CA1056538A - Adhesive compositions comprising epoxide resin, polymercaptan, polyene, and amino-nitrogen curing agent - Google Patents
Adhesive compositions comprising epoxide resin, polymercaptan, polyene, and amino-nitrogen curing agentInfo
- Publication number
- CA1056538A CA1056538A CA213,701A CA213701A CA1056538A CA 1056538 A CA1056538 A CA 1056538A CA 213701 A CA213701 A CA 213701A CA 1056538 A CA1056538 A CA 1056538A
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- polymercaptan
- carbon atoms
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- polyene
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Abstract of the Disclosure Compositions, useful as adhesives, comprise (a) an epoxide resin having glycidyl, .beta.-mehylglycidyl, or 2,3-epoxycyclo-pentyl groups directly attached to oxygen, nitrogen, or sulfur atoms (b) as curing agent for the epoxide resin, either one of certain (cyclo)aliphatic amines or one of certain ter-tiary amines, and also (c) a polymercaptan, and (d) a polyene having at least two activated ethylenic double bonds, each to an atom of oxygen, nitrogen, or sulfur, the sum of these double bonds and of the mercapean groups in the poly-mercaptan 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.
Description
1~5653~
THIS INV~NTïO~ lela~e~ to new a~le~ive co~*osition~, ~o ~ethods of bonding surface~ to~ether by means of these co~positions, and to structures prepared by these m~thods.
The usefulness and versatility of epoxide resin adhesive S compositions axe well known. Such coT~ositions are made up of two essential constituents,the epoxide resin t i.e., a subst~lce containing ~ore thsn one l,2-epoxîde group per ~v~rage molecule) and a catalyst ,r curing agant which ea~es the ~poxide resin to cro~s-link or itself reacts with the resin, these con~tituants reactin~ to for~ a cured product ha~in8 8 hi~h specific adhesion to a wide variety of substrates. P~rticulsrly useful ~hesives are those that cure at room temperatures, say,20C, or at moderate temperatures, s~y, at or belo~r 60C.
Most epoxide re3in adhesive compositions hitherto available lack "green strength", that is to say~ they are not tacky before they soiidify, an~ surfaces to be bonded to each other by the adhesive must be held togPther by ~igs, clips, presses, or other ~e~porary fasteners ~hilst solidi~ication takes place. Attemp~s have been made to over~ome this disadvantage by dissolving certain high-m~lec~lar
THIS INV~NTïO~ lela~e~ to new a~le~ive co~*osition~, ~o ~ethods of bonding surface~ to~ether by means of these co~positions, and to structures prepared by these m~thods.
The usefulness and versatility of epoxide resin adhesive S compositions axe well known. Such coT~ositions are made up of two essential constituents,the epoxide resin t i.e., a subst~lce containing ~ore thsn one l,2-epoxîde group per ~v~rage molecule) and a catalyst ,r curing agant which ea~es the ~poxide resin to cro~s-link or itself reacts with the resin, these con~tituants reactin~ to for~ a cured product ha~in8 8 hi~h specific adhesion to a wide variety of substrates. P~rticulsrly useful ~hesives are those that cure at room temperatures, say,20C, or at moderate temperatures, s~y, at or belo~r 60C.
Most epoxide re3in adhesive compositions hitherto available lack "green strength", that is to say~ they are not tacky before they soiidify, an~ surfaces to be bonded to each other by the adhesive must be held togPther by ~igs, clips, presses, or other ~e~porary fasteners ~hilst solidi~ication takes place. Attemp~s have been made to over~ome this disadvantage by dissolving certain high-m~lec~lar
2~ wel~;ht polymers in one or more components of the co~positior. to act as a tac~ifier. In general, such compositions suffer fro~ the ~ w~ack that tne blend of the added polym~r and the epoxide resin is viscous and beco~es tac~y too rapidly, leading to difficulties in mixing it with other constituents of the compositions or in ap?lying ;~ in a suffici2ntly ~hin layer. To cou~ter this, vola~ile ~L~5~S313 solvents could be incor?or~ted, but the solvent~containing compositions cannot always be spread in layers of the desired thickness, the solven~
may attack the object to be bonded, and many types of solventS introduce flammabilitv or toxicity ha~ards into the workshop We have now found that the desired objective of producing an epoxide resin adhesive ~hich can easily be mixed, dispensed9 and spread, and which w~ll become tacky in use, may be achieved, withou~ the need to add a volatile solvent, by employing certain combinations o~
apoxidc resins, polymercaptans, and polyenes with a curing agent for the epoxide resin. The curing agent may be one of certain aliphatic or cycloaliphatic polyaminessYhich cure the epoxide resin by a cross-linking addition reaction; or it may be one of certain tertiary amines which cure the epoxide resin by catalytically-induced polymerisation.
The present invention accordingly provides a composition comprising ta) an e~oxide resin having, per average molecule, more than one 1,2-epoxide group of formula R2, - CH - C - C - H
directly attached to oxygen, sulphur, or nitrogen, where either R
- and R2 independently of one another represent hydrogen, in which case Rl denotes hydrogen or methyl, or R and R~ conjointly represent -CH2C~2-, in which case R denotes hydrogen, (b~ a polymercaptan having at least two mercaptan groups per average molecule, (c) a polye~e having, per average molecule, at least tws ethylenic double bonds, each ~ to an atom of oxygen, r.itrogen, or sulphur, the sum of such ethylenic double bonds and oî the mercaptan groups in (b? being more than 4, and preferably from 5 to 8, and (d? as curing agent for the epoxide resin, either a compound havir,g at least three hydrogen atoms directly attached to ~OS6538 ali~hatic or cycloaliphatic amino nitrogen atoms 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.
This in~ention further pro~ides a method for bonding suraces together which comprises sandwiching between, and in contact wi.h, the surfaces a curable compositioll of this in~ention, and also articles havin~ surfaces bonded together by the aforesaid method.
A feature of this invention is that the compositions~presumably through the reaction o~ the polymercaptan (b) with the polyene (c)~ rapidly form a rubbery adhesive, which is sufficiently strong for many purposes, in an extremely short time t typically, in less than 1 hour and often in less than 15 minutes)~ which adhesive su`bsequently ir.creases in s~rength, presumably due to reaction of the curing agent (d) with the epoxide resin (a)7to give the high strength normally associated with epoxide resin adhesives.
In the usual ~ethods of manufacturing epoxide resins, mi~tures of compounds of differing molecular weight are obtained, these mixtures ordinarily containing a proportion of compounds whose epoxide groùps have undergone partial hydrolysis. The ~verage number of 1,2-e~oxide groups per molecule of the resin need not be an integer of at least 2;
it is generally a fractional number but must in any case be greater - than 1Ø
Examples of resins which may be used are polyglycidyl and poly(~-methylglycidyl) esters obtainable by reaction of a substance containing two or re carboxylic acid groups wit-n epichlorohydrin, glycerol dichlorohydrin, or ~-methylepichlorohydrin in the presence of ~S653~3 alkali. S~ch esters m~y be deri~ed fro~ alipllatic carboxylic acids, e.~., oxalic acid, succinic acid, adipic acid, seb~cic acid, and dimerised or trimerised linol~c acid, fro~ cycloaliphatic carboxylic acids such a5 hexahydrophthalic acid, 4~methylhexahydrophth~1ic acid, tetrahydrophthalic acid~ and 4 me~hyltetrahydrophthalic acid, and from aromatic carboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid.
Other epoxide resin~ which may be u~ed include polyglycidyl and poly( ~-methyl~lycidyl) ethers, such as those obtainable by reaction of a substance containi~g at least two alcoholic hydroxyl groups or at least two phenolic hydroxyl groups with th~ appropriate epichlorohydrin or glycerol dichlorohydrin u~der alkaline conditions or~ al~ernatively, in th~ presence of an acidic catalyst with subsequent treatment with alkali. Such ethers ma~ ~e derived from aliphatic alcohols, for ~xample, ethylene glycol, diethylene glycol, triethyl~ne glycol, and higher poly(ox~ethylene) glycols, propylene giycol and poly(oxypropylene) glycols, propane-1,3-d~ ol, butane-1,4-diol, pentane-1,5-diol, hexane-1,5-diol, hexane-1,2,6-triol, glycerol, l,l,l-trimethylolpropane, and pentaerythritol;~rom cycloaliphatic alcohols such as quinitol, l,l-bis(hydroxymethyl)cyclohex-3-en29 bis(4-hydroxycyclohexyl)~ethanP, and 2,2-bis(4-hydroxycyclohexyl~propane; and from alcohols containing aromatic nuclei, such as ~,N-bis(2-hydroxyethyl) aniline and _ _ 4,4-bis(2-hydroxyethylzmino)diphe~yl~thane. Preferably ~he ethers are polyglycidyl ethers of an at lea~ dihydric phenol, for exsmple, 25 resorcinol, catechol, hydro~inone, bis(4-hydroxyphenyl)meth2ne, ~OS~i~;38 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 4,4 _dihydroxyphenyl, bis(4-hydroxyphenyl) sulphone, and phenol-formaldehyde, alkylphenol_ formaldehyde, and chlorophenol-formaldehyde novolac resins, 2,2_bis(4_hydroxyphenyl)propane (otherwise known as bisphenol A), and 2,~-bis(3,5-dibromo-4-hydroxyphenyl)propane.
There may further by employed poly (N~glycidyl) and poly(N- ~ methyl-glycidyl) compounds, for example, those obtained by dehydrochlorination of the reaction products of the epichlorohydrin and amines containing at least two hydrogen atoms directly attached to nitrogen, such as aniline, n-butylamine, bis(4-aminophenyl)methane, bis~4-aminophenyl) sulphone~ and bis(4-methylaminophenyl)methane. Other poly (N-glycidyl) c~m~dunds that may be used include triglycidyl isocyanurate, N~NI-diglycidyl derivatives of cyclic alkylene ureas such as ethyleneurea and 1,3-propyleneurea, and N,N'-diglycidyl derivatives of hydantoins such as 5,5-dimethylhydantoin.
Compounds of formula I in which R and R conjointly represent -CH2CH2-and R denotes hydrogen include bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycylcopentyl glycidyl ether, and 1,2-bis(2 3 -epoxycyclopentyloxy)-ethane.
Especially suitable epoxide resins are polyglycidyl ethers of 2,2_bis(4-hydroxyphenyl~propane or of a novolac from phenol ( which may be substituted in the ring by chlorine or a hydrocarbon alkyl group of from 1 to 4 carbon atoms) and formaldehyde, having an epoxide content of at least 1.0 epoxide equivalent per kilogram.
Tha curing agent may be an alkylenepolyamine containing at least two primary a~ino groups, such as diethylenetriamine, triethylenetetramine, and their 1,2-propylene homologues, and he~amethylenediamine and its ~S653l~
2,2,4_ and 2,4,4_trimethyl ana~logues and cycloaliphatic amines such as 3-aminomethyl_3,5,5_trimethylcyclohexylamine (isophoronediamine).
Particularly suitable are poly(aminoamides) obtainiable in a known manner by the reaction of a polyalkylenepolyamine having at least four amino-hydrogen atoms per molecule with an at least dicarbocylia acid or an amide-forming derivative thereof (i.eO, a derivative in which carboxyl groups are replaced by groups~ such as carbalkoxy groups each of two to six carbon atoms, whieh react with a primary or secondary amine to produce amide groups) in sueh a manner that the product eontains, as already ind~cated, at least three amino-hydrogen atoms per molecule. me carbo~ylic acid is preferably a dimerised or trimerised ethylenically-unsaturated aliphatic monocar~
box~ic acid such as linoleic acid; it may be modified by incorpor-ation of styrene or other aromatic vinyl compound during oligomeri-sation, so forming an ara-~;phatic~acid.
Also suitable are adducts of such alkylenepolyamines and poly(aminoamides) with mono- or di-1,2-epoxides (for example, ethylene oxide, propylene oxide, and diglycidyl ethers of alcohols and phenols), it being understood that the adduct itself contains at least three hydrogen atoms directly attached to aliphatic or cycloaliphatic amino nitrogen atoms.
Suitable tertiary amines include N-benzyldimethylamine, pentakis (N-methyl)diethylenetriamine, tri-n-amylamine, triethyl-amine, triethanolamine,Mannich bases of the formula XIX set out hereinafter, especially tris(dialkylaminoalkyl)phenols such as 2,~6-tris(dimethylaminomethyl~-phenol, and primary-tertiary amines, for example ~N-dialkylalkylenediamines ~ 7 --- ~05653~3 such as N,N-dieth~lethane-1,2-diamine, N,~-dimethylpropane-l,
may attack the object to be bonded, and many types of solventS introduce flammabilitv or toxicity ha~ards into the workshop We have now found that the desired objective of producing an epoxide resin adhesive ~hich can easily be mixed, dispensed9 and spread, and which w~ll become tacky in use, may be achieved, withou~ the need to add a volatile solvent, by employing certain combinations o~
apoxidc resins, polymercaptans, and polyenes with a curing agent for the epoxide resin. The curing agent may be one of certain aliphatic or cycloaliphatic polyaminessYhich cure the epoxide resin by a cross-linking addition reaction; or it may be one of certain tertiary amines which cure the epoxide resin by catalytically-induced polymerisation.
The present invention accordingly provides a composition comprising ta) an e~oxide resin having, per average molecule, more than one 1,2-epoxide group of formula R2, - CH - C - C - H
directly attached to oxygen, sulphur, or nitrogen, where either R
- and R2 independently of one another represent hydrogen, in which case Rl denotes hydrogen or methyl, or R and R~ conjointly represent -CH2C~2-, in which case R denotes hydrogen, (b~ a polymercaptan having at least two mercaptan groups per average molecule, (c) a polye~e having, per average molecule, at least tws ethylenic double bonds, each ~ to an atom of oxygen, r.itrogen, or sulphur, the sum of such ethylenic double bonds and oî the mercaptan groups in (b? being more than 4, and preferably from 5 to 8, and (d? as curing agent for the epoxide resin, either a compound havir,g at least three hydrogen atoms directly attached to ~OS6538 ali~hatic or cycloaliphatic amino nitrogen atoms 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.
This in~ention further pro~ides a method for bonding suraces together which comprises sandwiching between, and in contact wi.h, the surfaces a curable compositioll of this in~ention, and also articles havin~ surfaces bonded together by the aforesaid method.
A feature of this invention is that the compositions~presumably through the reaction o~ the polymercaptan (b) with the polyene (c)~ rapidly form a rubbery adhesive, which is sufficiently strong for many purposes, in an extremely short time t typically, in less than 1 hour and often in less than 15 minutes)~ which adhesive su`bsequently ir.creases in s~rength, presumably due to reaction of the curing agent (d) with the epoxide resin (a)7to give the high strength normally associated with epoxide resin adhesives.
In the usual ~ethods of manufacturing epoxide resins, mi~tures of compounds of differing molecular weight are obtained, these mixtures ordinarily containing a proportion of compounds whose epoxide groùps have undergone partial hydrolysis. The ~verage number of 1,2-e~oxide groups per molecule of the resin need not be an integer of at least 2;
it is generally a fractional number but must in any case be greater - than 1Ø
Examples of resins which may be used are polyglycidyl and poly(~-methylglycidyl) esters obtainable by reaction of a substance containing two or re carboxylic acid groups wit-n epichlorohydrin, glycerol dichlorohydrin, or ~-methylepichlorohydrin in the presence of ~S653~3 alkali. S~ch esters m~y be deri~ed fro~ alipllatic carboxylic acids, e.~., oxalic acid, succinic acid, adipic acid, seb~cic acid, and dimerised or trimerised linol~c acid, fro~ cycloaliphatic carboxylic acids such a5 hexahydrophthalic acid, 4~methylhexahydrophth~1ic acid, tetrahydrophthalic acid~ and 4 me~hyltetrahydrophthalic acid, and from aromatic carboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid.
Other epoxide resin~ which may be u~ed include polyglycidyl and poly( ~-methyl~lycidyl) ethers, such as those obtainable by reaction of a substance containi~g at least two alcoholic hydroxyl groups or at least two phenolic hydroxyl groups with th~ appropriate epichlorohydrin or glycerol dichlorohydrin u~der alkaline conditions or~ al~ernatively, in th~ presence of an acidic catalyst with subsequent treatment with alkali. Such ethers ma~ ~e derived from aliphatic alcohols, for ~xample, ethylene glycol, diethylene glycol, triethyl~ne glycol, and higher poly(ox~ethylene) glycols, propylene giycol and poly(oxypropylene) glycols, propane-1,3-d~ ol, butane-1,4-diol, pentane-1,5-diol, hexane-1,5-diol, hexane-1,2,6-triol, glycerol, l,l,l-trimethylolpropane, and pentaerythritol;~rom cycloaliphatic alcohols such as quinitol, l,l-bis(hydroxymethyl)cyclohex-3-en29 bis(4-hydroxycyclohexyl)~ethanP, and 2,2-bis(4-hydroxycyclohexyl~propane; and from alcohols containing aromatic nuclei, such as ~,N-bis(2-hydroxyethyl) aniline and _ _ 4,4-bis(2-hydroxyethylzmino)diphe~yl~thane. Preferably ~he ethers are polyglycidyl ethers of an at lea~ dihydric phenol, for exsmple, 25 resorcinol, catechol, hydro~inone, bis(4-hydroxyphenyl)meth2ne, ~OS~i~;38 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 4,4 _dihydroxyphenyl, bis(4-hydroxyphenyl) sulphone, and phenol-formaldehyde, alkylphenol_ formaldehyde, and chlorophenol-formaldehyde novolac resins, 2,2_bis(4_hydroxyphenyl)propane (otherwise known as bisphenol A), and 2,~-bis(3,5-dibromo-4-hydroxyphenyl)propane.
There may further by employed poly (N~glycidyl) and poly(N- ~ methyl-glycidyl) compounds, for example, those obtained by dehydrochlorination of the reaction products of the epichlorohydrin and amines containing at least two hydrogen atoms directly attached to nitrogen, such as aniline, n-butylamine, bis(4-aminophenyl)methane, bis~4-aminophenyl) sulphone~ and bis(4-methylaminophenyl)methane. Other poly (N-glycidyl) c~m~dunds that may be used include triglycidyl isocyanurate, N~NI-diglycidyl derivatives of cyclic alkylene ureas such as ethyleneurea and 1,3-propyleneurea, and N,N'-diglycidyl derivatives of hydantoins such as 5,5-dimethylhydantoin.
Compounds of formula I in which R and R conjointly represent -CH2CH2-and R denotes hydrogen include bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycylcopentyl glycidyl ether, and 1,2-bis(2 3 -epoxycyclopentyloxy)-ethane.
Especially suitable epoxide resins are polyglycidyl ethers of 2,2_bis(4-hydroxyphenyl~propane or of a novolac from phenol ( which may be substituted in the ring by chlorine or a hydrocarbon alkyl group of from 1 to 4 carbon atoms) and formaldehyde, having an epoxide content of at least 1.0 epoxide equivalent per kilogram.
Tha curing agent may be an alkylenepolyamine containing at least two primary a~ino groups, such as diethylenetriamine, triethylenetetramine, and their 1,2-propylene homologues, and he~amethylenediamine and its ~S653l~
2,2,4_ and 2,4,4_trimethyl ana~logues and cycloaliphatic amines such as 3-aminomethyl_3,5,5_trimethylcyclohexylamine (isophoronediamine).
Particularly suitable are poly(aminoamides) obtainiable in a known manner by the reaction of a polyalkylenepolyamine having at least four amino-hydrogen atoms per molecule with an at least dicarbocylia acid or an amide-forming derivative thereof (i.eO, a derivative in which carboxyl groups are replaced by groups~ such as carbalkoxy groups each of two to six carbon atoms, whieh react with a primary or secondary amine to produce amide groups) in sueh a manner that the product eontains, as already ind~cated, at least three amino-hydrogen atoms per molecule. me carbo~ylic acid is preferably a dimerised or trimerised ethylenically-unsaturated aliphatic monocar~
box~ic acid such as linoleic acid; it may be modified by incorpor-ation of styrene or other aromatic vinyl compound during oligomeri-sation, so forming an ara-~;phatic~acid.
Also suitable are adducts of such alkylenepolyamines and poly(aminoamides) with mono- or di-1,2-epoxides (for example, ethylene oxide, propylene oxide, and diglycidyl ethers of alcohols and phenols), it being understood that the adduct itself contains at least three hydrogen atoms directly attached to aliphatic or cycloaliphatic amino nitrogen atoms.
Suitable tertiary amines include N-benzyldimethylamine, pentakis (N-methyl)diethylenetriamine, tri-n-amylamine, triethyl-amine, triethanolamine,Mannich bases of the formula XIX set out hereinafter, especially tris(dialkylaminoalkyl)phenols such as 2,~6-tris(dimethylaminomethyl~-phenol, and primary-tertiary amines, for example ~N-dialkylalkylenediamines ~ 7 --- ~05653~3 such as N,N-dieth~lethane-1,2-diamine, N,~-dimethylpropane-l,
3-diamine, and ~-(2-a~inoethy])pinera~ine~
An efective amount of the curing agent (d) is employed.
The proportion will depend upon its chemical struct~lre and the pr~perties sought in the curable composition and in.its.cu;red produ~t. The optimum proportion can readily be determined by methods familiar to tnose skilled in the art. When the curing agent is one having a~ least thr~e hydrogen a_oms directly attached to aliphatic or cycloaliphati.c amir.o-ni..rogen atoms there ~ill nor~aliy be used from GbOUt 0. 8 to 1.2 amino-hydrogen equivalents of the amine per 1,2-epoxide equivalent of the epoxide resin.
When the curing agent is a tertiary amine having at least one nitrogen atom attac.hed directly to aliphatic or cycloaiiphat~c groups exclusively, ~nd has at ~ost two hydro~en atoms attached to amino nitrogen atoms there is g~erally usPd fro~ 1 to 40 parts by weight per lOQ parts by weight of the epoxid2 resin.
A wide range o~ polym2rcap;~ns is suitable for use as component (c) in the com?osition o. this. i~ven-ion. Preferabl~ there are used ~6S38 polymercaptans con~aining up to 6 mercaptan groups per molecule.
One class comprises esters of monomercaptancarboxylic acids with polyhydric alcohols and of monomercaptanmonohydric alcohols with polycarbocylic acids.
rther preferred such esters are of the formula rOH 1 ~ ~ b(d) [ R3 ~ (Co)co(co)dR S~ II
\ COO~I ~
~ ~ ¦b(C) where R represents an aliphatic or araliphatic hydrocarbon radical of at least 2, and preferably at most 60, carbon atoms, which may 10contain not more than one ether oxygen atom, R represents a hydrocarbon radical, which may contain not more than one carbon~loxy group, and is preferably of from 1 to 4 carbon atoms, 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 sameO
Yet further preferred esters are polymercaptans of formula II
which are also of the formula R (OCGR SH)a III
where _ g _ 1(~56S3~
a has the meaning previously assigned, R is an aliphatic hydrocarbon radical of from 2 to 10 carbon atoms, and fH3 R6 denotes -CH2-, -(CH2)2-, or -CH-~
Also preferred are mercaptan-containing polyesters, i.ncluding esters of monomerca ~andicarbocylic acids, of formula R9 ~ )c- ~()d~ R7~0)d C()c - R SH ) IV
where c and d have the meaning previously assigned, e is an integer of from 1 to 6, R represents a divalent organic radical, linked through a carbon atom or carbon atoms thereof to the indicated ~0- or -C0- units, R represents a divalent organic radical, linked through a carbon atom~ or carbon atoms thereof to the indicated --SH group and -0- or -C0- unit~ and R represents an organic radical, which must contain at least one -SH group when e is 1, linke.dthrough a carbon atom or carbon atoms thereof to the indicated -0 or -C0- unitO
Preferably, R denotes, when c is zero, 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 oxygeniatoms and by carbonyloxy groups; while, when c is 1, R preferably denotes (a) a saturated al,phatic 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.
R8 preferably denotes, when c is zero, a saturated aliphatic hydrocarbon group of 1 to 3 carbon at~msD which may bear a carboxyl group~ and~ ~hen c is 1~ R8 preferably denotes a saturated allphatic hydrocarbon group of 2 to 4 carbon atoms which may be substituted by a hydroxyl group or by a chlorine atom.
~0 R preferably denotes (a) an aliphatic or cycloaliphatic-aliphatic hydrocarbon group of 2 to 51 carbon atoms, which may bear at least on -SH group.
(b) a mononuclear or dinuclear arylene hydrocarbon group of 6 to 15 carbon aeoms~
(c) a chain of 4 to 250 carbon atoms, interrupted by at least one ether oxygen a~om 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 ~y at least one -SH group.
Also suitable are esters and ethers which are of the general formula 653~
i ~O~alkylene)f OH jh ~O-alkylene)fO(CO~ IR ~ V
I
where each "alkylene" group contalns a chain of at least 2 and at most fi carbon atoms between consecutive oxygen atoms, f is a positive integer, preferably such that the average molecular weight of the polymercaptan is not more than 10000?
is ~ero or 1, H is zero or 8 positive integer such that (h ~ ~) is at most 6, is an integer of from 2 to 6, R10 represents the radical of a polyhydric aloohol after removal of (h + i) alcoholic hydroxyl groups, especially an aliphatic hydrocarbon radical of:from 2 to 10 carbon atoms, and R 1 represents an aliphatic radical containing at least one mercaptan group.
~ lkylenell units in individual poly(oxyalkylene) chains may be the same or different and ~hey may be substituted by, e.g.9 phenyl or chloromethyl groups. Preferably they are -C2H4- or -C3H6- groups~
Preferred amongst the compounds of formula V are ~he esters of formula _ ~
5 / ~(O-alkylene~ OH ~ h ~(-alkYlene)fococku2ksu 1 Vl and ethers of formula ;53~3 ¦ (0_alkylene)fO~ j h R ~ I VII
~` (O-alkylene)focH2cHcH2sH
OH
where "alkylene", R5, f, h, and ~ have the meanings previously assigned, and k is 1 or 2.
Yet other suitable polymercaptans are mercaptan-terminated sulphides of the general formula HS - _ R12(o~ (CHO) R SS i R (0) (CH0) R SH
where each R12 denotes an alkylene hydroca}bon group con~aining from 2 to 4 carbon atoms, o R13 denotes -H, -~H3, or -C2H5~
m is an integer which has an average value of at least 1, and is preferably such that the average molecular weight of the sulphide is at most 10000, and either n is zero, in which case p and ~ are each also zero, or n is 1, in which case p zero or 1 and q is 1.
The preferred sulphides are those of formula VIII where R 3 denotes hydrogen and n and ~ are each 1, m being such that the molecular weight of the sulphide is from 500 to 8000.
iO5GS38 Another class of polymercaptane comprises mercaptan terminated poly(butadienes) of the formula l I
HS- - (CH2~ - C~CH2 ~ ~C~l2 C )u ~ -. -SH IX
or 14 ~
H ~ C \- ~X - - CH2. - ~CH215~U ~ - SH
l ~ t r X
where each Rl4 represents -H or -CH3, R represents -CN, COOH, -CONH2, -COOR , -C6H5, or ~OCOR16, ~here R16 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, p~eferably such that the average number molecular weight of the polymercaptan is not more than 10000.
Preferably the polymercaptans of formula IX are also of the formula 1~653~
HS ~ CH2CH = CHCH2 ~ --~CH2iH ~ ]
and those of formula ~ are correspondingly of the formula HS ~ CH2 ~ ~CH2CH)~ ~ SH XII
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.
Yet another suitable class of polymercaptans comprises the mercaptan-terminated oxyalkylene compounds of the general formula ~14 R14 RS (CHCH20)y CHCH2SH XIII
where each R has *he meaning previously assigned and X is an integer of from 1 to 4.
A still further class comprises poly(monomercaptancarboxylates), - especially the thioglycollates and mercaptopropionates, of tris(2-hydroxyethyl3 isocyanurate or of tris(2-hydroxypropyl) isocyanurate, i.e., the compounds of formula ios6~s ~14 NGH2C~ S~
/\
C~ CO
Rl OC~CH2ll NCH2CHOCQR SH XIV
where R17 denotes -H or a group -CO~SH, and ea^h R6 and R14 have ehe meanings previously assi~ned.
S Polyenes preferred ~or the purposes of this invention have a~
: average molecular wei~ht of ~ot more than 2000 snd they contain a~
least two ethylenic double bonds each ~ to a c~rbo~ylo~y ~roup, e~pecially în the fo~m of ~aleic acid residues of formula , --OCCH~ CO_ Il Il XV
O O
directly attached at ea~h e~d to cRrbon ~tom~, or in th2 for~ of itaconic acid residues of fo~mula ~2CO~W
: I ~ 2 i~
directly attached at each end to carbon atoms9 or in the form of - acrylic residues of for~ula - CC - C~2 X~ll 16 _ . ` - ` ':.''' ` ' ~,1 ~05~;38 directly attached to carbon atoms, where R denotes -H, -Cl, -Br, or an alkyl group of 1 to 4 carbon atoms3 Preferably the polyenes contain, per molecule, up to six ethylenically-~nsaturated units of formula XV, XVI, or XVII.
Particularly preferred polyenes are maleic esters of poly(oxyalkylene) polyols and contain the repeating unit _ rO-alkylene OICH = C~CIl XVIII
L l where~'alkylene" has the meaning assigned above.
Preferably the polymercaptan is employed in a quantity sufficient to supply from 0.8 to 1.1 mercaptan groups per said e~hylenic double bond of the polyene, and the compositions contain from 10 to 150, and especially up to 75, parts by weight of the polymercaptan plus polyene per 100 parts by weight of the epoxide resin. The optimum amounts for a particular composition may readily be ascertained by simple experiment.
Desirably, at least one of the polyene and the polymercaptan has an average molecular weight of not more than 1000 The compositions may be heated, e~.g., at temperatures of from 35 C to 150 C, to increase the rate of curing, but often they will cure sufficiently rapidl~ at room temperatu~e for most purposes.
- ~)S6538 Conventional accelerators for promoting the curing of the epoxide resin ~a) by its curing agent (d) may also be included, particularly when that agent is a poly(aminoamide). Such accelerators include aliphatic amines containing at least one tertiary amino group and at most one primary amino group, such as N,N-dialkylethane-l, 2_diamines and N,N-dialkylpropane-1~3-diamines, especially the N~N-dimethyl and N,N,-diethyl derivati~es, and also Mannich bases of the formula R19(CH2NR R )a X~
~0 where al is an integer of at least 1 and is preferably 3 or 4, R represents the radical of a mononuclear or polynuclear phenol, which may be monohydric or polyhydric, the said radical having free valencies, and each R represents an aIkyl or hydroxyalkyl group of up to four carbon atoms.
A preferred Mannich base is 2,4,6-tris~dimethylaminomethyl) phenolO
me compositions may also contain an accelerator for the reaction between the polyene and the polymercaptan, this accelerator usually being an organic or inorganic Br~nsted base or a ~ree-radical catalyst. me latter are of general applicability and include organic or inorganic persxides and pers~lts such as benzoyl peroxide, hydrogen peroxide, ~ert.butyl hydroperoxide, di~ propyl peroxydicarbonate, and ammonium persulphateO
~56~3~
For the preferred polyenes, i.e., those ha~ing ethylenic double bonds a to carbonyloxy groups, Br~n3ted bases may be ~sed instead. Examples of suitable Br~nsted bases sre pri~ary, secondary, ~nd tertiary amines, such as triethylamine, N,N-dimeehyl~ni~ e, and N-ben~yldimethyi~ine, lower alkanol2mines ( e.g., m~no-, di-t and tri-eth~olamine), lower alkylenepolyaminss ( e.g., ethylenediamine, diethylenetriamine, triethylenetetramine 9 te~raethylenepentamine, propane~l,2-diamine, propane-1,3~digmine, and hexamethylenedia~ine), also quater~ary am~onium bases such as tetramethyla~onium ~ydroxide, and ~ater-soluble inorganic hydroxides ~ especially sodiu~ hydroxide) and inor~anic salts such as trisodiu~ pbosphate, sodium carbonate, sodium bicarbonate, sodium pyrophosphate, snd sodiu~ acetate.
Of course, some curing agents for epoxide resins are also Br~nsted bases, as are some accelerators for the curing of epoxide resins, and when such a curing agent or accelerator is used there is normally no advantage in employing another such base to promote the reaction between the polymercaptan and the polyenes.
Optionally, plasticisers may be incorporated and these include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate.
20 There may also be present so-called reactive diluents; especially monoepoxides such as n-butyl glycidyl ether, iso-octyl glycidyl ether, - phenyl glycidyl e~her, cresyl glycidyl ethe~s, glycidyl acrylate, -- lq --:~5~;~38 glyci~l meehacrylate~ a~d glyci~yl esters of br~ched tertiary, aliphatic monocaribo~lîc acids. The co~ositions may also con~ain fillers, colouring matter, flow-control age~ts, and flame inh~bitors. Suitable extenders and fillers are asphalt, bitum~n, glass fibres, ballotinig mica, suartz flour, calcium carbonate, talc, cellulose, kaol n~ wollasto~ite, ~nd colloidal silica having a large specific surface area-The co~positions of the present i~vention may be ~upplîed a~ a twc.-part psck; preferably~one part contains the epoxide resin (a~ and the polyene ~C~ and the other the curing agent G~) and the polymercapt~n (~), bacause~otherwise, the epoxide resin may be cured pL-ema~urely on storage by mean8 of the polymercaptan, and further, the curing age~t ~d),unless it is exclusively a tertiary amine, react a. the ethylenic double bonds of the polye~e (c~. Because, too, poly~ercap~anc2rboxylates reAct on prolo~ged contact with ~liphatic amines, it is preferred, ~here the co~po9itio~ iS to be packaged in parts, to use as component (b) a poly~ercaptan ~hich contains no car~oxylic ester groups.
A particularly pref~rred combination of curing age~t and polymerca?tan for prolonged storage ;s a poly( minoa~a~le) and a polymercaptan of the general fo-r~ula VII or VIII.
The co~sitions ~ay, of course, slso be supplied as a three-part pacX, the epoxide resin being mixed with the polysne ~c).
rne following Exac~ples illustr~te the i~vention. Unle~s o~herwi3~ indica~ed, par~s are by weigh~. Temperatures ar i~
degrees Ce;sius.
~ 20 -:lOS653B
Pol~mercaptan A
is substantially of the average formula CH2 - _ _ I f 3 1 CH _ ~ CH2CH)b OCH2CHCH2SH 3 where bl is an integer of average value 2,5 and was prepared as described in United States Patent Specification No. 3258495.
Polymercaptan B
is the commercially-available po~ysulphide substantially of the average formula US ~ CH2CS2l)cH20 CH2CH255 ~H2Æ120CH20C112CH25H
Pol~mercaptan C
is of the formula CH3CH - r T 3 CH2 - L(OC~2CH) OCOCH2SH ~ XXII
~, where cl is an integer of average value 3.16. The preparation of mercaptancarboxylates of polyoxyalkylene polyols such as Polymercaptans C to F and H is described in British Patent Specification No. 1278934.
Polymercaptan D
lS of the formula ~056538 CH~ 3 CH- ~ ~OCH2CH~d OCOCH2SH ¦ XXIlI
where d is an integer of average value 3.69.
Polymercaptans E and F
are of formula XXIII, where dl is an integer of average value 5.41 and 7~14, respectively.
is the tetrakis(3-mercaptopropionate) of pentaerythritol.
Polymercaptan H
is of the formula CH3 _ C ._--CH2 (OCH2CH) e OCOCH~SH XXIV
where el is an integer of average value 2.~5.
Poly~erca-2tan J
is a hydroxy7-terminated polyester from l,l,l-trimethylolpropane ( 1 mol.)~ adipic acid ( 3 mol.,), and butane-1,4-diol ( 3 mol.), ~sterified with 3 mol. of 3-mercaptopropionic acid, prepared by .he procedure described in British Patent Specification No. 1311090.
Poly~ercaptan K
- is a mercaptan-terminated butadiene-acrylonitrile copolymer and has the general formula andJor HS~ ~ CH2CH = CHCH2~ ~CH2CU~ ~ SH
~ CH t _ 22 _ ,. ~, ~1~56S3~3 Polyene I
This polyester is made in a conventional manner by the reaction of maleic anhydride (3.06 mol.) with dipropylene glycol (3.21 mol.).
Polyene II
This polyester is prepared similarly Erom dipropylene glycol (2.1 mol.), maleic a~hydride (l mol.), and adipic acid (1 mol.).
Polyene III
Butane-1,4-diol diglyci~yl ether OL epoxide ~ontent 7.4 equiv./kg (108 g), itaconic acid (65 g), n-butyl glycidyl ether (28.1 g), ~-ben2yldimethylamine (2 g), and hydroquinone (0.2 g) are mixed and heated to 120, when an exothermic reaction sets in, the tem?erature of the mixture rising to 250. The product is rapidly cooled to 120 , and heated at that temperature for one hour. Polyene III is substan~ially of ~he formula 1. ~
11 Il' H - [ (CH2)40 CH2CHCH2CC - CCCH2CHCH2 - (CH2)3CH3 XXV
Polyene IV
2,2-bis(4-Hydroxyphenyl)propane (114 g), n-butyl glycidyl et~er (130 g), and ~-benzyldimethylamine (2 g) are hea~ed at 120 for 1 hour, then cooled to 70. Maleic anhydride (98 g) is added and heating is con~inued at 120 for 100 minutes. The product, Polyolefin IV, is substantially of the for~ula 6~i38 ~ ~ OCH2CHOCOC~ - CHCOH XXVI
Il IocH~
CH3 2 ( 2)3 3 I
Polyene V
A glycerol-propylene oxide adduct of average molecular weight 1000 (200 g ) is heated for 2 hours at 120 with 58.8 g of maleic anhydride in the presence of 2.6 g of N-benzyldimethylamine.
Polyene ~l is substantially of the formula 1 2- ~ C~3 CH~ r(CH2CH)f OCCH = (~HCOH ¦ XXVII
where fl is an integer of average value 15.65.
Polye~e VI
.
This is made similarly from 100 g of a glycerol-propylene oxide adduct of average molecular weight 300 and maleic anhydride (98 g ) with 3 g of tr_ethylamine as catalyst. Polyene VI is substantially of formula XXVlI, where '1 is an integer of average value 3.59.
Polyene VII
Butane-1,4-diol (lOB g), maleic anhydride (98 gj, and xyle~e (135 g) are heated together with stirri~g under reflux for 2 hours. Water formed during the reaction is removed by azeotropic distillation using a Dean and Stark trap. Toluene-?-sulphonic acid (2 g) is added and heating at reflux is con~inued for a further 2 hours. The - 2~ -S05~53~
maxture is coolad ~o 50, neutralised wi~h a~ueous potas~ium bicarbonate solution, ~he water and xylene are dis~illed olf, and the resldue i8 filtered.
Polyene VII is substantially of the for~ula ~ O O
H_ O(CH2)4 OCCH ~ C~C O(CH~)40~ XXVIIX
Polyene VIII
A glycerol-propylene oxide adduct o~ average ~olecular wei~ht 600 ( 600 g,) i~ hea~ed with 294 g of maleic anhydride in the presence o~ 9 g of triethylamine for 2 hou~s at 120. Then n-butyl glycidyl ether of epo~ide content 7.7 equiv./kg. ~ 331 g) is added dropwise in an atmosphere of nitroge~ and the mixture is heated for 1~ hours at 120.
Polyene VIII is sùb~an~ially of the formula 1 2 _ ~ 1 3 CH - t (ocH2cH)g OCCH ~ CHCOCH2CHCH2 t ~ 3 3 ~ XXIX
_ 3 ~H2 ~
where ~1 is an integer of average value 8.76.
Polyene IX
Glycerol ( 92 ~,) and maleic anhydride (294 g) are heated for 2 hours at 120 in the presence of 3.8 g of N-benzyldi~ethylamine. ~hen 343 g o~ n-butyl glycidyl ether (epoxide content 7.0 equiv./kg3 is added dropwise, an exothermic - 2~ -reaction taking piace, and the mixtufe i6 heated for 2 hours at 120 in an at sphere of nitrogen.
Polyene IX is of formula ~YIX, where gl is zero.
Polyene X
2l2-bis(p-Glycidyloxyphenyl~propane, of epoxide content 5.2 equiv./kg (384 g )~is heated for 2 hours at 120 with 144 g of acrylic acid in the presence of 5.3 g of N-benzyldimethylamine as catalyst and 0.53 g of ~-methoxyphenol as polymerisation inhibitor Polyene X is of the formula .
1 ~ocH2c3c32occH = C~12~ xxx - Polyene XI
is the tetrakis(methacrylate) of the adduct of p~ntaerythritol and ethylene oxide, i.e., is of the formula O
Il -' "' C(C~zOCH2CH20CC = C.~2)4 ~ CH3 1 Epoxide resin I
S
denotes a polyglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane having a viscosity at 21 in the range 200 to 400 poises: its epoxide content is 5.1-5.4 equiv./kg. , , ~ ~6 ~
105~538 ~?oxide r~sin II
denotes a polyglycidyl ether of a phenol-formaldehyde novola~ of average ~olecular weight 420. It has an epoxide content of 5.5-5.7 equiv.lkg.
Epox;de resin III
den~tes bis(4-(diglycidylamino)phenyl)methane having an epoxide content of 7.5-8.5 equiv./kg.
E~xide resin IV
.~ ~
denotes a polyglyci~dyl ether of bis(4-hydroxyphenyl)~ethane having an e~oxide content of 5.8 equiv./kg.
~=
denotes diglycidyl hexahydrophthalate having an epoxide content of 6. 2-6. 8 equiv./kg.
Epoxide resin Vl denotes l-glycidyloxym2thyl-3-glycidyl-5,5-di~ethylhydantoin having an epoxide conte.lt of 7.0-7.4 equiv./kg.
Epoxide resin VlI
denotes 4-~diglycidyla~ino)phenyl glycidyl ether having an epoxide content of 9.4-10.5 equiv.Ikg.
., /
.
Hardener I
denotes a poly~aminoamide) obtained by reaction of diethylenetriamine with a mixture of dimerised and trimerised linoleic acid: its amine value is 210-220 mg KOH/g Hardeners II and III
denote polytaminoamide)s prepared in a similar manner to Hardener I but having an amine value of 350-400 mg KOH/g and 290-320 mg ~OH/g respectivelY~.
Hardener IY
denotes a poly(aminoamide) prepared from a monomeric fatty acid and an aIiphatic polyamine and.he.ving'an amine value of 580-620 mg KOH/g Hardener V
.
denotes a ,similar poly(aminoamide) havi~g an amine value of 350-3~0 mg KOH/g Hardener VI
denotes ~-~2-aminoethyl)piperazine L5 Hardener_VII
denotes isophoronediamine Hardener VIII
denotes a commercial mixture of 2~,4- and 2/4,4-~rimethyl-hexamethylene-' - diamine 0 Hardener IX
denotes triethylene~etramine Hardener X
denotes N,N-diethylpropane-1,3-diamine Hardener XI
. .
denotes 2~4,6-tris(dimethylaminomethyl)phenol 2~ -1~5~S38 Hardener XII
:
denotes 3,3'-dimethyl-4Jd~'-diaminodicyclohexylmetllane Hardener XIII
denotes a ~oly(o~ropYlene) triprimary amine ~i.e., a trihydric aliphatic alcohol having three oxypropylene chalns a~ttached to the hydroxyl groups, each terminated by a primary amino ~roup) of average molecular w~ight 400.
Accelerator I
.
is 2,4,6-tris(dimethylaminomethyl)phenol.
Shear strengths of joints were determined using aluminium alloy strips 1.63 mm thick obtained under the designation "2L 73 Alclad"
which had been degreased, picXled by the process prescribed in the British Ministry of Technology Aircraft Process Specification DTD-915B, washed in runn;ng water1and dried ~t room temperature ("Alclad" is a registered Trade ~ark). Single lap joints 12 mm x ' 15 25 mm were prepared. T-peel strengtns were determined by the procedure described in United States ~ilitary Specification ~: M~M-A-132. Sheets of "2L 61 Alclad", 0.056 mm thick and 24 mm wide were used. Gelation times were determined by ascertaining when - the mixture, stirred with a small wooden spatula, became a rubbery solid and/or formed 'Istrings'' when pulled.
~, i~ :
.
~1~565313 ~X~MPLE. I
The n~ix~u~c~ shown in T~le ~ were prepared and their ~elation times s~ room te~erature, on 10 8 ~amples, wPre measured.
TABLE I
. ~
Epo~ide . Accel- Polymer- Polymer- Polyene Polyene Gel resin Hardener erator captan captan I II time I I I A B (min~.) _ _ . . _ .. ..
lO0 40 2 _ _ _ _ >60 100 40 2 _ _ 10 ~ 60 . 100 40 ~ ~ _ 40 _ > 6~
100 40 2 10 _ lO _ 0.5 100 40 2 50 _ lO _ 0.25 100 40 2 lO _ 40 _ 0.5 ::100 40 2 _ 10 10 _ ,. 100 55 5 10 _ 5 _ `~ 100 55 5 15 _ 5 _ 2.
s~ 0 S5 5 lO _ _ 10 3 lOo 55 - 5 lO _ _ 15 l.S
~:: I lO0 55 - 5 15 _ _ 15 s. loO 55 5 20 _ _ 15 1 :20 lOo 55 5 _ 15 _ 15 1 . lOu 55 5 _ ~ ~ l5 ., .
In each experiment, except tne first three, the gelling mixtures became tacky.
-3~ -i~5~53l3 EXA~LE 2 To mixtures at room temperature com~rising 100 parts of~poxide resin I ~nd 23 or 7.5 parts, respectively, of N-(~-hydroxypropyl)triethylenetetramine or N9N-dimethylpropane-l, 3-diamine were added 15 parts of Polyene II and 15 parts of Polymercaptan A. The mixtures (lO g-portions~ gelled in half a minu~e and one minute, respectively~ and became tacky.
_ _ Mixtures were prepared, each containing 55 parts of Hardener I, 5 parts of Accelerator I~ and 15 parts of Polymercaptan A. To a 5 g portion of each mixture was added wi~h stirring 5 g portions of mixtures each comprising 100 parts of Epoxide resin I and 15 parts of a polyene ( Polyenes I to XI).
In every case the admixtures gelled within 10 minutes a~ roo~
temperature~ a~d became tacky. If, however, either Polymercaptan A or the polyene ~' were omitted, geliing did not take place within 30 minutes.
EXAMPLE 4 _ Mixtures were prepared, each containing 15 parts of Polyene II anà 1~0 parts of Epoxide resin I. Separately, mixturesj each contai~ing 55 parts of Hardener I, 5 parts of Accelerator I, and 15 parts of a Polymercaptan ( Polymercaptans C to J ;nclusive), were made, and portions, each 5 g, of the epoxide resin mixture were mixed with 5 g portions of the polymercaptan-containing mixture. In - every case the admixtures gelled within lO minutes at room te~peratureJ and 25 developed tack.
31 _ 1~5~S3~ , ~urther composi~ion~ were pr~pared, e~ch containing 100 parts of !
Epoxide resin I, 55 parts of . Hardener . I, S parts of Accele~ator:
I, and cer~ain Polym~rcaptans and Polyenes as indicated in Table II.
The compositions were c~lred, either at room temperature for 24 hours or at 100 for 30 ~inutes, ~d the lap shear strengths and T-peel serengths of bonds ~ormad with the compositions were measured.
TABIE II
_ . . __ Cured for , _ _ r _ Polym~rcaptan Polyene 24 hou-;~ nin~es et .
Desig- Desig-n~tion Parts nation Parts lap shear lap shear T-peel strength strength strength (~Pa) meas~ed ~a) measured (N/mm~ measur~
_ _ at 22 at 22 at 60 at 22 A 10 I lS 22.229.1 24.5 1.3 A 15 I 15 24.632.3 21.4 1.4 A 20 I 15 21.334.3 21.8 1.6 A 15 V 15 _ 22.8 30.4 1.6 ,. 15 A 15 ¦ VI 15 _ 22.8 21.7 0~9 A 15 VIII 15 _ 22.1 20.0 1.3 . A 15 IX 15 _ 22.1 20.6 1.2 : B 10 I 15 18.530.7 26.8 2.4 .
B 15 ¦ I 15 19.515.9 13.3 1.5 B 20 ¦ I 15 20.310.3 9.8 1.2 F 15 II 15 _ 31.2 21.7 2.8 G 15 II 15 _ 26.7 22.9 1.6 ! 15 I~ l5 _ 28.3 24.8 1.4 :
- deno~es not deter~ined In each case the compositions beca~ t2c~y.
1056~38 E ~'LE 6 Further compositions were prepared, each containing lO0 parts of an epoxide resin, a stoichiometric amount of Hardener II, 15 parts of Polyene II, 5 parts of Accelerator I~and 15 parts of Polymercaptan A. The compositions were cured for 30 minutes at 100 before determination of the lap shear and T-peel strengths. In all cases the compositions became tacky before curing. The res~llts are given in Table III.
TABLE III
_ __ ~. ~
10 Epoxide Hardener II Gel time Lap shear strength T-peel strength resin parts (mins) (MPa) measured ( N/m~measured at 22at 60 at 22 i I 55 1~ 34 29 1.2 ~
; II 60 3~ 18 13 1.8 III 55 3~ lS 14 1.1 IV 60 2 24 18 1.8 - V 70 ~ 31 10 3.4 V~ 75 2 27 15 1.8 VI~I 115 _ 24 22 l.S
When, for comparative purposes, Hardener II and Accelerator I were replaced by a conventional mixed aromatic amine curing agent - tm-Phenylenediamine and bis(p-aminophenyl)methane~by a conventional anhydride curing agent C maleic anhydride or methyl tetrahydrophthalic anhydride~,or by a con~entional latent curing agent ~dicyandiamide or boron trichloride-n-octyldimethylamine complex~, the mixtures did not gel within 30 minutes of mixing at room te~perature. These compositions - 33 ~
~056S38 were therefore not suitable as tacky adhesives.
- EXAMPLE 7_ Example 6 was repeated, using 100 parts of Epoxide resin I and various curing agents, the other components remaining the same as in ~xample 6. The results are given in Table IV.
T~BLE IV_ ~ _ Hardener Gel time Lap shear strength T-peel strength . . (~Pa) measured (N/mm) measured .` Type parts(mlns)at 22at 60 at 22 . _ _ . _ ~ I- 100 4~ 29 11 2.6 :~ 10 III 85 1 25 13 3.0 IV 40 ~ * * *
~, V 60 ~ _ ~__ _ _ .'~ .
* these tests could not be carried out as the composition gelled . before the specimens could be prepared.
EX~u~2LE 8 Example 6 was repèated, using 100 parts of Epoxide reSiD
I-7 55 parts of E1ardener II7 15 parts of Polymercaptan B or K, with ~he other components the same as in Example 6. The results are given in Table V.
TABLE V
.
Polymercaptan Gel ti~e Lap shear strength T-peel strengt'n ¦
mins~ (MPa~ measured (~/mm) ~easured at 22at 60 at 22 B 1~ 1? 23 1.2 i ~ _ 3 _ ___ 23 2.7 __ :"
--l~S6~;38 E~MPLF, 9 .
Example 6 was repeated, using 100 parts OI Epoxide resin I~15 parts of Polymercaptan A, 15 parts of Polyene II, and various curing agents. The results are given in Table VI.
TABLE VI
.. _ . . _ _. __ __ _ Hardener Gel time Lap shear strengtlt T-peel strength Type Parts (MPa) measured (N/nml) measured at 23 at 60 at 23 __ _ __ _ . _ VI 13 25 sec. * * *
VII 22.5 20 sec. * * *
VIII 21 20 sec. * * *
IX 12 15 sec. * * *
X 10 13 sec. * *
XI 11 3~ min. 20.7 ~5.2 1.6 XII 32 11 min. 7.6 5.3 _ XIII 38 1~l6.0 _ _ 3.5 * these tests could not be performed as the composition gelled before the specimens could be prepared - denotes that tnis test ~as not carried out.
_35~ _
An efective amount of the curing agent (d) is employed.
The proportion will depend upon its chemical struct~lre and the pr~perties sought in the curable composition and in.its.cu;red produ~t. The optimum proportion can readily be determined by methods familiar to tnose skilled in the art. When the curing agent is one having a~ least thr~e hydrogen a_oms directly attached to aliphatic or cycloaliphati.c amir.o-ni..rogen atoms there ~ill nor~aliy be used from GbOUt 0. 8 to 1.2 amino-hydrogen equivalents of the amine per 1,2-epoxide equivalent of the epoxide resin.
When the curing agent is a tertiary amine having at least one nitrogen atom attac.hed directly to aliphatic or cycloaiiphat~c groups exclusively, ~nd has at ~ost two hydro~en atoms attached to amino nitrogen atoms there is g~erally usPd fro~ 1 to 40 parts by weight per lOQ parts by weight of the epoxid2 resin.
A wide range o~ polym2rcap;~ns is suitable for use as component (c) in the com?osition o. this. i~ven-ion. Preferabl~ there are used ~6S38 polymercaptans con~aining up to 6 mercaptan groups per molecule.
One class comprises esters of monomercaptancarboxylic acids with polyhydric alcohols and of monomercaptanmonohydric alcohols with polycarbocylic acids.
rther preferred such esters are of the formula rOH 1 ~ ~ b(d) [ R3 ~ (Co)co(co)dR S~ II
\ COO~I ~
~ ~ ¦b(C) where R represents an aliphatic or araliphatic hydrocarbon radical of at least 2, and preferably at most 60, carbon atoms, which may 10contain not more than one ether oxygen atom, R represents a hydrocarbon radical, which may contain not more than one carbon~loxy group, and is preferably of from 1 to 4 carbon atoms, 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 sameO
Yet further preferred esters are polymercaptans of formula II
which are also of the formula R (OCGR SH)a III
where _ g _ 1(~56S3~
a has the meaning previously assigned, R is an aliphatic hydrocarbon radical of from 2 to 10 carbon atoms, and fH3 R6 denotes -CH2-, -(CH2)2-, or -CH-~
Also preferred are mercaptan-containing polyesters, i.ncluding esters of monomerca ~andicarbocylic acids, of formula R9 ~ )c- ~()d~ R7~0)d C()c - R SH ) IV
where c and d have the meaning previously assigned, e is an integer of from 1 to 6, R represents a divalent organic radical, linked through a carbon atom or carbon atoms thereof to the indicated ~0- or -C0- units, R represents a divalent organic radical, linked through a carbon atom~ or carbon atoms thereof to the indicated --SH group and -0- or -C0- unit~ and R represents an organic radical, which must contain at least one -SH group when e is 1, linke.dthrough a carbon atom or carbon atoms thereof to the indicated -0 or -C0- unitO
Preferably, R denotes, when c is zero, 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 oxygeniatoms and by carbonyloxy groups; while, when c is 1, R preferably denotes (a) a saturated al,phatic 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.
R8 preferably denotes, when c is zero, a saturated aliphatic hydrocarbon group of 1 to 3 carbon at~msD which may bear a carboxyl group~ and~ ~hen c is 1~ R8 preferably denotes a saturated allphatic hydrocarbon group of 2 to 4 carbon atoms which may be substituted by a hydroxyl group or by a chlorine atom.
~0 R preferably denotes (a) an aliphatic or cycloaliphatic-aliphatic hydrocarbon group of 2 to 51 carbon atoms, which may bear at least on -SH group.
(b) a mononuclear or dinuclear arylene hydrocarbon group of 6 to 15 carbon aeoms~
(c) a chain of 4 to 250 carbon atoms, interrupted by at least one ether oxygen a~om 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 ~y at least one -SH group.
Also suitable are esters and ethers which are of the general formula 653~
i ~O~alkylene)f OH jh ~O-alkylene)fO(CO~ IR ~ V
I
where each "alkylene" group contalns a chain of at least 2 and at most fi carbon atoms between consecutive oxygen atoms, f is a positive integer, preferably such that the average molecular weight of the polymercaptan is not more than 10000?
is ~ero or 1, H is zero or 8 positive integer such that (h ~ ~) is at most 6, is an integer of from 2 to 6, R10 represents the radical of a polyhydric aloohol after removal of (h + i) alcoholic hydroxyl groups, especially an aliphatic hydrocarbon radical of:from 2 to 10 carbon atoms, and R 1 represents an aliphatic radical containing at least one mercaptan group.
~ lkylenell units in individual poly(oxyalkylene) chains may be the same or different and ~hey may be substituted by, e.g.9 phenyl or chloromethyl groups. Preferably they are -C2H4- or -C3H6- groups~
Preferred amongst the compounds of formula V are ~he esters of formula _ ~
5 / ~(O-alkylene~ OH ~ h ~(-alkYlene)fococku2ksu 1 Vl and ethers of formula ;53~3 ¦ (0_alkylene)fO~ j h R ~ I VII
~` (O-alkylene)focH2cHcH2sH
OH
where "alkylene", R5, f, h, and ~ have the meanings previously assigned, and k is 1 or 2.
Yet other suitable polymercaptans are mercaptan-terminated sulphides of the general formula HS - _ R12(o~ (CHO) R SS i R (0) (CH0) R SH
where each R12 denotes an alkylene hydroca}bon group con~aining from 2 to 4 carbon atoms, o R13 denotes -H, -~H3, or -C2H5~
m is an integer which has an average value of at least 1, and is preferably such that the average molecular weight of the sulphide is at most 10000, and either n is zero, in which case p and ~ are each also zero, or n is 1, in which case p zero or 1 and q is 1.
The preferred sulphides are those of formula VIII where R 3 denotes hydrogen and n and ~ are each 1, m being such that the molecular weight of the sulphide is from 500 to 8000.
iO5GS38 Another class of polymercaptane comprises mercaptan terminated poly(butadienes) of the formula l I
HS- - (CH2~ - C~CH2 ~ ~C~l2 C )u ~ -. -SH IX
or 14 ~
H ~ C \- ~X - - CH2. - ~CH215~U ~ - SH
l ~ t r X
where each Rl4 represents -H or -CH3, R represents -CN, COOH, -CONH2, -COOR , -C6H5, or ~OCOR16, ~here R16 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, p~eferably such that the average number molecular weight of the polymercaptan is not more than 10000.
Preferably the polymercaptans of formula IX are also of the formula 1~653~
HS ~ CH2CH = CHCH2 ~ --~CH2iH ~ ]
and those of formula ~ are correspondingly of the formula HS ~ CH2 ~ ~CH2CH)~ ~ SH XII
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.
Yet another suitable class of polymercaptans comprises the mercaptan-terminated oxyalkylene compounds of the general formula ~14 R14 RS (CHCH20)y CHCH2SH XIII
where each R has *he meaning previously assigned and X is an integer of from 1 to 4.
A still further class comprises poly(monomercaptancarboxylates), - especially the thioglycollates and mercaptopropionates, of tris(2-hydroxyethyl3 isocyanurate or of tris(2-hydroxypropyl) isocyanurate, i.e., the compounds of formula ios6~s ~14 NGH2C~ S~
/\
C~ CO
Rl OC~CH2ll NCH2CHOCQR SH XIV
where R17 denotes -H or a group -CO~SH, and ea^h R6 and R14 have ehe meanings previously assi~ned.
S Polyenes preferred ~or the purposes of this invention have a~
: average molecular wei~ht of ~ot more than 2000 snd they contain a~
least two ethylenic double bonds each ~ to a c~rbo~ylo~y ~roup, e~pecially în the fo~m of ~aleic acid residues of formula , --OCCH~ CO_ Il Il XV
O O
directly attached at ea~h e~d to cRrbon ~tom~, or in th2 for~ of itaconic acid residues of fo~mula ~2CO~W
: I ~ 2 i~
directly attached at each end to carbon atoms9 or in the form of - acrylic residues of for~ula - CC - C~2 X~ll 16 _ . ` - ` ':.''' ` ' ~,1 ~05~;38 directly attached to carbon atoms, where R denotes -H, -Cl, -Br, or an alkyl group of 1 to 4 carbon atoms3 Preferably the polyenes contain, per molecule, up to six ethylenically-~nsaturated units of formula XV, XVI, or XVII.
Particularly preferred polyenes are maleic esters of poly(oxyalkylene) polyols and contain the repeating unit _ rO-alkylene OICH = C~CIl XVIII
L l where~'alkylene" has the meaning assigned above.
Preferably the polymercaptan is employed in a quantity sufficient to supply from 0.8 to 1.1 mercaptan groups per said e~hylenic double bond of the polyene, and the compositions contain from 10 to 150, and especially up to 75, parts by weight of the polymercaptan plus polyene per 100 parts by weight of the epoxide resin. The optimum amounts for a particular composition may readily be ascertained by simple experiment.
Desirably, at least one of the polyene and the polymercaptan has an average molecular weight of not more than 1000 The compositions may be heated, e~.g., at temperatures of from 35 C to 150 C, to increase the rate of curing, but often they will cure sufficiently rapidl~ at room temperatu~e for most purposes.
- ~)S6538 Conventional accelerators for promoting the curing of the epoxide resin ~a) by its curing agent (d) may also be included, particularly when that agent is a poly(aminoamide). Such accelerators include aliphatic amines containing at least one tertiary amino group and at most one primary amino group, such as N,N-dialkylethane-l, 2_diamines and N,N-dialkylpropane-1~3-diamines, especially the N~N-dimethyl and N,N,-diethyl derivati~es, and also Mannich bases of the formula R19(CH2NR R )a X~
~0 where al is an integer of at least 1 and is preferably 3 or 4, R represents the radical of a mononuclear or polynuclear phenol, which may be monohydric or polyhydric, the said radical having free valencies, and each R represents an aIkyl or hydroxyalkyl group of up to four carbon atoms.
A preferred Mannich base is 2,4,6-tris~dimethylaminomethyl) phenolO
me compositions may also contain an accelerator for the reaction between the polyene and the polymercaptan, this accelerator usually being an organic or inorganic Br~nsted base or a ~ree-radical catalyst. me latter are of general applicability and include organic or inorganic persxides and pers~lts such as benzoyl peroxide, hydrogen peroxide, ~ert.butyl hydroperoxide, di~ propyl peroxydicarbonate, and ammonium persulphateO
~56~3~
For the preferred polyenes, i.e., those ha~ing ethylenic double bonds a to carbonyloxy groups, Br~n3ted bases may be ~sed instead. Examples of suitable Br~nsted bases sre pri~ary, secondary, ~nd tertiary amines, such as triethylamine, N,N-dimeehyl~ni~ e, and N-ben~yldimethyi~ine, lower alkanol2mines ( e.g., m~no-, di-t and tri-eth~olamine), lower alkylenepolyaminss ( e.g., ethylenediamine, diethylenetriamine, triethylenetetramine 9 te~raethylenepentamine, propane~l,2-diamine, propane-1,3~digmine, and hexamethylenedia~ine), also quater~ary am~onium bases such as tetramethyla~onium ~ydroxide, and ~ater-soluble inorganic hydroxides ~ especially sodiu~ hydroxide) and inor~anic salts such as trisodiu~ pbosphate, sodium carbonate, sodium bicarbonate, sodium pyrophosphate, snd sodiu~ acetate.
Of course, some curing agents for epoxide resins are also Br~nsted bases, as are some accelerators for the curing of epoxide resins, and when such a curing agent or accelerator is used there is normally no advantage in employing another such base to promote the reaction between the polymercaptan and the polyenes.
Optionally, plasticisers may be incorporated and these include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate.
20 There may also be present so-called reactive diluents; especially monoepoxides such as n-butyl glycidyl ether, iso-octyl glycidyl ether, - phenyl glycidyl e~her, cresyl glycidyl ethe~s, glycidyl acrylate, -- lq --:~5~;~38 glyci~l meehacrylate~ a~d glyci~yl esters of br~ched tertiary, aliphatic monocaribo~lîc acids. The co~ositions may also con~ain fillers, colouring matter, flow-control age~ts, and flame inh~bitors. Suitable extenders and fillers are asphalt, bitum~n, glass fibres, ballotinig mica, suartz flour, calcium carbonate, talc, cellulose, kaol n~ wollasto~ite, ~nd colloidal silica having a large specific surface area-The co~positions of the present i~vention may be ~upplîed a~ a twc.-part psck; preferably~one part contains the epoxide resin (a~ and the polyene ~C~ and the other the curing agent G~) and the polymercapt~n (~), bacause~otherwise, the epoxide resin may be cured pL-ema~urely on storage by mean8 of the polymercaptan, and further, the curing age~t ~d),unless it is exclusively a tertiary amine, react a. the ethylenic double bonds of the polye~e (c~. Because, too, poly~ercap~anc2rboxylates reAct on prolo~ged contact with ~liphatic amines, it is preferred, ~here the co~po9itio~ iS to be packaged in parts, to use as component (b) a poly~ercaptan ~hich contains no car~oxylic ester groups.
A particularly pref~rred combination of curing age~t and polymerca?tan for prolonged storage ;s a poly( minoa~a~le) and a polymercaptan of the general fo-r~ula VII or VIII.
The co~sitions ~ay, of course, slso be supplied as a three-part pacX, the epoxide resin being mixed with the polysne ~c).
rne following Exac~ples illustr~te the i~vention. Unle~s o~herwi3~ indica~ed, par~s are by weigh~. Temperatures ar i~
degrees Ce;sius.
~ 20 -:lOS653B
Pol~mercaptan A
is substantially of the average formula CH2 - _ _ I f 3 1 CH _ ~ CH2CH)b OCH2CHCH2SH 3 where bl is an integer of average value 2,5 and was prepared as described in United States Patent Specification No. 3258495.
Polymercaptan B
is the commercially-available po~ysulphide substantially of the average formula US ~ CH2CS2l)cH20 CH2CH255 ~H2Æ120CH20C112CH25H
Pol~mercaptan C
is of the formula CH3CH - r T 3 CH2 - L(OC~2CH) OCOCH2SH ~ XXII
~, where cl is an integer of average value 3.16. The preparation of mercaptancarboxylates of polyoxyalkylene polyols such as Polymercaptans C to F and H is described in British Patent Specification No. 1278934.
Polymercaptan D
lS of the formula ~056538 CH~ 3 CH- ~ ~OCH2CH~d OCOCH2SH ¦ XXIlI
where d is an integer of average value 3.69.
Polymercaptans E and F
are of formula XXIII, where dl is an integer of average value 5.41 and 7~14, respectively.
is the tetrakis(3-mercaptopropionate) of pentaerythritol.
Polymercaptan H
is of the formula CH3 _ C ._--CH2 (OCH2CH) e OCOCH~SH XXIV
where el is an integer of average value 2.~5.
Poly~erca-2tan J
is a hydroxy7-terminated polyester from l,l,l-trimethylolpropane ( 1 mol.)~ adipic acid ( 3 mol.,), and butane-1,4-diol ( 3 mol.), ~sterified with 3 mol. of 3-mercaptopropionic acid, prepared by .he procedure described in British Patent Specification No. 1311090.
Poly~ercaptan K
- is a mercaptan-terminated butadiene-acrylonitrile copolymer and has the general formula andJor HS~ ~ CH2CH = CHCH2~ ~CH2CU~ ~ SH
~ CH t _ 22 _ ,. ~, ~1~56S3~3 Polyene I
This polyester is made in a conventional manner by the reaction of maleic anhydride (3.06 mol.) with dipropylene glycol (3.21 mol.).
Polyene II
This polyester is prepared similarly Erom dipropylene glycol (2.1 mol.), maleic a~hydride (l mol.), and adipic acid (1 mol.).
Polyene III
Butane-1,4-diol diglyci~yl ether OL epoxide ~ontent 7.4 equiv./kg (108 g), itaconic acid (65 g), n-butyl glycidyl ether (28.1 g), ~-ben2yldimethylamine (2 g), and hydroquinone (0.2 g) are mixed and heated to 120, when an exothermic reaction sets in, the tem?erature of the mixture rising to 250. The product is rapidly cooled to 120 , and heated at that temperature for one hour. Polyene III is substan~ially of ~he formula 1. ~
11 Il' H - [ (CH2)40 CH2CHCH2CC - CCCH2CHCH2 - (CH2)3CH3 XXV
Polyene IV
2,2-bis(4-Hydroxyphenyl)propane (114 g), n-butyl glycidyl et~er (130 g), and ~-benzyldimethylamine (2 g) are hea~ed at 120 for 1 hour, then cooled to 70. Maleic anhydride (98 g) is added and heating is con~inued at 120 for 100 minutes. The product, Polyolefin IV, is substantially of the for~ula 6~i38 ~ ~ OCH2CHOCOC~ - CHCOH XXVI
Il IocH~
CH3 2 ( 2)3 3 I
Polyene V
A glycerol-propylene oxide adduct of average molecular weight 1000 (200 g ) is heated for 2 hours at 120 with 58.8 g of maleic anhydride in the presence of 2.6 g of N-benzyldimethylamine.
Polyene ~l is substantially of the formula 1 2- ~ C~3 CH~ r(CH2CH)f OCCH = (~HCOH ¦ XXVII
where fl is an integer of average value 15.65.
Polye~e VI
.
This is made similarly from 100 g of a glycerol-propylene oxide adduct of average molecular weight 300 and maleic anhydride (98 g ) with 3 g of tr_ethylamine as catalyst. Polyene VI is substantially of formula XXVlI, where '1 is an integer of average value 3.59.
Polyene VII
Butane-1,4-diol (lOB g), maleic anhydride (98 gj, and xyle~e (135 g) are heated together with stirri~g under reflux for 2 hours. Water formed during the reaction is removed by azeotropic distillation using a Dean and Stark trap. Toluene-?-sulphonic acid (2 g) is added and heating at reflux is con~inued for a further 2 hours. The - 2~ -S05~53~
maxture is coolad ~o 50, neutralised wi~h a~ueous potas~ium bicarbonate solution, ~he water and xylene are dis~illed olf, and the resldue i8 filtered.
Polyene VII is substantially of the for~ula ~ O O
H_ O(CH2)4 OCCH ~ C~C O(CH~)40~ XXVIIX
Polyene VIII
A glycerol-propylene oxide adduct o~ average ~olecular wei~ht 600 ( 600 g,) i~ hea~ed with 294 g of maleic anhydride in the presence o~ 9 g of triethylamine for 2 hou~s at 120. Then n-butyl glycidyl ether of epo~ide content 7.7 equiv./kg. ~ 331 g) is added dropwise in an atmosphere of nitroge~ and the mixture is heated for 1~ hours at 120.
Polyene VIII is sùb~an~ially of the formula 1 2 _ ~ 1 3 CH - t (ocH2cH)g OCCH ~ CHCOCH2CHCH2 t ~ 3 3 ~ XXIX
_ 3 ~H2 ~
where ~1 is an integer of average value 8.76.
Polyene IX
Glycerol ( 92 ~,) and maleic anhydride (294 g) are heated for 2 hours at 120 in the presence of 3.8 g of N-benzyldi~ethylamine. ~hen 343 g o~ n-butyl glycidyl ether (epoxide content 7.0 equiv./kg3 is added dropwise, an exothermic - 2~ -reaction taking piace, and the mixtufe i6 heated for 2 hours at 120 in an at sphere of nitrogen.
Polyene IX is of formula ~YIX, where gl is zero.
Polyene X
2l2-bis(p-Glycidyloxyphenyl~propane, of epoxide content 5.2 equiv./kg (384 g )~is heated for 2 hours at 120 with 144 g of acrylic acid in the presence of 5.3 g of N-benzyldimethylamine as catalyst and 0.53 g of ~-methoxyphenol as polymerisation inhibitor Polyene X is of the formula .
1 ~ocH2c3c32occH = C~12~ xxx - Polyene XI
is the tetrakis(methacrylate) of the adduct of p~ntaerythritol and ethylene oxide, i.e., is of the formula O
Il -' "' C(C~zOCH2CH20CC = C.~2)4 ~ CH3 1 Epoxide resin I
S
denotes a polyglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane having a viscosity at 21 in the range 200 to 400 poises: its epoxide content is 5.1-5.4 equiv./kg. , , ~ ~6 ~
105~538 ~?oxide r~sin II
denotes a polyglycidyl ether of a phenol-formaldehyde novola~ of average ~olecular weight 420. It has an epoxide content of 5.5-5.7 equiv.lkg.
Epox;de resin III
den~tes bis(4-(diglycidylamino)phenyl)methane having an epoxide content of 7.5-8.5 equiv./kg.
E~xide resin IV
.~ ~
denotes a polyglyci~dyl ether of bis(4-hydroxyphenyl)~ethane having an e~oxide content of 5.8 equiv./kg.
~=
denotes diglycidyl hexahydrophthalate having an epoxide content of 6. 2-6. 8 equiv./kg.
Epoxide resin Vl denotes l-glycidyloxym2thyl-3-glycidyl-5,5-di~ethylhydantoin having an epoxide conte.lt of 7.0-7.4 equiv./kg.
Epoxide resin VlI
denotes 4-~diglycidyla~ino)phenyl glycidyl ether having an epoxide content of 9.4-10.5 equiv.Ikg.
., /
.
Hardener I
denotes a poly~aminoamide) obtained by reaction of diethylenetriamine with a mixture of dimerised and trimerised linoleic acid: its amine value is 210-220 mg KOH/g Hardeners II and III
denote polytaminoamide)s prepared in a similar manner to Hardener I but having an amine value of 350-400 mg KOH/g and 290-320 mg ~OH/g respectivelY~.
Hardener IY
denotes a poly(aminoamide) prepared from a monomeric fatty acid and an aIiphatic polyamine and.he.ving'an amine value of 580-620 mg KOH/g Hardener V
.
denotes a ,similar poly(aminoamide) havi~g an amine value of 350-3~0 mg KOH/g Hardener VI
denotes ~-~2-aminoethyl)piperazine L5 Hardener_VII
denotes isophoronediamine Hardener VIII
denotes a commercial mixture of 2~,4- and 2/4,4-~rimethyl-hexamethylene-' - diamine 0 Hardener IX
denotes triethylene~etramine Hardener X
denotes N,N-diethylpropane-1,3-diamine Hardener XI
. .
denotes 2~4,6-tris(dimethylaminomethyl)phenol 2~ -1~5~S38 Hardener XII
:
denotes 3,3'-dimethyl-4Jd~'-diaminodicyclohexylmetllane Hardener XIII
denotes a ~oly(o~ropYlene) triprimary amine ~i.e., a trihydric aliphatic alcohol having three oxypropylene chalns a~ttached to the hydroxyl groups, each terminated by a primary amino ~roup) of average molecular w~ight 400.
Accelerator I
.
is 2,4,6-tris(dimethylaminomethyl)phenol.
Shear strengths of joints were determined using aluminium alloy strips 1.63 mm thick obtained under the designation "2L 73 Alclad"
which had been degreased, picXled by the process prescribed in the British Ministry of Technology Aircraft Process Specification DTD-915B, washed in runn;ng water1and dried ~t room temperature ("Alclad" is a registered Trade ~ark). Single lap joints 12 mm x ' 15 25 mm were prepared. T-peel strengtns were determined by the procedure described in United States ~ilitary Specification ~: M~M-A-132. Sheets of "2L 61 Alclad", 0.056 mm thick and 24 mm wide were used. Gelation times were determined by ascertaining when - the mixture, stirred with a small wooden spatula, became a rubbery solid and/or formed 'Istrings'' when pulled.
~, i~ :
.
~1~565313 ~X~MPLE. I
The n~ix~u~c~ shown in T~le ~ were prepared and their ~elation times s~ room te~erature, on 10 8 ~amples, wPre measured.
TABLE I
. ~
Epo~ide . Accel- Polymer- Polymer- Polyene Polyene Gel resin Hardener erator captan captan I II time I I I A B (min~.) _ _ . . _ .. ..
lO0 40 2 _ _ _ _ >60 100 40 2 _ _ 10 ~ 60 . 100 40 ~ ~ _ 40 _ > 6~
100 40 2 10 _ lO _ 0.5 100 40 2 50 _ lO _ 0.25 100 40 2 lO _ 40 _ 0.5 ::100 40 2 _ 10 10 _ ,. 100 55 5 10 _ 5 _ `~ 100 55 5 15 _ 5 _ 2.
s~ 0 S5 5 lO _ _ 10 3 lOo 55 - 5 lO _ _ 15 l.S
~:: I lO0 55 - 5 15 _ _ 15 s. loO 55 5 20 _ _ 15 1 :20 lOo 55 5 _ 15 _ 15 1 . lOu 55 5 _ ~ ~ l5 ., .
In each experiment, except tne first three, the gelling mixtures became tacky.
-3~ -i~5~53l3 EXA~LE 2 To mixtures at room temperature com~rising 100 parts of~poxide resin I ~nd 23 or 7.5 parts, respectively, of N-(~-hydroxypropyl)triethylenetetramine or N9N-dimethylpropane-l, 3-diamine were added 15 parts of Polyene II and 15 parts of Polymercaptan A. The mixtures (lO g-portions~ gelled in half a minu~e and one minute, respectively~ and became tacky.
_ _ Mixtures were prepared, each containing 55 parts of Hardener I, 5 parts of Accelerator I~ and 15 parts of Polymercaptan A. To a 5 g portion of each mixture was added wi~h stirring 5 g portions of mixtures each comprising 100 parts of Epoxide resin I and 15 parts of a polyene ( Polyenes I to XI).
In every case the admixtures gelled within 10 minutes a~ roo~
temperature~ a~d became tacky. If, however, either Polymercaptan A or the polyene ~' were omitted, geliing did not take place within 30 minutes.
EXAMPLE 4 _ Mixtures were prepared, each containing 15 parts of Polyene II anà 1~0 parts of Epoxide resin I. Separately, mixturesj each contai~ing 55 parts of Hardener I, 5 parts of Accelerator I, and 15 parts of a Polymercaptan ( Polymercaptans C to J ;nclusive), were made, and portions, each 5 g, of the epoxide resin mixture were mixed with 5 g portions of the polymercaptan-containing mixture. In - every case the admixtures gelled within lO minutes at room te~peratureJ and 25 developed tack.
31 _ 1~5~S3~ , ~urther composi~ion~ were pr~pared, e~ch containing 100 parts of !
Epoxide resin I, 55 parts of . Hardener . I, S parts of Accele~ator:
I, and cer~ain Polym~rcaptans and Polyenes as indicated in Table II.
The compositions were c~lred, either at room temperature for 24 hours or at 100 for 30 ~inutes, ~d the lap shear strengths and T-peel serengths of bonds ~ormad with the compositions were measured.
TABIE II
_ . . __ Cured for , _ _ r _ Polym~rcaptan Polyene 24 hou-;~ nin~es et .
Desig- Desig-n~tion Parts nation Parts lap shear lap shear T-peel strength strength strength (~Pa) meas~ed ~a) measured (N/mm~ measur~
_ _ at 22 at 22 at 60 at 22 A 10 I lS 22.229.1 24.5 1.3 A 15 I 15 24.632.3 21.4 1.4 A 20 I 15 21.334.3 21.8 1.6 A 15 V 15 _ 22.8 30.4 1.6 ,. 15 A 15 ¦ VI 15 _ 22.8 21.7 0~9 A 15 VIII 15 _ 22.1 20.0 1.3 . A 15 IX 15 _ 22.1 20.6 1.2 : B 10 I 15 18.530.7 26.8 2.4 .
B 15 ¦ I 15 19.515.9 13.3 1.5 B 20 ¦ I 15 20.310.3 9.8 1.2 F 15 II 15 _ 31.2 21.7 2.8 G 15 II 15 _ 26.7 22.9 1.6 ! 15 I~ l5 _ 28.3 24.8 1.4 :
- deno~es not deter~ined In each case the compositions beca~ t2c~y.
1056~38 E ~'LE 6 Further compositions were prepared, each containing lO0 parts of an epoxide resin, a stoichiometric amount of Hardener II, 15 parts of Polyene II, 5 parts of Accelerator I~and 15 parts of Polymercaptan A. The compositions were cured for 30 minutes at 100 before determination of the lap shear and T-peel strengths. In all cases the compositions became tacky before curing. The res~llts are given in Table III.
TABLE III
_ __ ~. ~
10 Epoxide Hardener II Gel time Lap shear strength T-peel strength resin parts (mins) (MPa) measured ( N/m~measured at 22at 60 at 22 i I 55 1~ 34 29 1.2 ~
; II 60 3~ 18 13 1.8 III 55 3~ lS 14 1.1 IV 60 2 24 18 1.8 - V 70 ~ 31 10 3.4 V~ 75 2 27 15 1.8 VI~I 115 _ 24 22 l.S
When, for comparative purposes, Hardener II and Accelerator I were replaced by a conventional mixed aromatic amine curing agent - tm-Phenylenediamine and bis(p-aminophenyl)methane~by a conventional anhydride curing agent C maleic anhydride or methyl tetrahydrophthalic anhydride~,or by a con~entional latent curing agent ~dicyandiamide or boron trichloride-n-octyldimethylamine complex~, the mixtures did not gel within 30 minutes of mixing at room te~perature. These compositions - 33 ~
~056S38 were therefore not suitable as tacky adhesives.
- EXAMPLE 7_ Example 6 was repeated, using 100 parts of Epoxide resin I and various curing agents, the other components remaining the same as in ~xample 6. The results are given in Table IV.
T~BLE IV_ ~ _ Hardener Gel time Lap shear strength T-peel strength . . (~Pa) measured (N/mm) measured .` Type parts(mlns)at 22at 60 at 22 . _ _ . _ ~ I- 100 4~ 29 11 2.6 :~ 10 III 85 1 25 13 3.0 IV 40 ~ * * *
~, V 60 ~ _ ~__ _ _ .'~ .
* these tests could not be carried out as the composition gelled . before the specimens could be prepared.
EX~u~2LE 8 Example 6 was repèated, using 100 parts of Epoxide reSiD
I-7 55 parts of E1ardener II7 15 parts of Polymercaptan B or K, with ~he other components the same as in Example 6. The results are given in Table V.
TABLE V
.
Polymercaptan Gel ti~e Lap shear strength T-peel strengt'n ¦
mins~ (MPa~ measured (~/mm) ~easured at 22at 60 at 22 B 1~ 1? 23 1.2 i ~ _ 3 _ ___ 23 2.7 __ :"
--l~S6~;38 E~MPLF, 9 .
Example 6 was repeated, using 100 parts OI Epoxide resin I~15 parts of Polymercaptan A, 15 parts of Polyene II, and various curing agents. The results are given in Table VI.
TABLE VI
.. _ . . _ _. __ __ _ Hardener Gel time Lap shear strengtlt T-peel strength Type Parts (MPa) measured (N/nml) measured at 23 at 60 at 23 __ _ __ _ . _ VI 13 25 sec. * * *
VII 22.5 20 sec. * * *
VIII 21 20 sec. * * *
IX 12 15 sec. * * *
X 10 13 sec. * *
XI 11 3~ min. 20.7 ~5.2 1.6 XII 32 11 min. 7.6 5.3 _ XIII 38 1~l6.0 _ _ 3.5 * these tests could not be performed as the composition gelled before the specimens could be prepared - denotes that tnis test ~as not carried out.
_35~ _
Claims (37)
1. A composition comprising (a) an epoxide resin having, per average molecule, more than one 1,2-epoxide group of formula directly attached to oxygen, sulfur, or nitrogen, where either R
and R2 independently of one another represent hydrogen, in which case R1 denotes hydrogen or methyl, or R and R2 conjointly represent -CH2CH2-, in which case R1 deontes hydrogen, (b) a polymercaptan having at least two mercaptan groups per average molecule, (c) a polyene having, per average molecule, at least two ethylenic double bonds, each 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, 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.
and R2 independently of one another represent hydrogen, in which case R1 denotes hydrogen or methyl, or R and R2 conjointly represent -CH2CH2-, in which case R1 deontes hydrogen, (b) a polymercaptan having at least two mercaptan groups per average molecule, (c) a polyene having, per average molecule, at least two ethylenic double bonds, each 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, 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.
2. A composition according to claim 1, wherein the epoxide resin is a polyglycidyl ester, a poly(.beta. -methylglycidyl) ester, a polyglycidyl ether, a poly (.beta.-methylglycidyl) ether, a poly(N-glycidyl) compound or a poly(N-.beta.-methylglycidyl) compound.
3. A composition according to claim 1, wherein the polymercaptan contains up to 6 mercaptan groups per average molecule.
4. 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.
5. A composition according to claim 4, wherein the polymercaptan is of the formula where R3 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, R4 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.
6. A composition according to claim 5, in which the polymercaptan is of the formula R5(OCOR6SH)a where a is as defined in claim 5, R5 is an aliphatic hydrocarbon radical of from 2 to 10 carbon atoms, and R6 denotes -CH2-, or .
7. A composition according to claim 4, wherein the polymercaptan is of the formula where c and d are as defined in claim 5, e is an integer of from 1 to 6, R7 represents a divalent organic radical, linked through a carbon atom or carbon atoms thereof to the indicated -O- or -CO- units, R8 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 R9 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.
8. A composition according to claim 7, where either c is zero and R7 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 R7 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.
9. A composition according to claim 7, wherein, when c is zero, R8 represents a saturated aliphatic hydrocarbon group of 1 to 3 carbon atoms, which may bear a carboxyl group, and, when c is 1, R8 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.
10. A composition according to claim 7, wherein R9 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.
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.
11. A composition according to claim 3, wherein the polymercaptan is of the formula 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 not 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, R10 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 R11 represents an aliphatic radical containing at least one mercaptan group.
12. A composition according to claim 11, wherein the polymercaptan is an ester of the formula or an ether of the formula where R5 is as defined in claim 6, "alkylene", f, h, and j, are as defined in claim 11, and k is 1 or 2.
13. A composition according to claim 3, wherein the polymercaptan is a mercaptan-terminated sulfide of the general formula where each R12 denotes an alkylene hydrocarbon group containing from 2 to 4 carbon atoms, R13 denotes -H, -CH3, or C2H5, 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.
14. A composition accroding to claim 13, where R13 denotes hydrogen and n and p are each 1.
15. A composition according to claim 3, wherein the polymercaptan is a mercaptan-terminated poly(butadiene) of the formula or where each R14 represents -H or -CH3, R15 represents -CN, -COOH, -CONH2, -COOR16, -C6H5, or -OCOR16, where R16 is an allyl 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.
16. A composition according to claim 15, wherein the polymercaptan is of the formula or 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.
17. A composition according to claim 3, wherein the polymercaptan is a mercaptan-terminated oxyalkylene compound of the general formula where each R14 has the meaning assigned in claim 15, and y is an integer of from 1 to 4.
18. A composition according to claim 3, wherein the polymercaptan is of the formula where each R6 is as defined in claim 6, each R14 is as defined in claim 15, and R R17 denotes -H or a group -COR6SH.
19. 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 .alpha. to a carbonyloxy group.
20. A composition according to claim 19, wherein the polyene contains at least two maleic acid residues of formula directly attached to each end to carbon atoms, or itaconic acid residues of formula directly attached at each end to carbon atoms, or acrylic residues of formula directly attached to carbon atoms, where R18 denotes -H, -Cl, -Br or an alkyl group of 1 to 4 carbon atoms.
21. A composition according to claim 20, wherein the polyene contains at most six such ethylenically-unsaturated units.
22. A composition according to claim 20, wherein the polyene is a maleic ester of a poly(oxyalkylene) polyol and contains the repeating unit where "alkylene" is as defined in claim 11.
23. A composition according to claim 1, wherein the polymercaptan (b) is employed in a quantity sufficient to supply from 0.8 to 1.1 mercaptan groups per ethylenic double bond of the polyene (c).
24. A composition according to claim 1, which contains from 10 to 150 parts by weight of the polymercaptan plus polyene per 100 parts by weight of the epoxide resin.
25. 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.
26. A composition according to claim 17 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.
27, 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.
28. 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.
29. 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.
30. A composition according to claim 1, which further contains an accelerator for the reaction between the polymercaptan (b) and the polyene (c).
31. A composition according to claim 20, wherein the accelerator is a Br?nsted base or a free-radical catalyst.
32. 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).
33, A composition according to claim 32, 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.
34. 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.
35. A pack as claimed in claim 34, wherein the polymercaptan contains no carboxylic ester groups.
36. 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, and a second part containing a polymercaptan, and the third part containing a curing agent.
37. 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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB5329873 | 1973-11-16 | ||
| GB3756474*[A GB1460571A (en) | 1973-11-16 | 1974-08-28 | Adhesive compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1056538A true CA1056538A (en) | 1979-06-12 |
Family
ID=26263501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA213,701A Expired CA1056538A (en) | 1973-11-16 | 1974-11-14 | Adhesive compositions comprising epoxide resin, polymercaptan, polyene, and amino-nitrogen curing agent |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5083432A (en) |
| CA (1) | CA1056538A (en) |
| DE (1) | DE2453874A1 (en) |
| FR (1) | FR2251599B1 (en) |
| GB (1) | GB1460571A (en) |
| NL (1) | NL7414951A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016105913A1 (en) * | 2014-12-24 | 2016-06-30 | Dow Global Technologies Llc | Rapid-set epoxy resin systems and process of coating pipelines using the epoxy resin system |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2901686A1 (en) * | 1978-01-20 | 1979-07-26 | Ciba Geigy Ag | MIXTURES BASED ON ALKENYL-SUBSTITUTED PHENOLS AND POLYMER CAPTANES |
| US4260720A (en) * | 1979-10-31 | 1981-04-07 | Ppg Industries, Inc. | Novel mercapto chain extended products and their use in cationic electrodeposition |
| US4631300A (en) * | 1982-03-15 | 1986-12-23 | Interez, Inc. | Process for preparing low viscosity UV curable polyacrylates |
| ATE45368T1 (en) * | 1984-04-28 | 1989-08-15 | Ciba Geigy Ag | CURABLE COMPOSITIONS. |
| ATE138084T1 (en) * | 1988-11-23 | 1996-06-15 | Ciba Geigy Ag | CUREABLE EPOXY RESIN MIXTURES CONTAINING POLYOXYALKYLENEDITHIOLS AND POLYAMINES |
| EP2658939B1 (en) | 2010-12-29 | 2021-06-16 | 3M Innovative Properties Company | Structural hybrid adhesives |
| KR20150036272A (en) | 2012-07-03 | 2015-04-07 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Method of making structured hybrid adhesive articles |
| WO2014100238A2 (en) * | 2012-12-21 | 2014-06-26 | Dow Global Technologies Llc | Phase-segmented non-isocyanate elastomers |
| JP6379110B2 (en) * | 2012-12-21 | 2018-08-29 | ダウ グローバル テクノロジーズ エルエルシー | Non-isocyanate sealant for electrical cable connection |
| BR112015014765A2 (en) | 2012-12-21 | 2017-07-11 | Dow Global Technologies Llc | process to form an elastomeric polymer |
| WO2014100239A2 (en) * | 2012-12-21 | 2014-06-26 | Dow Global Technologies Llc | Non-isocyanate sealant for glass sealing |
| CA2933688C (en) * | 2013-12-18 | 2022-01-18 | Dow Global Technologies Llc | Process for forming an organic polymer in a reaction of a polyene, an epoxy resin and a mixture of thiol and amine curing agents |
| CN114207023A (en) * | 2019-11-11 | 2022-03-18 | 东丽精细化工株式会社 | Epoxy resin composition |
| CN111040133A (en) * | 2019-12-17 | 2020-04-21 | 山东益丰生化环保股份有限公司 | High-temperature-resistant epoxy resin curing agent, and preparation method and application thereof |
-
1974
- 1974-08-28 GB GB3756474*[A patent/GB1460571A/en not_active Expired
- 1974-11-13 DE DE19742453874 patent/DE2453874A1/en not_active Withdrawn
- 1974-11-14 CA CA213,701A patent/CA1056538A/en not_active Expired
- 1974-11-15 NL NL7414951A patent/NL7414951A/en not_active Application Discontinuation
- 1974-11-15 FR FR7437693A patent/FR2251599B1/fr not_active Expired
- 1974-11-16 JP JP49132435A patent/JPS5083432A/ja active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016105913A1 (en) * | 2014-12-24 | 2016-06-30 | Dow Global Technologies Llc | Rapid-set epoxy resin systems and process of coating pipelines using the epoxy resin system |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5083432A (en) | 1975-07-05 |
| NL7414951A (en) | 1975-05-21 |
| GB1460571A (en) | 1977-01-06 |
| DE2453874A1 (en) | 1975-05-28 |
| FR2251599A1 (en) | 1975-06-13 |
| FR2251599B1 (en) | 1976-10-22 |
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