US4126505A
Expired / Lapsed
US
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Adhesive compositions
Assignee: BASF Corp
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Filing: 1976-10-28
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Granted: 1978-11-21
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Expires: 1996-10-28
Abstract
Abstract Compositions, useful as adhesives, comprise (i) an epoxide resin having glycidyl, β-methylglycidyl, or 2,3-epoxycyclopentyl groups directly attached to oxygen, nitrogen, or sulfur atoms, (ii) as curing agent for the epoxide resin, either one of certain (cyclo)aliphatic amines or one of certain tertiary amines, and also (iii) a polymercaptan, and (iv) a polyene having at least two activated ethylenic double bonds, each β to an atom of oxygen, nitrogen, or sulfur, the sum of these double bonds and of the mercaptan groups in the polymercaptan being at least 5. The compositions rapidly develop tack, so avoiding the need to hold, for a prolonged period in jigs, clamps, or other devices, objects being bonded together while the epoxide resin cures.
Inventors
- 👤 Edward W. Garnish
- 👤 Robert G. Wilson
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 09:26
CPC Classifications
C; C09; C09J; C09J163/00; C08; C08G; C08G59/00; C08G59/18; C08G59/40; C08G59/50; C08G59/56; C08G75/00; C08G75/02; C08G75/04; C08G75/045; C08G75/12; C09J181/00; C09J181/02; C08L; C08L2666/00; C08L2666/02; C08L2666/14; C08L2666/22
Claims Analysis
Total Claims: 36
Claim 1
Independent Claim
292 words
A composition which rapidly develops tack after mixing consisting essentially of (a) an epoxide resin having, per epoxide molecule, more than one 1,2-epoxide group of formula ##STR30## directly attached to oxygen, sulfur, or nitrogen, where either R and R 2 independently of one another represent hydrogen, in which case R 1 denotes hydrogen or methyl, or R and R 2 conjointly represent --CH.sub. 2 CH 2 --, in which case R 1 denotes hydrogen, (b) a polymercaptan having at least two mercaptan groups per average molecule, (c) a polyene having an average molecular weight of not more than 2,000, per average molecule, at least two ethylenic double bonds, each β to an atom of oxygen, sulfur, or nitrogen, the sum of such ethylenic double bonds in (c) and of mercaptan groups in (b) being at least 5, and (d) a curing agent for the epoxide resin, which is either a compound having at least three hydrogen atoms directly attached to aliphatic or cycloaliphatic amino nitrogen atoms present in an amount of from about 0.8 to 1.2 amino-hydrogen equivalents of the amine per 1,2-epoxide equivalent of the epoxide resin, or a tertiary amine having at least one nitrogen atom directly attached to carbon atoms of aliphatic or cycloaliphatic groups exclusively and at most two hydrogen atoms attached to amino nitrogen atoms present in an amount of from 1 to 40 parts by weight per 100 parts by weight of the epoxide resin, and wherein the polymercaptan is employed in a quantity sufficient to supply from 0.8 to 1.1 mercaptan groups per ethylenic double bond of the polyene and the polymercaptan plus polyene are present in amount of from 10 to 150 parts by weight per 100 parts by weight of the epoxide resin.
Claim 2
Dependent Claim
292 words
A composition which rapidly develops tack after mixing consisting essentially of (a) an epoxide resin having, per epoxide molecule, more than one 1,2-epoxide group of formula ##STR30## directly attached to oxygen, sulfur, or nitrogen, where either R and R 2 independently of one another represent hydrogen, in which case R 1 denotes hydrogen or methyl, or R and R 2 conjointly represent --CH.sub. 2 CH 2 --, in which case R 1 denotes hydrogen, (b) a polymercaptan having at least two mercaptan groups per average molecule, (c) a polyene having an average molecular weight of not more than 2,000, per average molecule, at least two ethylenic double bonds, each β to an atom of oxygen, sulfur, or nitrogen, the sum of such ethylenic double bonds in (c) and of mercaptan groups in (b) being at least 5, and (d) a curing agent for the epoxide resin, which is either a compound having at least three hydrogen atoms directly attached to aliphatic or cycloaliphatic amino nitrogen atoms present in an amount of from about 0.8 to 1.2 amino-hydrogen equivalents of the amine per 1,2-epoxide equivalent of the epoxide resin, or a tertiary amine having at least one nitrogen atom directly attached to carbon atoms of aliphatic or cycloaliphatic groups exclusively and at most two hydrogen atoms attached to amino nitrogen atoms present in an amount of from 1 to 40 parts by weight per 100 parts by weight of the epoxide resin, and wherein the polymercaptan is employed in a quantity sufficient to supply from 0.8 to 1.1 mercaptan groups per ethylenic double bond of the polyene and the polymercaptan plus polyene are present in amount of from 10 to 150 parts by weight per 100 parts by weight of the epoxide resin.
Claim 3
Dependent Claim
30 words
A composition according to claim 1, wherein the epoxide resin is a polyglycidyl ester, a poly(β-methylglycidyl) ester, a polyglycidyl ether, a poly(β-methylglycidyl) ether, a poly(N-glycidyl) compound or a poly(N-β-methylglycidyl) compound.
Claim 4
Dependent Claim
18 words
A composition according to claim 1, wherein the polymercaptan contains up to 6 mercaptan groups per average molecule.
Claim 5
Dependent Claim
29 words
A composition according to claim 1, wherein the polymercaptan is an ester of a monomercaptancarboxylic acid with a polyhydric alcohol or of a monomercaptanmonohydric alcohol with a polycarboxylic acid.
Claim 6
Dependent Claim
108 words
A composition according to claim 4, wherein the polymercaptan is of the formula ##STR31## where R 3 represents an aliphatic or araliphatic hydrocarbon radical of at least 2 and at most 60 carbon atoms, which may contain not more than one ether oxygen atom, R 4 represents a hydrocarbon radical of 1 to 4 carbon atoms, which may contain not more than one carbonyloxy group, a is an integer of from 2 to 6, b is zero or a positive integer of at most 3, such that (a + b) is at most 6, and c and d each represent zero or 1, but are not the same.
Claim 7
Dependent Claim
52 words
A composition according to claim 5, in which the polymercaptan is of the formula R.sup.5 (OCOR.sup.6 SH).sub.a where a is as defined in claim 5, R 5 is an aliphatic hydrocarbon radical of from 2 to 10 carbon atoms, and R 6 denotes --CH 2 --, --(CH.sub. 2) 2 --, or ##STR32##
Claim 8
Dependent Claim
125 words
A composition according to claim 5, wherein the polymercaptan is of the formula R.sup.9 -(O).sub.c --CO(O).sub.d -- R.sup.7 (O).sub.d --CO(O).sub.c --R.sup.8 SH).sub.e where c and d are as defined in claim 5, e is an integer of from 1 to 6, R 7 represents a divalent organic radical, linked through a carbon atom or carbon atoms thereof to the indicated --O-- or --CO-- units, R 8 represents a divalent organic radical, linked through a carbon atom or carbon atoms thereof to the indicated -SH group and -O- or --CO-- unit, and R 9 represents an organic radical, which must contain at least one --SH group when e is 1, linked through a carbon atom or carbon atoms thereof to the indicated --O-- or --CO-- unit.
Claim 9
Dependent Claim
105 words
A composition according to claim 7, where either c is zero and R 7 represents a saturated aliphatic hydrocarbon chain of 2 to 250 carbon atoms, which may be substituted by methyl groups and by -SH groups and which may be interrupted by ether oxygen atoms and by carbonyloxy groups, or c is 1 and R 7 represents (a) a saturated aliphatic hydrocarbon group of 2 to 10 carbon atoms, which may bear an --SH group, (b) a cycloaliphatic-aliphatic hydrocarbon group of 5 to 34 carbon atoms, which may contain ethylenic unsaturation, or (c) a mononuclear arylene hydrocarbon group of 6 to 12 carbon atoms.
Claim 10
Dependent Claim
63 words
A composition according to claim 7, wherein, when c is zero, R 8 represents a saturated aliphatic hydrocarbon group of 1 to 3 carbon atoms, which may bear a carboxyl group, and, when c is 1, R 8 denotes a saturated aliphatic hydrocarbon group of 2 to 4 carbon atoms which may be substituted by a hydroxyl group or by a chlorine atom.
Claim 11
Dependent Claim
106 words
A composition according to claim 7, wherein R 9 denotes (a) an aliphatic or cycloaliphatic-aliphatic hydrocarbon group of 2 to 51 carbon atoms, which may bear at least one -SH group (b) a mononuclear or dinuclear arylene hydrocarbon group of 6 to 15 carbon atoms, (c) a chain of 4 to 250 carbon atoms, interrupted by at least one ether oxygen atom and optionally substituted by at least one --SH group, or (d) a chain of 6 to 750 carbon atoms, interrupted by at least one carbonyloxy group, optionally interrupted by at least one ether oxygen atom and optionally substituted by at least one --SH group.
Claim 12
Dependent Claim
123 words
A composition according to claim 3, wherein the polymercaptan is of the formula ##STR33## where each "alkylene" group contains a chain of at least 2 and at most 6 carbon atoms between consecutive oxygen atoms, f is a positive integer, such that the average molecular weight of the polymercaptan is more than 10,000, g is zero or 1, h is zero or a positive integer such that (h + j) is at most 6, j is an integer of from 2 to 6, R 10 represents the aliphatic hydrocarbon radical, containing from 2 to 10 carbon atoms, of a polyhydric alcohol after removal of (h + j) alcoholic hydroxyl groups, and R 11 represents an aliphatic radical containing at least one mercaptan group.
Claim 13
Dependent Claim
49 words
A composition according to claim 11, wherein the polymercaptan is an ester of the formula ##STR34## or an ether of the formula ##STR35## where R 5 is as defined in claim 6, "alkylene", f, h, and j, are as defined in claim 11, and k is 1 or 2.
Claim 14
Dependent Claim
104 words
A composition according to claim 3, wherein the polymercaptan is a mercaptan-terminated sulfide of the general formula ##STR36## where each R 12 denotes an alkylene hydrocarbon group containing from 2 to 4 carbon atoms, R 13 denotes --H, --CH 3 , or --C 2 H 5 , m is an integer which has an average value of at least 1, such that the average molecular weight of the sulfide is at most 10,000, and either n is zero, in which case p and q are each also zero, or n is 1, in which case p is zero or 1 and q is 1.
Claim 15
Dependent Claim
18 words
A composition according to claim 13, where R 13 denotes hydrogen and n and p are each 1.
Claim 16
Dependent Claim
97 words
A composition according to claim 3, wherein the polymercaptan is a mercaptan-terminated poly(butadiene) of the formula ##STR37## each R 14 represents --H or --CH 3 , R 15 represents --CN, --COOH, --CONH 2 , --COOR 16 , --C 6 H 5 , or --OCOR 16 , where R 16 is an alkyl group of one to eight carbon atoms, t is an integer of at least one, u is zero or a positive integer, and r is an integer of more than one, such that the average molecular weight of the polymercaptan is not more than 10,000.
Claim 17
Dependent Claim
63 words
A composition according to claim 15, wherein the polymercaptan is of the formula ##STR38## where v is either zero, in which case w is 1, or it is 1, in which case w is an integer of from 2 to 5, and x is an integer such that the average molecular weight of the polymercaptan is at least 1250 and at most 5000.
Claim 18
Dependent Claim
40 words
A composition according to claim 3, wherein the polymercaptan is a mercaptan-terminated oxyalkylene compound of the general formula ##STR39## where each R 14 has the meaning assigned in claim 15, and y is an integer of from 1 to 4.
Claim 19
Dependent Claim
44 words
A composition according to claim 3, wherein the polymercaptan is of the formula ##STR40## where each R 6 is as defined in claim 6, each R 14 is as defined in claim 15, and R 17 denotes --H or a group --COR 6 SH.
Claim 20
Dependent Claim
33 words
A composition according to claim 1, wherein the polyene has an average molecular weight of not more than 2000 and contains at least two ethylenic double bonds, each α to a carbonyloxy group.
Claim 21
Dependent Claim
70 words
A composition according to claim 19, wherein the polyene contains at least two maleic acid residues of formula ##STR41## directly attached to each end to carbon atoms, or itaconic acid residues of formula ##STR42## directly attached at each end to carbon atoms, or acrylic residues of formula ##STR43## directly attached to carbon atoms, where R 18 denotes --H, --Cl, --Br or an alkyl group of 1 to 4 carbon atoms.
Claim 22
Dependent Claim
16 words
A composition according to claim 20, wherein the polyene contains at most six such ethylenically-unsaturated units.
Claim 23
Dependent Claim
31 words
A composition according to claim 20, wherein the polyene is a maleic ester of a poly(oxyalkylene) polyol and contains the repeating unit ##STR44## where "alkylene" is as defined in claim 11.
Claim 24
Dependent Claim
26 words
A composition according to claim 1, wherein at least one of the polyene and the polymercaptan has an average molecular weight of not more than 1000.
Claim 25
Dependent Claim
48 words
A composition according to claim 1, wherein the curing agent (d) is a compound having at least three hydrogen atoms directly attached to aliphatic or cycloaliphatic amino nitrogen atoms and provides from 0.8 to 1.2 aliphatic or cycloaliphatic amino nitrogen atoms per 1,2-epoxide group of the epoxide resin.
Claim 26
Dependent Claim
68 words
A composition according to claim 1, wherein the curing agent (d) is a tertiary amine having at least one nitrogen atom directly attached to carbon atoms of aliphatic or cycloaliphatic groups exclusively and at most two hydrogen atoms attached to amino nitrogen atoms and there is used from 1 to 40 parts by weight of such a curing agent per 100 parts by weight of the epoxide resin.
Claim 27
Dependent Claim
58 words
A composition according to claim 1, wherein the curing agent (d) is an alkylenepolyamine containing at least two primary amino groups, a poly(aminoamide) obtainable by reaction of such an alkylenepolyamine with an at least dicarboxylic acid or an amide-forming derivative thereof, or an adduct of such an alkylenepolyamine or of such a poly(aminoamide) with a mono- or di-1,2-epoxide.
Claim 28
Dependent Claim
56 words
A composition according to claim 1, wherein the curing agent (d) is a cycloaliphatic polyamine containing at least two primary amino groups, a poly(aminoamide) obtainable by reaction of such a cycloaliphatic polyamine with an at least dicarboxylic acid or an adduct of such a cycloaliphatic polyamine or of such a poly(aminoamide) with a mono- or di-1,2-epoxide.
Claim 29
Dependent Claim
22 words
A composition according to claim 1, which further contains an accelerator for the reaction between the polymercaptan (b) and the polyene (c).
Claim 30
Dependent Claim
17 words
A composition according to claim 20, wherein the accelerator is a Bronsted base or a free-radical catalyst.
Claim 31
Dependent Claim
30 words
A composition according to claim 1, in which the curing agent (d) is a poly(aminoamide) and the composition further contains an accelerator for the curing of the epoxide resin (a).
Claim 32
Dependent Claim
33 words
A composition according to claim 30, in which the accelerator is an aliphatic amine containing at least one tertiary amino group and at most one primary amino group or is a Mannich base.
Claim 33
Dependent Claim
37 words
A two-part pack, the contents of which, on mixing, provide a composition as claimed in claim 1, one part containing an epoxide resin and a polyene and the other part containing a curing agent and a polymercaptan.
Claim 34
Dependent Claim
15 words
A pack as claimed in claim 32, wherein the polymercaptan contains no carboxylic ester groups.
Claim 35
Dependent Claim
40 words
A three-part pack, the contents of which, on mixing, provide a composition as claimed in claim 1, one part containing an epoxide resin and a polyene, a second part containing a polymercaptan, and the third part containing a curing agent.
Claim 36
Dependent Claim
27 words
A method for bonding surfaces together which comprises sandwiching between, and in contact with, the surfaces a composition as claimed in claim 1 and curing the composition.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-11-20 | 1982-05-22 | 1982-11-21 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-11-20 | 1986-05-22 | 1986-11-21 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-11-20 | 1990-05-22 | 1990-11-21 | $7700.00 | Window Closed / Lapsed |