.
Claim 37
Dependent Claim
31 words
A composition of claim 20 wherein the acid has a pK a between about 3 and about 6 and the concentration of the acid is at least about 5% by weight.
Claim 38
Dependent Claim
10 words
A composition of claim 20 which has anaerobic curing properties.
Claim 39
Dependent Claim
14 words
A composition of claim 20 containing in addition an accelerating amount of a sulfimide.
Claim 40
Dependent Claim
11 words
A composition of claim 37 wherein the sulfimide is benzoic sulfimide.
Claim 41
Dependent Claim
166 words
A two-part, curable adhesive and sealant composition comprising a first part comprising a room temperature polymerizable acrylate ester, an acid having a pK a at room temperature of about 1 to about 6, and a peroxy free radical initiator in an amount sufficient to initiate polymerization of said ester; and a second part comprising a polymerization accelerator having the formula wherein R 1 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl and R 2 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkoxy, aryloxy, carbonyl group connected to an unreactive lower alkyl group of 1 to 4 carbons, amino, and the following groups: ##STR20## wherein R 10 is selected from the group consisting of alkyl groups containing one to about 10 carbon atoms, alkenyl groups containing two to about 10 carbon atoms, and aryl groups containing up to about 10 carbon atoms, said accelerator being present in an amount sufficient to accelerate the polymerization at room temperature.
Claim 42
Dependent Claim
166 words
A two-part, curable adhesive and sealant composition comprising a first part comprising a room temperature polymerizable acrylate ester, an acid having a pK a at room temperature of about 1 to about 6, and a peroxy free radical initiator in an amount sufficient to initiate polymerization of said ester; and a second part comprising a polymerization accelerator having the formula wherein R 1 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl and R 2 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkoxy, aryloxy, carbonyl group connected to an unreactive lower alkyl group of 1 to 4 carbons, amino, and the following groups: ##STR20## wherein R 10 is selected from the group consisting of alkyl groups containing one to about 10 carbon atoms, alkenyl groups containing two to about 10 carbon atoms, and aryl groups containing up to about 10 carbon atoms, said accelerator being present in an amount sufficient to accelerate the polymerization at room temperature.
Claim 43
Dependent Claim
166 words
A two-part, curable adhesive and sealant composition comprising a first part comprising a room temperature polymerizable acrylate ester, a peroxy free radical initiator in an amount sufficient to initiate polymerization of said ester and a polymerization accelerator having the formula ##STR21## wherein R 1 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl and R 2 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkoxy, aryloxy, carbonyl group connected to an unreactive lower alkyl group of 1 to 4 carbons, amino, and the following groups: ##STR22## where R 10 is selected from the group consisting of alkyl groups containing one to about 10 carbon atoms, alkenyl groups containing two to about 10 carbon atoms, and aryl groups containing up to about 10 carbon atoms, said accelerator being present in an amount sufficient to accelerate the polymerization at room temperature; and a second part comprising an acid having a pK a at room temperature of less than about 3.
Claim 44
Dependent Claim
166 words
A two-part, curable adhesive and sealant composition comprising a first part comprising a room temperature polymerizable acrylate ester, a peroxy free radical initiator in an amount sufficient to initiate polymerization of said ester and a polymerization accelerator having the formula ##STR21## wherein R 1 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl and R 2 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkoxy, aryloxy, carbonyl group connected to an unreactive lower alkyl group of 1 to 4 carbons, amino, and the following groups: ##STR22## where R 10 is selected from the group consisting of alkyl groups containing one to about 10 carbon atoms, alkenyl groups containing two to about 10 carbon atoms, and aryl groups containing up to about 10 carbon atoms, said accelerator being present in an amount sufficient to accelerate the polymerization at room temperature; and a second part comprising an acid having a pK a at room temperature of less than about 3.
Claim 45
Dependent Claim
19 words
A composition of claim 40 wherein R 1 is selected from the group consisting of alkyl, aryl and aralkyl.
Claim 46
Dependent Claim
19 words
A composition of claim 40 wherein R 1 is phenyl substituted with a C 1 -C 4 alkyl group.
Claim 47
Dependent Claim
20 words
A composition of claim 40 wherein R 2 is selected from the group consisting of hydrogen, alkyl, aryl and alkoxy.
Claim 48
Dependent Claim
18 words
A composition of claim 43 wherein R 2 is selected from the group consisting of hydrogen and alkyl.
Claim 49
Dependent Claim
11 words
A composition of claim 40 wherein the accelerator is 1-acetyl-2-phenyl hydrazine.
Claim 50
Dependent Claim
11 words
A composition of claim 40 wherein the accelerator is 1-acetyl-2(p-tolyl) hydrazine.
Claim 51
Dependent Claim
11 words
A composition of claim 40 wherein the accelerator is 1-formyl-2-phenyl hydrazine.
Claim 52
Dependent Claim
11 words
A composition of claim 40 wherein the initiator is a hydroperoxide.
Claim 53
Dependent Claim
11 words
A composition of claim 48 wherein the hydroperoxide is cumene hydroperoxide.
Claim 54
Dependent Claim
11 words
A composition of claim 40 wherein the initiator is hydrogen peroxide.
Claim 55
Dependent Claim
10 words
A composition of claim 40 wherein the initiator is perester.
Claim 56
Dependent Claim
12 words
A composition of claim 40 wherein the initiator is a diacyl peroxide.
Claim 57
Dependent Claim
17 words
A composition of claim 40 wherein the acid has a pK a of less than about 2.
Claim 58
Dependent Claim
10 words
A composition of claim 40 which has anaerobic curing properties.
Claim 59
Dependent Claim
14 words
A composition of claim 40 containing in addition an accelerating amount of a sulfimide.
Claim 60
Dependent Claim
11 words
A composition of claim 55 wherein the sulfimide is benzoic sulfimide.
Claim 61
Dependent Claim
33 words
A process of adhering or sealing surfaces comprising applying to at least one of said surfaces a composition of claim 1, placing said surfaces in abutting relationship, and allowing the composition to cure.
Claim 62
Dependent Claim
44 words
A process of adhering or sealing surfaces comprising a first part of a composition of claim 20, applying to another of said surfaces a second part of a composition of claim 20, placing said surfaces in abutting relationship, and allowing the composition to cure.
Claim 63
Dependent Claim
44 words
A process of adhering or sealing surfaces comprising a first part of a composition of claim 39, applying to another of said surfaces a second part of a composition of claim 39, placing said surfaces in abutting relationship, and allowing the composition to cure.
Claim 64
Dependent Claim
44 words
A process of adhering or sealing surfaces comprising a first part of a composition of claim 40, applying to another of said surfaces a second part of a composition of claim 40, placing said surfaces in abutting relationship, and allowing the composition to cure.
References Cited (Backward Citations)
US3491076A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1982-12-24 | 1983-06-25 | 1983-12-25 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-12-24 | 1987-06-25 | 1987-12-25 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-12-24 | 1991-06-25 | 1991-12-25 | $7700.00 | Window Closed / Lapsed |