CA1229600A - Diurethane diureas and the use thereof - Google Patents
Diurethane diureas and the use thereofInfo
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- CA1229600A CA1229600A CA000465247A CA465247A CA1229600A CA 1229600 A CA1229600 A CA 1229600A CA 000465247 A CA000465247 A CA 000465247A CA 465247 A CA465247 A CA 465247A CA 1229600 A CA1229600 A CA 1229600A
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- diurethane
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- diisocyanate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
- C07D295/215—Radicals derived from nitrogen analogues of carbonic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
- C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
- C07C275/14—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
- C07C275/18—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C275/40—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/808—Monoamines
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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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
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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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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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
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
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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
- C08G2190/00—Compositions for sealing or packing joints
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Diurethane diureas and the use thereof Abstract Diurethane diureas of the formula
Description
SKYE
Case 3-14615/+
Diurethane Doris and the use thereof The present invention relates to novel diurethane Doris, to the use thereof in curable epoxide resin mixtures, and to the products obtained from these mixtures by curing.
The use of specific moo-, dip and pullers as curing agents for epo~ide resins is known from the US. Patent Specification No. 3,386,956. These prior known curable epoxide resin mixtures are in general stable in storage at room temperature, buy on being cured they leave much to be desired with regard to reactivity.
The object of the invention was to provide epoxide resin mixtures which would have a high level of latency and rapidly cure at elevated temperature. It has been found that certain diurethane Doria compounds largely satisfy these requirements, and can be used both as curing agents and as curing accelerators.
The present invention thus relates to diurethane Doris of the formula I
I " (I) ~N-CONH-R-NHCO-O--R'-O-OCN~-R-NHCO-wherein
Case 3-14615/+
Diurethane Doris and the use thereof The present invention relates to novel diurethane Doris, to the use thereof in curable epoxide resin mixtures, and to the products obtained from these mixtures by curing.
The use of specific moo-, dip and pullers as curing agents for epo~ide resins is known from the US. Patent Specification No. 3,386,956. These prior known curable epoxide resin mixtures are in general stable in storage at room temperature, buy on being cured they leave much to be desired with regard to reactivity.
The object of the invention was to provide epoxide resin mixtures which would have a high level of latency and rapidly cure at elevated temperature. It has been found that certain diurethane Doria compounds largely satisfy these requirements, and can be used both as curing agents and as curing accelerators.
The present invention thus relates to diurethane Doris of the formula I
I " (I) ~N-CONH-R-NHCO-O--R'-O-OCN~-R-NHCO-wherein
2 9 R is in each case a radical derived from a diisocyanate and having at most 20 C atoms, R' is a radical derived from a dill and having a molecular weight of at most 1500, and the radicals Roll are each methyl or ethyl or both radicals R" bound to the same N atom form together with the N atom the piperidino, morpholino or pyrrolidino radical.
The meanings of the symbols in formula I are preferably as follows:
R is in each case a radical of an aromatic diisocyanate, R' is a radical of an aliphatic dill or of a polyalkylene glycol, and I" is in each case methyl or ethyl.
Particularly interesting diurethane Doris of the formula I are those wherein:
R is in each case phenylene or methylphenylene, Al is hexamethylene or the radical of a polyethylene or polypropylene glycol having a molecular weight of at most 500, and R" is in each case methyl.
The radicals R derived from diisocyanates can be aliphatic, cycloaliphatic, aromatic or araliphatic radicals.
The aliphatic radicals R can be straight-chain or branched-chain. The aromatic and cycloaliphatic radicals R can optionally contain substi~uents that are not reactive Jo epoxide resins for example halogen atoms, -N02 and Cl-C4-alkyl, preferably methyl, or Cl-C4-alkoxy.
Diisocyananates containing a radical R are for example:
ethylenediisocyanate, tetramethylene-1,4-diisocyanate~
hexamethylene-l,~-diisocyanate, dodecane-1,12-diisocyanate, 12; :~600 isometric mixtures of 2,2,4- and 2,4,4-trimethylhexanethylene-diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, and also any chosen mixtures of these isomers, hexahydrotoluylene-2,4- and -2,6-diisocyanate, parader'- or -4,4-diphenylmethane-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexylisocyanate ("isophoronediisocyanate"), Arlene-diisocyanates, which can be substituted by Cl-C4-alkyl, such as m- and p~phenylenediisocyanate, naphthylene-diisocyanates, diphenylmethane-4,4'-diisocyanate, methyl-phenylenediisocyanate, such as 2,4- and 2,6-methylphenylene-diisocyanate and mixtures thereof, diisopropylbenzene-diisocyanates, aralkyldiisocyanates, such as l-(isocyanato-phenyl)-ethylisocyanate or m- and p-xylylenediisocyanate, as well as polyisocyanates of the above-mentioned types substituted by various groups, for example by Cl-C4-alkoxy, phonics (wherein phenol can be substituted by Cl-C/~-alkyl), N02 or Of. The aromatic diisocyanates are preferred, for example 2,4- and 2,6-toluylenediisocyanate, annul also any mixtures of these isomers, diphenylmethane-4,4~-diiso-Senate and m- and p-phenylenediisocyanate.
The radicals R' derived from dills can be aliphatic, cycloaliphatic and/or araliphatic radicals having Ho groups bound to non aromatic C atoms. The aliphatic radicclls can be straight-chain or branched-chain, and can also be interrupted by one or more Selfware or oxygen atoms preferably by oxygen atoms. Dills containing a radical R' are for example glycols, such as ethylene glycol, propylene glycol, butane-1,4-diol, neopentyl glycol, hexane-1,6-diol, thiodiethylene glycol, the ether alcohols, such as dip or triethylene glycol, dip or tripropylene glycol, the higher poly(oxyethylene)- and poly(oxypropylene) glycols, oxyethylated or oxypropylated bisphenols or hydantoins, 122~ 0 such as are obtained, in a known manner, by an addition reaction of ethylene oxide or propylene oxide with these compounds; perhydrobisphenols, such as bis-~4-hydroxy-cyclohexyl)-methane and 2,2-bis-(4-hydroxycyclohexyl)-propane, l,l-bis-(hydroxymethyl)-3-cyclohexane or cyclohexane-1,3-diol and -Doyle.
The compounds of the formula I according to the invention can be produced by reacting, in a first stage, a diisocyanate of the formula II
OCN-R-NCO (II) with a dill of the formula III
O'ER' OH (III), in the molar ratio of 2:1, to a diisocyanatodiurethane of the formula IV
OCN-R-NHCO-O-R'-O-OCNH-R-NCO (IV);
and then, in a second stage, reacting the diisocyanato-diurethane with a secondary amine of the formula V
OR"
Ho TV), wherein R, R' and R" are as defined under the formula I, in the molar ratio of 1:2, to obtain a diurethane Doria of the formula I.
In the case of the secondary amine ox the formula V, these are, according to definition, dimethylaminea deathly-amine, methylethylamine, piperidine, morph Olin and pyrrolidine. Readily volatile or gaseous secondary amine, for example dimethylamine, are advantageously used ion excess.
The reaction of the diisocyanate of the formula II
with a dill ox the formula III can be performed using o customary methods for producing urethanes. The reaction can be carried out at room temperature or at elevated temperature, and in the presence or absence of organic solvents or of catalysts. Suitable solvents are for example Tulane or Dixon, and suitable catalysts are for example tert-amines.
As mentioned at the commencement, the diurethane Doris according to the invention are valuable curing agents and curing accelerators in curable epoxide resin mixtures. The diurethane Doris exhibit good compatibility with epoxide resins and can be easily processed therewith.
Forming further subject matter of the invention are therefore also hot-curable mixtures which contain a) an epoxide resin and b) an effective amount of a diurethane Doria of the formula I.
When the epoxide resin mixtures according to the invention contain the diurethane Doris of the formula I
in an amount sufficient for curing, that is, as curing agents where are present in the curable mixture in general 5 to 25, preferably 10 to 20, parts by weight of (b) per 10~ parts by weight of epoxide resin (a).
In the mixtures according to the invention, the epoxide resins (a) preferably used are those having at least two glycidyl or ~-methylglycidyl groups bound directly to an oxygen, nitrogen or sulfur atom or atoms.
Mentioned as examples of such resins are the polyglycidyl-and poly-(~-methylglycidyl) esters, which can be obtained by reaction of a compound containing two or more carboxylic acid groups per molecule with epichlorohydrin, glycerol dichlorohydrin or ~-methylepîchlorohydrin in the presence ox an alkali. These polyglycidyl esters can be derived ~22g~
from aliphatic polycarboxylic acids, for example from oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sub Eric acid, azelaic acid, sebacic acid or dimerised or trimerised linoleic acid; from cycle-aliphatic polycarboxylic acids, such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid and 4-methylhexahydrophthalic acid; as well as from aromatic polycarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid.
Further examples are polyglycidyl- and polyp methylglycidyl) ethers, which are obtainable by reaction of a compound containing at least two free alcoholic and/or finlike hydroxyl groups per molecule with the corresponding epichlorohydrin under alkaline conditions; or also in the presence of an acid catalyst with a subsequent alkali treatment. These ethers can be produced from cyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly-(oxyethylene) glycols, propane-1,2-diol and poly-(oxypropylene) glycols, propane-1,3-diol, butane-1,4-diol, poly-(oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, l,l,l-trimethylpropane, pentaerythritol, sorbitol and polyepichlorohydrins; from cycloaliphatic alcohols, such as resorcitol, quaintly, bis-(4-hydroxycyclohexyl)-methane, 2,2-bis-(4-hydroxycyclohexyl)-propane and l,l-bis-(hydroxymethyl)-3-cyclohexene; and from alcohols having aromatic nuclei, such as N,N-bis-(2-hydroxyethyl)-aniline and p,p'-bis-(2-hydroxyethylamino)-diphenylmethane. They can also be produced from novolaks formed from mononuclear phenols, such as resorcinol and hydroquinone, and from polynuclear phenols, such as bis-(4-hydroxyphenyl)-methane, 4,4'-dihydroxydiphenyl, bis-(4-hydroxyphenyl)-sul~one, 1,1,2,2-tetrakis-(4-hydroxyphenyl)-ethane, Boyce-96~)~
(4-hydroxyphenyl)-propane and 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane; and also from aldehydes, such as formaldehyde, acetaldehyde, choral and furfurol with phenols, such as phenol itself, and phenol ring-substituted by chlorine atoms or alkyd groups each having up to 9 carbon atoms, such as 4-chlorophenol, 2-methylphenol and 4-tert-butylphenol.
Pylon glycidyl) compounds embrace for example those which are obtained by dehydrochlorination of the reaction products of epichlorohydrin with amine containing at least two amino hydrogen atoms, such as aniline, n-butylamine, bis-(4-aminophenyl)-methane, m-xylyenediamine and Boyce-methylaminophenyl)-methane; trig].ycidylisocyanurate, as well as N,N'-diglycidyl derivatives of cyclic alkyleneureas, such as ethylene urea and 1,3-propyleneurea; and hydantoins, such as 5,5-dimethylhydantoin.
Poly-(S-glycidyl) compounds are for example the di-S-glycidyl derivatives of deathless, such as ethanes deathly and bis-(4-mercaptomethylphenyl.) ether.
Also suitable are for example epoxide resins in which the glycidyl groups are bound to hotter atoms of varying nature, for example the N,N,O-tri.glycidyl derivative of 4-aminophenol, of glycidyl ethers/glycidyl esters of salicylic acid, N-glycidyl-N'-(2-glycidyloxypropyl)-S,5-dimethylhydantoin and 2-glycidyloxy-1,3-bis-(5,5-dimethyl-l-glycidylhydantoin-3 ye) propane.
Suitable for the hot-curable mixtures according to the invention are also the cycloaliphatic epoxide resins wherein the epoxide group is part of the aliphatic ring system, for example bis-(~,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl-glycidyl ether and Boyce-epoxycyclopentyloxy)-ethane.
A mixture of epoxide resins can if desired be used.
Preferred epoxide resins are polyglycidyl ethers, polyglycidyl esters and poly-(N-glycidyl) derivatives of aromatic amine. Specially preferred resins are the polyglycidyl ethers of 2,2-bis-(4-hydroxyphenyl)-propane, bis-(4-hydroxyphenyl)-methane, or of a novolak formed from formaldehyde and phenol, or phenol ring-substituted by a chlorine atom or an alkyd having 1 to 4 C atoms, and having a 1,2~epoxide content of at least 0.5 equivalent per kilogram; bis-(4-(diglycidylamino)-phenyl)-methane and p-(diglycidylamino)-phenyl-glycidyl ether It has also been found that the diurethane Doris of the formula I according to the invention are moreover valuable accelerators in the hot-curing of epoxide resins with hot-curing agents, preferably dicyandiamide, cyan-acutely compounds and polycarboxylic acid androids.
Further subject matter is hence formed by hot-curable mixtures according to the invention which additionally contain (c) a large amount by weight, relative to the amount by weight of the diurethane Doria (b), of the dicyandiamide, of a cyanoacetyl compound of the formula VI
o (N--c-cH2 CUR"' (VI) wherein R"' is a radical derived from an n-valent alcohol or n-valent amine and having a partial molecular weight of ~2000, and n is a number from 1 to 4, or of a polycarboxylic acid android.
The cyanoacetyl compounds of the formula VI and the use thereof as curing agents for epoxide resins are known from the US. Patent Specification No. 4,283,520, and, as is stated therein, the cyanoacetyl compounds are used, ~:29 in curable epoxide resin mixtures, in such amounts that to one cya~oacetyl group there are 3 to 4 epoxide groups.
Dicyandiamide and the polycarboxylic acid androids are used in the customary amounts for curing agents.
In the curable epoxide resin mixtures according to the invention which contain the component (by as the accelerator, the diurethane Doria compounds (b) are in general used in amounts ox 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, per 10~ parts by weight of epoxide resin.
Suitable cyanoacetyl compounds of the formula VI are for example: neopentyl glycol-bis-cyanoacetic acid ester, cyanoacetic acid-N-isobutylamide, ethylene glycol-bis-cyanoacetic acid ester, 1,4-cyclohexanedimethanol bus-Cenozoic acid ester and cyanoacetic acid-N-(N-dimethyl-aminopropylamide).
The polycarboxylic acid androids employed are preferably the customary aliphatic, cycloaliphatic or aromatic polycarboxylic acid androids suitable or curing epoxide resins, for example phthalic android, tetrahydrophthalic android, hexahydrophthalic android, dodecylsuccinic android, hexachloroendomethylene-tetrahydrophthalic android and endomethylenetetrahydro-phthalic android and mixtures thereof, malefic anhydLide, succinic android 9 pyromellitic android, benzophenone-3,3'-4~4'-tetracarb2xylic~dianhydride, polysebacic android and polyazelaic android, as well as isophthalic android, terephthalic android, citric android or mellitic android.
The curable mixtures according to the invention can also contain plasticizers, such as dib~ltyl phthalate7 ductile phthalate or tricresyl phosphate, or additives ~L229~0 such as extenders, fillers, reinforcing agents, coloring agents, flow-promoting agents and mound release agents.
Suitable extenders, fillers and reinforcing agents are for example: asbestos, asphalt, bitumen, glass fibrous, textile fires, carbon or boron fires, mica, alumina, gypsum, titanium dioxide, chalk, quartz flour, cellulose, kaolin, ground dolomite, wollastonite, siliceous earth having a large specific surface obtainable under the trade-name of Aerosol ), alumina modified with long-chain amine (obtainable under the trade-name of Ben tone ), powdered polyvinyl chloride, polyolefin or aminoplasts, metal powders, such as aluminum or iron powders. Also fireproofing agents, such as antimony oxide, can be added to the curable mixtures.
The curable compositions according to the invention can be used as laminating, impregnating and casting resins, powder coatings, mounding compounds, bonding cements and sealing compounds, embedding and insulating compounds for the electrical industry, but particularly as adhesives and priming for adhesives.
The compositions according to the invention are preferably cured by heating them to a temperature within the range of 100 to 180C, especially 100 to 140C. A
heating time of 30 to 120 minutes usually suffices for curing.
The following Examples further illustrate the invent lion. Parts are parts by weight.
~2~296~
Example Preparation of ox Thwack\ 3 ; NHCOO~CH2 SHEEHAN Jo 348 parts by weight of toluylene-2,4-diisocyanate are diluted with 400 parts of Tulane; the temperature is then raised to 80C and 90 parts of butanediol-1~4 are added with vigorous stirring. The Tulane is afterwards distilled off in vacua; 350 parts of Dixon are added, and 200 parts of gaseous dimethyl~nine are subsequently introduced at 22-?5C. Excess dimethylamine and Dixon is then removed at 140C and 19.9 mar in a rotary evaporator. There are thus obtained 519.6 parts (98.3% of theory) of a pale yellow solid resin having a glass transition temperature TUG of 73.5C.
Analysis calculated for found % C: 59.08 59.4 % H: 6.86 7.1 % N: 15.91 15.6 Example 2: Preparation of ~N-COTH OH KIWI 3 it SHEA CoocH2cH2oc~2cH2oocHN~ Ross The procedure is carried out as in Example 1 except that 106.1 parts of diethylene glycol are added drops in place of butanediol-1,4. Introduction of dimethylamine:
320 parts.
Yield : 533 parts (98% of theory) TUG : 75.5C
Analysis : calculated for found % C: 57.34 57.~
% H: 6.66 7.0 % N: 15.43 15.5 Example 3: Preparation of kiwi KIWI
, if '! !
HCOO-cH2cH2scH2cH200cHN/ OH
Ho 3 Starting : toluylene-2,4-diisocyanate 348 parts materials thio-diethylene glycol 122.2 parts Tulane 500 parts Dixon 350 parts dimethylamine 250.2 parts Procedure as in Example 1.
Yield : 536 parts (95.7% of theory) TUG : 81C
Analysis : calculated for found % C:55.69 55.5 % H:6.47 6.6 % N:14.98 14.7 % S:5.71 5.7 ~229~0C~
Example 4: Preparation of
The meanings of the symbols in formula I are preferably as follows:
R is in each case a radical of an aromatic diisocyanate, R' is a radical of an aliphatic dill or of a polyalkylene glycol, and I" is in each case methyl or ethyl.
Particularly interesting diurethane Doris of the formula I are those wherein:
R is in each case phenylene or methylphenylene, Al is hexamethylene or the radical of a polyethylene or polypropylene glycol having a molecular weight of at most 500, and R" is in each case methyl.
The radicals R derived from diisocyanates can be aliphatic, cycloaliphatic, aromatic or araliphatic radicals.
The aliphatic radicals R can be straight-chain or branched-chain. The aromatic and cycloaliphatic radicals R can optionally contain substi~uents that are not reactive Jo epoxide resins for example halogen atoms, -N02 and Cl-C4-alkyl, preferably methyl, or Cl-C4-alkoxy.
Diisocyananates containing a radical R are for example:
ethylenediisocyanate, tetramethylene-1,4-diisocyanate~
hexamethylene-l,~-diisocyanate, dodecane-1,12-diisocyanate, 12; :~600 isometric mixtures of 2,2,4- and 2,4,4-trimethylhexanethylene-diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, and also any chosen mixtures of these isomers, hexahydrotoluylene-2,4- and -2,6-diisocyanate, parader'- or -4,4-diphenylmethane-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexylisocyanate ("isophoronediisocyanate"), Arlene-diisocyanates, which can be substituted by Cl-C4-alkyl, such as m- and p~phenylenediisocyanate, naphthylene-diisocyanates, diphenylmethane-4,4'-diisocyanate, methyl-phenylenediisocyanate, such as 2,4- and 2,6-methylphenylene-diisocyanate and mixtures thereof, diisopropylbenzene-diisocyanates, aralkyldiisocyanates, such as l-(isocyanato-phenyl)-ethylisocyanate or m- and p-xylylenediisocyanate, as well as polyisocyanates of the above-mentioned types substituted by various groups, for example by Cl-C4-alkoxy, phonics (wherein phenol can be substituted by Cl-C/~-alkyl), N02 or Of. The aromatic diisocyanates are preferred, for example 2,4- and 2,6-toluylenediisocyanate, annul also any mixtures of these isomers, diphenylmethane-4,4~-diiso-Senate and m- and p-phenylenediisocyanate.
The radicals R' derived from dills can be aliphatic, cycloaliphatic and/or araliphatic radicals having Ho groups bound to non aromatic C atoms. The aliphatic radicclls can be straight-chain or branched-chain, and can also be interrupted by one or more Selfware or oxygen atoms preferably by oxygen atoms. Dills containing a radical R' are for example glycols, such as ethylene glycol, propylene glycol, butane-1,4-diol, neopentyl glycol, hexane-1,6-diol, thiodiethylene glycol, the ether alcohols, such as dip or triethylene glycol, dip or tripropylene glycol, the higher poly(oxyethylene)- and poly(oxypropylene) glycols, oxyethylated or oxypropylated bisphenols or hydantoins, 122~ 0 such as are obtained, in a known manner, by an addition reaction of ethylene oxide or propylene oxide with these compounds; perhydrobisphenols, such as bis-~4-hydroxy-cyclohexyl)-methane and 2,2-bis-(4-hydroxycyclohexyl)-propane, l,l-bis-(hydroxymethyl)-3-cyclohexane or cyclohexane-1,3-diol and -Doyle.
The compounds of the formula I according to the invention can be produced by reacting, in a first stage, a diisocyanate of the formula II
OCN-R-NCO (II) with a dill of the formula III
O'ER' OH (III), in the molar ratio of 2:1, to a diisocyanatodiurethane of the formula IV
OCN-R-NHCO-O-R'-O-OCNH-R-NCO (IV);
and then, in a second stage, reacting the diisocyanato-diurethane with a secondary amine of the formula V
OR"
Ho TV), wherein R, R' and R" are as defined under the formula I, in the molar ratio of 1:2, to obtain a diurethane Doria of the formula I.
In the case of the secondary amine ox the formula V, these are, according to definition, dimethylaminea deathly-amine, methylethylamine, piperidine, morph Olin and pyrrolidine. Readily volatile or gaseous secondary amine, for example dimethylamine, are advantageously used ion excess.
The reaction of the diisocyanate of the formula II
with a dill ox the formula III can be performed using o customary methods for producing urethanes. The reaction can be carried out at room temperature or at elevated temperature, and in the presence or absence of organic solvents or of catalysts. Suitable solvents are for example Tulane or Dixon, and suitable catalysts are for example tert-amines.
As mentioned at the commencement, the diurethane Doris according to the invention are valuable curing agents and curing accelerators in curable epoxide resin mixtures. The diurethane Doris exhibit good compatibility with epoxide resins and can be easily processed therewith.
Forming further subject matter of the invention are therefore also hot-curable mixtures which contain a) an epoxide resin and b) an effective amount of a diurethane Doria of the formula I.
When the epoxide resin mixtures according to the invention contain the diurethane Doris of the formula I
in an amount sufficient for curing, that is, as curing agents where are present in the curable mixture in general 5 to 25, preferably 10 to 20, parts by weight of (b) per 10~ parts by weight of epoxide resin (a).
In the mixtures according to the invention, the epoxide resins (a) preferably used are those having at least two glycidyl or ~-methylglycidyl groups bound directly to an oxygen, nitrogen or sulfur atom or atoms.
Mentioned as examples of such resins are the polyglycidyl-and poly-(~-methylglycidyl) esters, which can be obtained by reaction of a compound containing two or more carboxylic acid groups per molecule with epichlorohydrin, glycerol dichlorohydrin or ~-methylepîchlorohydrin in the presence ox an alkali. These polyglycidyl esters can be derived ~22g~
from aliphatic polycarboxylic acids, for example from oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sub Eric acid, azelaic acid, sebacic acid or dimerised or trimerised linoleic acid; from cycle-aliphatic polycarboxylic acids, such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid and 4-methylhexahydrophthalic acid; as well as from aromatic polycarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid.
Further examples are polyglycidyl- and polyp methylglycidyl) ethers, which are obtainable by reaction of a compound containing at least two free alcoholic and/or finlike hydroxyl groups per molecule with the corresponding epichlorohydrin under alkaline conditions; or also in the presence of an acid catalyst with a subsequent alkali treatment. These ethers can be produced from cyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly-(oxyethylene) glycols, propane-1,2-diol and poly-(oxypropylene) glycols, propane-1,3-diol, butane-1,4-diol, poly-(oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, l,l,l-trimethylpropane, pentaerythritol, sorbitol and polyepichlorohydrins; from cycloaliphatic alcohols, such as resorcitol, quaintly, bis-(4-hydroxycyclohexyl)-methane, 2,2-bis-(4-hydroxycyclohexyl)-propane and l,l-bis-(hydroxymethyl)-3-cyclohexene; and from alcohols having aromatic nuclei, such as N,N-bis-(2-hydroxyethyl)-aniline and p,p'-bis-(2-hydroxyethylamino)-diphenylmethane. They can also be produced from novolaks formed from mononuclear phenols, such as resorcinol and hydroquinone, and from polynuclear phenols, such as bis-(4-hydroxyphenyl)-methane, 4,4'-dihydroxydiphenyl, bis-(4-hydroxyphenyl)-sul~one, 1,1,2,2-tetrakis-(4-hydroxyphenyl)-ethane, Boyce-96~)~
(4-hydroxyphenyl)-propane and 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane; and also from aldehydes, such as formaldehyde, acetaldehyde, choral and furfurol with phenols, such as phenol itself, and phenol ring-substituted by chlorine atoms or alkyd groups each having up to 9 carbon atoms, such as 4-chlorophenol, 2-methylphenol and 4-tert-butylphenol.
Pylon glycidyl) compounds embrace for example those which are obtained by dehydrochlorination of the reaction products of epichlorohydrin with amine containing at least two amino hydrogen atoms, such as aniline, n-butylamine, bis-(4-aminophenyl)-methane, m-xylyenediamine and Boyce-methylaminophenyl)-methane; trig].ycidylisocyanurate, as well as N,N'-diglycidyl derivatives of cyclic alkyleneureas, such as ethylene urea and 1,3-propyleneurea; and hydantoins, such as 5,5-dimethylhydantoin.
Poly-(S-glycidyl) compounds are for example the di-S-glycidyl derivatives of deathless, such as ethanes deathly and bis-(4-mercaptomethylphenyl.) ether.
Also suitable are for example epoxide resins in which the glycidyl groups are bound to hotter atoms of varying nature, for example the N,N,O-tri.glycidyl derivative of 4-aminophenol, of glycidyl ethers/glycidyl esters of salicylic acid, N-glycidyl-N'-(2-glycidyloxypropyl)-S,5-dimethylhydantoin and 2-glycidyloxy-1,3-bis-(5,5-dimethyl-l-glycidylhydantoin-3 ye) propane.
Suitable for the hot-curable mixtures according to the invention are also the cycloaliphatic epoxide resins wherein the epoxide group is part of the aliphatic ring system, for example bis-(~,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl-glycidyl ether and Boyce-epoxycyclopentyloxy)-ethane.
A mixture of epoxide resins can if desired be used.
Preferred epoxide resins are polyglycidyl ethers, polyglycidyl esters and poly-(N-glycidyl) derivatives of aromatic amine. Specially preferred resins are the polyglycidyl ethers of 2,2-bis-(4-hydroxyphenyl)-propane, bis-(4-hydroxyphenyl)-methane, or of a novolak formed from formaldehyde and phenol, or phenol ring-substituted by a chlorine atom or an alkyd having 1 to 4 C atoms, and having a 1,2~epoxide content of at least 0.5 equivalent per kilogram; bis-(4-(diglycidylamino)-phenyl)-methane and p-(diglycidylamino)-phenyl-glycidyl ether It has also been found that the diurethane Doris of the formula I according to the invention are moreover valuable accelerators in the hot-curing of epoxide resins with hot-curing agents, preferably dicyandiamide, cyan-acutely compounds and polycarboxylic acid androids.
Further subject matter is hence formed by hot-curable mixtures according to the invention which additionally contain (c) a large amount by weight, relative to the amount by weight of the diurethane Doria (b), of the dicyandiamide, of a cyanoacetyl compound of the formula VI
o (N--c-cH2 CUR"' (VI) wherein R"' is a radical derived from an n-valent alcohol or n-valent amine and having a partial molecular weight of ~2000, and n is a number from 1 to 4, or of a polycarboxylic acid android.
The cyanoacetyl compounds of the formula VI and the use thereof as curing agents for epoxide resins are known from the US. Patent Specification No. 4,283,520, and, as is stated therein, the cyanoacetyl compounds are used, ~:29 in curable epoxide resin mixtures, in such amounts that to one cya~oacetyl group there are 3 to 4 epoxide groups.
Dicyandiamide and the polycarboxylic acid androids are used in the customary amounts for curing agents.
In the curable epoxide resin mixtures according to the invention which contain the component (by as the accelerator, the diurethane Doria compounds (b) are in general used in amounts ox 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, per 10~ parts by weight of epoxide resin.
Suitable cyanoacetyl compounds of the formula VI are for example: neopentyl glycol-bis-cyanoacetic acid ester, cyanoacetic acid-N-isobutylamide, ethylene glycol-bis-cyanoacetic acid ester, 1,4-cyclohexanedimethanol bus-Cenozoic acid ester and cyanoacetic acid-N-(N-dimethyl-aminopropylamide).
The polycarboxylic acid androids employed are preferably the customary aliphatic, cycloaliphatic or aromatic polycarboxylic acid androids suitable or curing epoxide resins, for example phthalic android, tetrahydrophthalic android, hexahydrophthalic android, dodecylsuccinic android, hexachloroendomethylene-tetrahydrophthalic android and endomethylenetetrahydro-phthalic android and mixtures thereof, malefic anhydLide, succinic android 9 pyromellitic android, benzophenone-3,3'-4~4'-tetracarb2xylic~dianhydride, polysebacic android and polyazelaic android, as well as isophthalic android, terephthalic android, citric android or mellitic android.
The curable mixtures according to the invention can also contain plasticizers, such as dib~ltyl phthalate7 ductile phthalate or tricresyl phosphate, or additives ~L229~0 such as extenders, fillers, reinforcing agents, coloring agents, flow-promoting agents and mound release agents.
Suitable extenders, fillers and reinforcing agents are for example: asbestos, asphalt, bitumen, glass fibrous, textile fires, carbon or boron fires, mica, alumina, gypsum, titanium dioxide, chalk, quartz flour, cellulose, kaolin, ground dolomite, wollastonite, siliceous earth having a large specific surface obtainable under the trade-name of Aerosol ), alumina modified with long-chain amine (obtainable under the trade-name of Ben tone ), powdered polyvinyl chloride, polyolefin or aminoplasts, metal powders, such as aluminum or iron powders. Also fireproofing agents, such as antimony oxide, can be added to the curable mixtures.
The curable compositions according to the invention can be used as laminating, impregnating and casting resins, powder coatings, mounding compounds, bonding cements and sealing compounds, embedding and insulating compounds for the electrical industry, but particularly as adhesives and priming for adhesives.
The compositions according to the invention are preferably cured by heating them to a temperature within the range of 100 to 180C, especially 100 to 140C. A
heating time of 30 to 120 minutes usually suffices for curing.
The following Examples further illustrate the invent lion. Parts are parts by weight.
~2~296~
Example Preparation of ox Thwack\ 3 ; NHCOO~CH2 SHEEHAN Jo 348 parts by weight of toluylene-2,4-diisocyanate are diluted with 400 parts of Tulane; the temperature is then raised to 80C and 90 parts of butanediol-1~4 are added with vigorous stirring. The Tulane is afterwards distilled off in vacua; 350 parts of Dixon are added, and 200 parts of gaseous dimethyl~nine are subsequently introduced at 22-?5C. Excess dimethylamine and Dixon is then removed at 140C and 19.9 mar in a rotary evaporator. There are thus obtained 519.6 parts (98.3% of theory) of a pale yellow solid resin having a glass transition temperature TUG of 73.5C.
Analysis calculated for found % C: 59.08 59.4 % H: 6.86 7.1 % N: 15.91 15.6 Example 2: Preparation of ~N-COTH OH KIWI 3 it SHEA CoocH2cH2oc~2cH2oocHN~ Ross The procedure is carried out as in Example 1 except that 106.1 parts of diethylene glycol are added drops in place of butanediol-1,4. Introduction of dimethylamine:
320 parts.
Yield : 533 parts (98% of theory) TUG : 75.5C
Analysis : calculated for found % C: 57.34 57.~
% H: 6.66 7.0 % N: 15.43 15.5 Example 3: Preparation of kiwi KIWI
, if '! !
HCOO-cH2cH2scH2cH200cHN/ OH
Ho 3 Starting : toluylene-2,4-diisocyanate 348 parts materials thio-diethylene glycol 122.2 parts Tulane 500 parts Dixon 350 parts dimethylamine 250.2 parts Procedure as in Example 1.
Yield : 536 parts (95.7% of theory) TUG : 81C
Analysis : calculated for found % C:55.69 55.5 % H:6.47 6.6 % N:14.98 14.7 % S:5.71 5.7 ~229~0C~
Example 4: Preparation of
3 kiwi ` kiwi i it if !
it' \NHC~cH2cH2o~cH2cH2ocoN~ I
Starting : toluylene-2,4-diisocyanate 348 parts materials triethylene glycol l.50 parts Tulane 400 parts Dixon 350 parts dimethylamine 200 parts Procedure as in Example 1.
yield : 570 parts (97% of theory) ova pale yellow solid resin TUG : 67C
Analysis: calculated for found % C 57.13 57.0 % H 6.85 6.9 % N 14.28 14.2 Example I: Preparation of KIWI . KIWI 3 \, ./
/~-/ \NHCOO~CH2~00CHN SHEA
~L2~:9600 Starting : Desmodur T (commercial mixture of materials 2,4- and 2,6-toluylenediisocyanate;
commercially obtainable product of BAYER AGO : 348 parts hexanediol-1,6 118 parts Tulane 500 parts Dixon 350 parts dimethylamine 171 parts Procedure as in Example 1.
Yield : 535.2 parts of a yellow solid resin (owe) TUG : 75C
Analysis: calculated for found % C 60.48 59.7 % H 7.58 7.3 % N 15.11 14.8 Example 6: Preparation of ~-coNH~cH2~THcoo~cH2-cHo3~cH2cHoocNH~c~l2~
Stating : hexamethylene-1,6-diisocyanate 168 parts materials polypropylene glycol 425 212.5 parts Tulane 300 parts Dixon 300 parts dimethylamine 86.7 parts Procedure as in Example 1. There are obtained 410 parts of a partially crystalline, wax-like substance (96.4%
of theory) having a nitrogen content of 10.2%
(calculated 9.87%).
~22960~
Example 7: Preparation of I Jo OH NH
I /- \.~-Ho 0 2 11 if mu/ I
ICKY SHEA KIWI
starting : diphenylmethane-4,4'-diisocyanate 218 parts materials hexanedlol-l,6 51.5 parts Tulane 300 parts Dixon 300 parts dime-thylamine 62 parts Procedure as in Example 1.
Yield: 301 parts (97.5% of theory) TUG : 163C
Analysis: calculated for found % C 67.78 68.4 % H 6.83 6.6 % N 11.86 11.2 9~00 Example 8: Preparation of H3C~ I Kiwi \ / 7 2 3 ! '!
I .
I Jo \.
1 '! Q
I/ OCH2CH20~ 3 Ho C112NH-~ C
- 158 parts of 2,2-bis-[4-(2-hydroxyethyl)phenoxy]-propane are dissolved in 500 parts of Tulane, and this solution is added drops at 85-90C, with stirring, to 222.27 parts of isophorone-diisocyanate. The mixture is allowed to subsequently react for 2 hours, and 73.14 parts of diethylamine are then introduced. After further reaction for 2 hours at 90C, the Tulane is removed in vacua at 150C in a rotary evaporator. There are obtained 359 parts of a solid resin (79.2% of theory) having a glass transition temperature of 90.5C.
Analysis: calculated for found % C 66.63 67.15 % H 9.36 9.18 TV N 9.52 9.26 - 17 - ~Zz9600 Example 9: Preparation of I Chicano I' Jo SHEA
H3C~C~CH2 Oily SHEA
3 Shea Cay \ / 2 5 H C/ OH NO
Starting : isophorone-diisocyanate222.27 parts materials neopentyl glycol 52.07 parts Tulane 400 parts diethylamine 73.14 parts Procedure as in Example 8.
yield: 327.2 parts, corresponding to 94.2% of theory.
Analysis: calculated for found % C 63.94 63.54 % H 10.15 10.17 % N 12.09 11.98 TUG: 72C
Example 10: Preparation of H3C~ shoeshine I
C_. H3C/ SHEA
No 2 SHEA
Starting : isophorone-diisocyanate222.27 parts materials polyethylene glycol 1000250 parts Tulane 500 parts morpholine 43.56 parts Procedure as in Example 8.
yield: 502 parts of a yellow viscous resin, corresponding to 97.3% of theory.
Analysis: found % C 57.12 % H 8.58 % N 5.26 Application Examples A) Curing of an epoxide resin with diurethane Doria resins In each case, 85 parts of an epoxide resin based on bisphenol-A having an epoxide content of 5.1 - 5.5 val/kg and a viscosity of 9000-13000 maps (epoxide resin I) are mixed with 15 parts of each of the diurethane Doris produced in Examples 1 to 5. The golfing times of these mixtures and the properties of the mounded materials obtained from these mixtures by curing (2 hours at 100C
and 8 hours at 140C) are given in the following Table.
~2g6~3~
Us I boy .,, Jo c e.
Jo e ox o a) D
'o o o O o o I Jo Us V O O
o a) Cal O o o o o I Ed u V
O J
I Al CO
V O O O O
Jo ^ .~:
e en H Jo us ._ æ 'I Z æ z z .. . . o o o o a ye I'`' O! C I I I
I O I C I: O O O O
.,1 I .,~ .,1 .,1 .,1 ,1 I Jo MU U
e. e. e I
o 5 I
boy Jo V O
_ .
~2%96~
B) Acceleration of the dicyandiamide curing owe an epoxide resin celling time at 120C
12 parts of epoxide resin I l 1.33 parts of dicyandiamide 3 ~18 hours and additionally owe part of diurethane Doria according to Example 1: 13.0 min.
0.266 part of diurethane Doria according to Example 2: 10.67 min.
0.266 part of diurethane Doria according to Example 3: 13.15 min.
owe part of diurethane Doria according to Example 4: 13.0 min.
owe part of diurethane Doria according to Example 5: 10.83 min.
0.266 part of diurethane Doria according to Example 6: 33.63 min.
(:).266 part of di.urethane Doria according to Example 7: 46.68 min.
0.266 part of diurethane Doria according to Example 8: 71 min.
owe part Go diurethane Doria according to Example 9: 69 min.
0.266 part of diurethane Doria according to Example 10: Z65 min.
C) Acceleration of the Sweeney ethyl curing of an epoxide resin Julienne time Attica 8.45 parts of epoxide resin-I l SHEA > 16 hours 1.55 parts of NC-CH2-CONH-CH2CH
SHEA
and additionally o .2 part of diurethane Doria according to Example 1: 31.0 min.
I I
0.2 part of diurethane Doria according to Example 2: 34.35 min.
0.2 part ox diurethane Doria according to Example 3: 31.50 min.
Q.2 part of diurethane Doria according to Example 4: 33. 3 min.
0.2 part of diurethane Doria according to Example 5: 30.07 min.
0.2 part of diurethane Doria according to Example 6: 82.5 min.
0.2 part of diurethane Doria according to Example 7: 176,3 min.
0.2 part of diurethane Doria according to Example 8: 187 min.
0.2 part of diurethane Doria according to Example 9: 177.5 min.
0.2 part of diurethane Doria according to Example 10: 339 min.
D) Acceleration of the android curing of an eddy resin 8~0 parts of epoxide resin I are mixed with 5.~1 parts of cis-hexahydrophthalic android. This mixture has a golfing time ox 674 minutes at 120C.
If there is added in each case to such a mixture 0.27 part (2%) of each of the diurethane Doris according to Examples 1-10, there are obtained the following results:
celling time at 120C
Curable mixture containing diurethane Doria according to Example 1:88 min.
diurethane Doria according to Example 2:88 min.
diurethane Doria according to Example 3:105 min.
diurethane Doria according to Example min.
diurethane Doria according to Example 5:111 min.
diurethane Doria according to Example 6:77 min.
diurethane Doria according to Example 7:14 min.
diurethane Doria according to Example 8:62 min.
diurethane Doria according to Example 9: 112 min.
diurethane Doria according to Example 10: 73 min.
The storage stability of the curable mixtures catalyzed with the diurethane Doris according to Examples 1-10 is only slightly reduced.
E) Curing of N,N,N',N'-te _ aglycidyl-4,4'-diamino-diphenylmethane N,N,N',N'-Tetraglycidyl-4,4'-diaminodiphenylmethanno having an epoxide equivalent weight of 133 (epoxide resin II) and the diurethane Doria produced in Example 5 are mixed together in the mixture ratios given in the following Table, and subsequently cured. The curing conditions (hours (h)/C) and the properties of the mounded materials obtained are likewise shown in the Table.
Table Example E 1 Eye E 3 E 4 Epoxide resin II (go 95 90 85 80 diurethane Doria 5 10 15 20 according to Example 5 go golfing (h/C) 2/90 curing ho 40/140 ~6/190 glass transition 140 193 231 239 temperature ( C3 flexural strength (N/mm2) 47 31 54 38 impact bend strength 2.0 1.0 2.0 1.6 (kJ/m2~
cold water absorption 0.33 0.57 0.68 1.31
it' \NHC~cH2cH2o~cH2cH2ocoN~ I
Starting : toluylene-2,4-diisocyanate 348 parts materials triethylene glycol l.50 parts Tulane 400 parts Dixon 350 parts dimethylamine 200 parts Procedure as in Example 1.
yield : 570 parts (97% of theory) ova pale yellow solid resin TUG : 67C
Analysis: calculated for found % C 57.13 57.0 % H 6.85 6.9 % N 14.28 14.2 Example I: Preparation of KIWI . KIWI 3 \, ./
/~-/ \NHCOO~CH2~00CHN SHEA
~L2~:9600 Starting : Desmodur T (commercial mixture of materials 2,4- and 2,6-toluylenediisocyanate;
commercially obtainable product of BAYER AGO : 348 parts hexanediol-1,6 118 parts Tulane 500 parts Dixon 350 parts dimethylamine 171 parts Procedure as in Example 1.
Yield : 535.2 parts of a yellow solid resin (owe) TUG : 75C
Analysis: calculated for found % C 60.48 59.7 % H 7.58 7.3 % N 15.11 14.8 Example 6: Preparation of ~-coNH~cH2~THcoo~cH2-cHo3~cH2cHoocNH~c~l2~
Stating : hexamethylene-1,6-diisocyanate 168 parts materials polypropylene glycol 425 212.5 parts Tulane 300 parts Dixon 300 parts dimethylamine 86.7 parts Procedure as in Example 1. There are obtained 410 parts of a partially crystalline, wax-like substance (96.4%
of theory) having a nitrogen content of 10.2%
(calculated 9.87%).
~22960~
Example 7: Preparation of I Jo OH NH
I /- \.~-Ho 0 2 11 if mu/ I
ICKY SHEA KIWI
starting : diphenylmethane-4,4'-diisocyanate 218 parts materials hexanedlol-l,6 51.5 parts Tulane 300 parts Dixon 300 parts dime-thylamine 62 parts Procedure as in Example 1.
Yield: 301 parts (97.5% of theory) TUG : 163C
Analysis: calculated for found % C 67.78 68.4 % H 6.83 6.6 % N 11.86 11.2 9~00 Example 8: Preparation of H3C~ I Kiwi \ / 7 2 3 ! '!
I .
I Jo \.
1 '! Q
I/ OCH2CH20~ 3 Ho C112NH-~ C
- 158 parts of 2,2-bis-[4-(2-hydroxyethyl)phenoxy]-propane are dissolved in 500 parts of Tulane, and this solution is added drops at 85-90C, with stirring, to 222.27 parts of isophorone-diisocyanate. The mixture is allowed to subsequently react for 2 hours, and 73.14 parts of diethylamine are then introduced. After further reaction for 2 hours at 90C, the Tulane is removed in vacua at 150C in a rotary evaporator. There are obtained 359 parts of a solid resin (79.2% of theory) having a glass transition temperature of 90.5C.
Analysis: calculated for found % C 66.63 67.15 % H 9.36 9.18 TV N 9.52 9.26 - 17 - ~Zz9600 Example 9: Preparation of I Chicano I' Jo SHEA
H3C~C~CH2 Oily SHEA
3 Shea Cay \ / 2 5 H C/ OH NO
Starting : isophorone-diisocyanate222.27 parts materials neopentyl glycol 52.07 parts Tulane 400 parts diethylamine 73.14 parts Procedure as in Example 8.
yield: 327.2 parts, corresponding to 94.2% of theory.
Analysis: calculated for found % C 63.94 63.54 % H 10.15 10.17 % N 12.09 11.98 TUG: 72C
Example 10: Preparation of H3C~ shoeshine I
C_. H3C/ SHEA
No 2 SHEA
Starting : isophorone-diisocyanate222.27 parts materials polyethylene glycol 1000250 parts Tulane 500 parts morpholine 43.56 parts Procedure as in Example 8.
yield: 502 parts of a yellow viscous resin, corresponding to 97.3% of theory.
Analysis: found % C 57.12 % H 8.58 % N 5.26 Application Examples A) Curing of an epoxide resin with diurethane Doria resins In each case, 85 parts of an epoxide resin based on bisphenol-A having an epoxide content of 5.1 - 5.5 val/kg and a viscosity of 9000-13000 maps (epoxide resin I) are mixed with 15 parts of each of the diurethane Doris produced in Examples 1 to 5. The golfing times of these mixtures and the properties of the mounded materials obtained from these mixtures by curing (2 hours at 100C
and 8 hours at 140C) are given in the following Table.
~2g6~3~
Us I boy .,, Jo c e.
Jo e ox o a) D
'o o o O o o I Jo Us V O O
o a) Cal O o o o o I Ed u V
O J
I Al CO
V O O O O
Jo ^ .~:
e en H Jo us ._ æ 'I Z æ z z .. . . o o o o a ye I'`' O! C I I I
I O I C I: O O O O
.,1 I .,~ .,1 .,1 .,1 ,1 I Jo MU U
e. e. e I
o 5 I
boy Jo V O
_ .
~2%96~
B) Acceleration of the dicyandiamide curing owe an epoxide resin celling time at 120C
12 parts of epoxide resin I l 1.33 parts of dicyandiamide 3 ~18 hours and additionally owe part of diurethane Doria according to Example 1: 13.0 min.
0.266 part of diurethane Doria according to Example 2: 10.67 min.
0.266 part of diurethane Doria according to Example 3: 13.15 min.
owe part of diurethane Doria according to Example 4: 13.0 min.
owe part of diurethane Doria according to Example 5: 10.83 min.
0.266 part of diurethane Doria according to Example 6: 33.63 min.
(:).266 part of di.urethane Doria according to Example 7: 46.68 min.
0.266 part of diurethane Doria according to Example 8: 71 min.
owe part Go diurethane Doria according to Example 9: 69 min.
0.266 part of diurethane Doria according to Example 10: Z65 min.
C) Acceleration of the Sweeney ethyl curing of an epoxide resin Julienne time Attica 8.45 parts of epoxide resin-I l SHEA > 16 hours 1.55 parts of NC-CH2-CONH-CH2CH
SHEA
and additionally o .2 part of diurethane Doria according to Example 1: 31.0 min.
I I
0.2 part of diurethane Doria according to Example 2: 34.35 min.
0.2 part ox diurethane Doria according to Example 3: 31.50 min.
Q.2 part of diurethane Doria according to Example 4: 33. 3 min.
0.2 part of diurethane Doria according to Example 5: 30.07 min.
0.2 part of diurethane Doria according to Example 6: 82.5 min.
0.2 part of diurethane Doria according to Example 7: 176,3 min.
0.2 part of diurethane Doria according to Example 8: 187 min.
0.2 part of diurethane Doria according to Example 9: 177.5 min.
0.2 part of diurethane Doria according to Example 10: 339 min.
D) Acceleration of the android curing of an eddy resin 8~0 parts of epoxide resin I are mixed with 5.~1 parts of cis-hexahydrophthalic android. This mixture has a golfing time ox 674 minutes at 120C.
If there is added in each case to such a mixture 0.27 part (2%) of each of the diurethane Doris according to Examples 1-10, there are obtained the following results:
celling time at 120C
Curable mixture containing diurethane Doria according to Example 1:88 min.
diurethane Doria according to Example 2:88 min.
diurethane Doria according to Example 3:105 min.
diurethane Doria according to Example min.
diurethane Doria according to Example 5:111 min.
diurethane Doria according to Example 6:77 min.
diurethane Doria according to Example 7:14 min.
diurethane Doria according to Example 8:62 min.
diurethane Doria according to Example 9: 112 min.
diurethane Doria according to Example 10: 73 min.
The storage stability of the curable mixtures catalyzed with the diurethane Doris according to Examples 1-10 is only slightly reduced.
E) Curing of N,N,N',N'-te _ aglycidyl-4,4'-diamino-diphenylmethane N,N,N',N'-Tetraglycidyl-4,4'-diaminodiphenylmethanno having an epoxide equivalent weight of 133 (epoxide resin II) and the diurethane Doria produced in Example 5 are mixed together in the mixture ratios given in the following Table, and subsequently cured. The curing conditions (hours (h)/C) and the properties of the mounded materials obtained are likewise shown in the Table.
Table Example E 1 Eye E 3 E 4 Epoxide resin II (go 95 90 85 80 diurethane Doria 5 10 15 20 according to Example 5 go golfing (h/C) 2/90 curing ho 40/140 ~6/190 glass transition 140 193 231 239 temperature ( C3 flexural strength (N/mm2) 47 31 54 38 impact bend strength 2.0 1.0 2.0 1.6 (kJ/m2~
cold water absorption 0.33 0.57 0.68 1.31
4 days at 25C (%) hot water absorption 0.41 0.38 0.47 1.87 1 hour at 100C (%) _ . I.
Claims (10)
1. A diurethane diurea of the formula I
(I) wherein R is in each case a radical derived from a diisocyanate and having at most 20 C atoms, R' is a radical derived from a diol and having a molecular weight of at most 1500, and the radicals R" are each methyl or ethyl, or both radicals R" bound to the same N atom form together with the N atom the piperidino, morpholino or pyrrolidino radical.
(I) wherein R is in each case a radical derived from a diisocyanate and having at most 20 C atoms, R' is a radical derived from a diol and having a molecular weight of at most 1500, and the radicals R" are each methyl or ethyl, or both radicals R" bound to the same N atom form together with the N atom the piperidino, morpholino or pyrrolidino radical.
2. A diurethane diurea according to claim 1, wherein in the formula I
R is in each case a radical of an aromatic diisocyanate, R' is a radical of an aliphatic diol or of a polyalkylene glycol, and R" is in each case methyl or ethyl.
R is in each case a radical of an aromatic diisocyanate, R' is a radical of an aliphatic diol or of a polyalkylene glycol, and R" is in each case methyl or ethyl.
3. A diurethane diurea according to claim 1, wherein in the formula I
R is in each case phenylene or methylphenylene, R' is hexamethylene or the radical of a polyethylene or polypropylene glycol having a molecular weight of at most 500, and R" is in each case methyl.
R is in each case phenylene or methylphenylene, R' is hexamethylene or the radical of a polyethylene or polypropylene glycol having a molecular weight of at most 500, and R" is in each case methyl.
4. A process for producing a diurethane diurea of the formula I according to claim 1, which process comprises reacting, in a first stage, a diisocyanate of the formula II
OCN-R-NCO (II) with a diol of the formula III
HO-R'-OH (III), in the molar ratio of 2:1, to a diisocyanate diurethane of the formula IV
OCN-R-NHCO-O-R'-O-OCNH-R-NCO (IV);
and then, in a second stage, reacting the diisocyanato-diurethane with a secondary amine of the formula V
(V), wherein R, R' and R" are as defined under the formula I, in the molar ratio of 1:2, to obtain a diurethane diurea of the formula I.
OCN-R-NCO (II) with a diol of the formula III
HO-R'-OH (III), in the molar ratio of 2:1, to a diisocyanate diurethane of the formula IV
OCN-R-NHCO-O-R'-O-OCNH-R-NCO (IV);
and then, in a second stage, reacting the diisocyanato-diurethane with a secondary amine of the formula V
(V), wherein R, R' and R" are as defined under the formula I, in the molar ratio of 1:2, to obtain a diurethane diurea of the formula I.
5. A hot-curable mixture which contains (a) an epoxide resin and (b) an effective amount of a diurethane diurea of the formula I according to claim 1.
6. A mixture according to claim 5 which contains 5 to 25 parts by weight of (b) per 100 parts by weight of (a).
7. A mixture according to claim 5, which additionally contains (c) a large amount by weight, relative to the amount by weight of (b), of the dicyandiamide, of a cyanoacetyl compound of the formula VI
(VI) wherein R''' is a radical derived from an n-valent alcohol or n-valent amine and having a partial molecular weight of ?2000, and n is a number from 1 to 4, or of a polycarboxylic acid anhydride.
(VI) wherein R''' is a radical derived from an n-valent alcohol or n-valent amine and having a partial molecular weight of ?2000, and n is a number from 1 to 4, or of a polycarboxylic acid anhydride.
8. A mixture according to claim 5, wherein (a) contains at least two glycidyl or .beta.-methylglycidyl groups which are bound directly to an oxygen, nitrogen or sulfur atom or atoms.
9. A mixture according to claim 5, wherein (a) is a polyglycidyl ether, a polyglycidyl ester or a poly-(N-glycidyl) derivative of an aromatic amine.
10. The products obtained by the hot-curing of a mixture according to claim 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH5605/83-8 | 1983-10-14 | ||
| CH560583 | 1983-10-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1229600A true CA1229600A (en) | 1987-11-24 |
Family
ID=4296405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000465247A Expired CA1229600A (en) | 1983-10-14 | 1984-10-12 | Diurethane diureas and the use thereof |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0138769B1 (en) |
| JP (1) | JPS60104055A (en) |
| CA (1) | CA1229600A (en) |
| DE (1) | DE3471652D1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4906722A (en) * | 1987-12-02 | 1990-03-06 | Ciba-Geigy Corporation | Thermosetting reactive systems |
| EP0520627A3 (en) * | 1991-06-27 | 1993-07-21 | Minnesota Mining And Manufacturing Company | Polyisocyanates partially blocked by amines and selfcuring resinous adducts derived therefrom |
| EP0603131A1 (en) * | 1992-12-18 | 1994-06-22 | Ciba-Geigy Ag | Aromatic urea compound used as hardening accelerator for a composition of epoxy resin and dicyandiamide |
| JP3739282B2 (en) | 1998-09-04 | 2006-01-25 | 旭化成ケミカルズ株式会社 | New color former and recording material |
| US7635662B2 (en) | 1998-09-04 | 2009-12-22 | Chemipro Kasei Kaisha, Ltd. | Compound for color-producing composition, and recording material |
| US6737163B2 (en) * | 2002-05-31 | 2004-05-18 | Ppg Industries Ohio, Inc. | Low-cure powder coatings and methods for using the same |
| JP6095766B2 (en) * | 2013-02-26 | 2017-03-15 | 富士フイルム株式会社 | Cellulose acylate film, novel compound, polarizing plate and liquid crystal display device |
| CN105384951B (en) | 2014-09-03 | 2020-09-18 | 富士胶片株式会社 | Polymer film, polarizing plate and liquid crystal display device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1535730A (en) * | 1975-04-30 | 1978-12-13 | Shell Int Research | Carbamates and their use as antioxidants |
-
1984
- 1984-10-08 DE DE8484810490T patent/DE3471652D1/en not_active Expired
- 1984-10-08 EP EP84810490A patent/EP0138769B1/en not_active Expired
- 1984-10-12 CA CA000465247A patent/CA1229600A/en not_active Expired
- 1984-10-15 JP JP59216025A patent/JPS60104055A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0138769B1 (en) | 1988-06-01 |
| EP0138769A2 (en) | 1985-04-24 |
| DE3471652D1 (en) | 1988-07-07 |
| EP0138769A3 (en) | 1986-04-02 |
| JPS60104055A (en) | 1985-06-08 |
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