CA1219986A

CA1219986A - Hardenable urethane-epoxy resin mixtures

Info

Publication number: CA1219986A
Application number: CA000442530A
Authority: CA
Inventors: Christian Burba; Hermann-Josef Lucas; Bernd Neffgen
Original assignee: Schering AG
Current assignee: Bayer Pharma AG
Priority date: 1982-12-15
Filing date: 1983-12-05
Publication date: 1987-03-31

Abstract

ABSTRACT OF THE DISCLOSURE

What are disclosed are curable synthetic resin mix-tures formed from a glycidyl compound having an average of more than one epoxy group per molecule and from a polyether urethane urea amine having two or more reactive amino hydrogen atoms per molecule, produced by the reaction of a di- or poly-functional aryl carbamate ester with at least one di- and/or polyfunctional amino compound having at least two reactive amino hydrogen atoms per molecule, or one reactive amino hydrogen atom and at least one azomethine group per molecule, the amine then being liberated by hydrolysis from the com-pounds containing azomethine groups, said mixtures optionally containing conventional fillers, pigments, accelerators, vis-cosity regulators, and other additives.

Description

(`) L~ L ,q~

HARDENABLE llR~THANE-EPOXY R~IN MIXTURE
The present invention pertains to h~rdenable, i.e.
curab].e, synthetic resin mixtures comprising (1) a glycidyl compound having an average of more than one epoxy group per moiecule and (2) the reaction product formed between prepolymeric aryl esters of carbamic acid and di- or poly-functional amino compounds having two or more active hydrogen atoms per molecule.
Synthetic resins comprising epoxy resins cured with polyamines are distinguished in practice bv a number of desirable properties, such as qood adhesion to organic and inorganic substrates, good solvent stability, and high resistance to the action of chemicals. Because of their high cro.sslinking density, amine cured epoxy resins, and especially those comprising diphenylpropane and epichlorohydrin, are hard and brittle, with ~lass transition t.emperatures above 20C.
~ owever, these synthetic resins fall short o meeting actual requirements in all field of use where impact stren~th and shock resistance as well as ~lexibility are required. This is true especially of the constru~tion field, where shrinXage cracks in concrete, ~or example, must be permanently filled.
To some extent, an internal increase in flexibility can he obtained by reducinq the crosslinking '`'`~

density, and an external increase in flexibility by the addition of plasticizers.
External elasticizers such as tar, phthalate esters, high-boiling alcohols, vinyl polymers and the like are nonreactive and are not incorporated into the thermoset plastic network. They merely result in an expansion throuyh the filling out of space.
Internal elasticization can be secured by reducing the functionality of the curing agent.
Although the long chain amino amides of low functionality comprising dimerized fatty acids, which have been in use for a long time and on a large scale, do offer a satisfactory combination of properties as flexible curina agents for epoxy resins, they cannot be used as desired in some areas.
German patent application DE-AS 21 52 506 describes curable synthetic resin ~ixtures consisting of (a~
certain glycidyl ethers and ~b) certain phenyl esters of carbamic acid formed from prepolymeric isocvanates and alkvl phenol~s, and (c) polyamines or polyamino amides. However, because of the high viscosities of their components, mixtures of carbamic acid phenyl esters and epoxy resins have a final viscosity that is too high for practical use.
The preparation of a mixture ready for use therefore requires the addition of a diluent. Another problem is that because of the widely differing equivalent weights of the resin and curin~ agent com~onents, rel~tivelv large proportions of resin (epoxy plus polyurethane~ must be mixed with relatively small pr~portions of curing agent, so that homo~enization is far from simple and requires great care, al~o because of poor miscibility ~ue to the difference in the viscosity of the resin and curing agent components.
According to German patent application DE-O~ 23 38 256, high molecular weight amine ter~inated polvether urethane ureas are~prepared by the reaction of prepolymers containing free isocvanate groups with amines in strongly diluted solutions and are then curea with epoxy resins.
Although the use of solvents, and especially of aromatic solvents, is d~leterious in practice and undesirable for both health and technical reasons~ it is essential in this process because gelling would otherwise occur. On the other hand, the ~riscosity of the solventless reaction products selectively obtained according to ~erman patent application D~-OS 23 38 256 is far too high for actual use.
German patent application DE-AS 2 418 041 describes a process for the production of elast,ici2ed molded parts and sheetlike articles in which certain epoxv compounds are re~cted with amino compounds obtained by the hydrolysis of certain prepolymeric ketimines or,enamines.
This process permits the production of durable thermoset resin (clurorners) which are resistan-t to chemicals and have improved properties. However, during the hydrolysis of -these compounds, ketones or aldehydes are libera-ted and rnust be removed.
Moreover, s-till further improvement oE -the flexihility of the cured products is desirable.
The object of -the present invention is to overcome these drawbacks and to provide curable synthetic resin mixtures which give coa-tings that have chemical resis-tance and good adhe-sion, adhesives, shee-tlike articles, sealing and caulking com-pounds, and molded ar-ticles possessing high impact strength and shock resistance as well as improved flexibility.
According to -the present invention there is provided the method of hardening a glycidyl compound having more than one epoxy group per molecule, which method comprises admixing wi-th said glycidyl compound an approximately s-toichiometric amount of an amino hardener which is a polyether urethane urea amine pre-pared by the reaction of: (1) a prepolymer having a blocked iso-cyanate groups, prepared by reacting a phenol or alkylphenol wi-th the reaction product of a polyether polyol or polythioether polyol with an excess of a polyisocyanate, with (2) a polyfunc-tional amino compound having (a) at least two reactive amino hydrogen atollls per molecule or (b) at least one reactive arnino hydrogen atom and at least one azornethine group per molecule, the amine then being liberated from the reaction product formed between (1) arld 2(b) by hydrolysis of the azome-thine group.

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The polyfunctional amine compouna used according to (A)(2) is prepared by the reaction of a polyfunckional masked aliphatic or cycloaliphatic isocyanate, preferably an isocyanate of an optionally substituted aliphatic or cycloaliphatic hydrocarbon, with an excess of at least one polyfunctional amino compound having two or more active amino hydrogen atoms per molecule, and/or with an amino compound having at least one reactive amino hydrogen atom and at least one azomethine group per molecule.
The compounds containing polyfunctional masked isocyanate groups which are used in this reaction may be products containing linear or branched reaction products containing hydroxyl or sulfhydryl groups and obtained by prior art processes by the reaction of polyalkylene polyether polyols and/or polyalkylene thioether polyols with polyisocyanates (including diisocyanates)in an NCO/OH(SH) ~ --I , - ~ ) ratio of from 1.5 to 2.5, followed by reaction of the terminal NCO group with the masking agents col~monly used in this field.
Suitable linear or branched polyols having an average molecular weight ranging from 150 to 10,000, preferably from 40Q to 5000, and more preferably of about 2000, are polyalkylene polyether polyols such as are ob~ained by the copolymerization, bulk copolymerization, or anionic polymerization of alkylene oxides, and in particular of ethylene oxide and propylene oxide, with di- or polyfunctional alcohols such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, and particularly alcohols with higher functionality, such as l,l,l-trimethylolethane, l,l,l-trimethylolpropane, glycerol, and 1,2,6-hexanetriol~
or with amines such as ethylene diamine and 1,6-hexamethylene diamine as starting components, or they may be made by cationic polymerization and copolymerization of cyclic ethers such as tetrahydrofuran, ethylene oxide, and propylene oxide with acidic catalysts, or by polycondensation of polycondensable glycols such as 1,6-hexanediol in the presense of acidic etherification catalysts.
Suitable polyalkylene thioether polyols are primarily the polycondensation products of thiodiglycol with itself and with diols and/or polyols, for example, 1,6-hexanediol, triethylene glycol,

2,~-dimethyl-1,3-propanediol and l,l,l-trimethylolpropane, ~) ) ~l2~

in the presence of acidic etherification catalysts such as phosphoxic acid and phosphorous acid.
A suitable polyacetal is the polycondensation product of formaldehyde and diols and/or polyols, for example diethylene glycol, triethylene glycol, 1,4-butanediol, 1,6-hexanediol, thiodiglycol, and l,l,l-trimethylolpropane, with acidic catalysts such as phosphoric acid and para-toluene sulfonic acid.
Further suitable polyol components are the addition pxoducts of compounds containing reactive multiple bonds and polyhydroxyl and sulfhydryl components such as polyisobutylenediol and polyisoprenediol as well as the corresponding compounds containing terminal SH groups. (See U.S. Patent 3,984,370).
These hydroxyl or sulfhydryl components are conventionally reacted with a polyfunctional isocyanate in an NCO/OH ratio ranging from 1.5 to 2.5, and preferably from 1.8 to 2.2, to give the corresponding prepolymeric compounds having terminal N~O groups.
Suitable aliphatic and cycloaliphatic polyisocyanates include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 2,4,4,(2,2,4)-trimethyl-1,6-diisocyanathohexane, l-methyl-2,4(2,6~-diisocyanatocyclohexane, methylenebis(4-cyclohexylisocyanate), and the isocyanate prepared by conventional methods from dimeric fatty diamine.

~2~3~6 The terminal NCO groups of the polyfunctional prepolymeric compounds are then reacted with the maskiny agents commonly used in this field in at least stoichiometric amounts at temperatures ranging from 50 to 120C, optionally by the use of catalysts.
In accordance with the invention, preferred masking agents are phenols and alkylphenols, wherein the by alkyl substituent has from 1 to 18 carbon atoms, for example, butylphenols, tetramethylbutylphenols, amylphenols, hexylphenols, heptylphe~ols, and especially 4-butylphenol mixtures of 4-nonylphenol isomers.
Suitable polyfunctional amino compounds to be used in the further reaction are diprimary, disecondary, and primary/secondary aliphatic, cycloali.phatic, heterocyclic, and araliphatic amines as well as their condensation products with carboxylic acids (polyaminoamides)~ These amines, which may be substituted and which have at least two active amino hydrogen atoms per molecule, are reacted in a ratio of amino group to masked NCO group ranging from 1.5 to 2.5, and preferably from 1.8 to 2.2, at temperatures ranging from 40 to 100C, and preferably from 60 to 80~C, with the component containing the aryl carbamate ester groups to give the corresponding prepolymeric amino compounds alone or in admixture.

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It is also possihle to use the amine component in larger amounts and to remove the excess on completion of the reaction, by distillation for example. ~he phenol component liberated during the reaction can remain in the reaction mixture.
In accordance with the invention, one or more of the following compounds are used as amino compounds:
(~ ) Amines of the formula R - NH - Rl - NH - R (I), wherein R is linear or branched alkyl having from 1 to 4 carbon atoms, or hydrogen, and Rl is linear or branched aliphatic, cycloaliphatic, or araliphatic hydrocarbon, which may be substituted, having from 2 to 20 carbon atoms, and in particular 1,2-diaminopropane, or Rl is the alkyl portion of a dimeric fatty diamine which may be interrupted by hetero atoms, and in particular oxygen atoms;
(~ ) an amine of the formula R2-(~3-NH ) -R3-R lII), wherein R is -N=C~R4)(R ), R3 is -CH2-CH2- and/or -CH2-C}~2-CH2- ~

R4 and R' are the same or different and arè -CH3, -CH2-CH3, or -C(CH3)3, and m is 1 or ~;

~ ~ - ~

( ~3 an aminP o~ the formula HN X - R5 (IIIl~
~ .
wherein R5 is H, or wherein R5 is -(C~k - R2 and k is 2 or

3, or wherein ~5 is (-CH2)h - ~ ~ (CH2)k -R6~

~nd R is -NHR or-R , h is 0, 1, 2, or 3, and X is C
or N; and/or (~) condensation products of these amines with carboxylic acids wherein, when an amine of formula ~II) is used with m being 1 and~or an amine of formula (III) is used with R6 being R2, the ratio of amino groups to carhamate aryl ester groups is 1:1, and wherein, when an amine of formulas (I) or (II) is used with m being 2, or an amine is used of formula (III) with R~ being -NHR, the ratio of amino groups to carbamate aryl ester groups ranges from 1.8:1 to 2:1, and wherein the amino group is liberated by hydrolysis from the compounds containing the group R2.
Examples of polyamines suitable for use in accordance with the invention are:
Ethylene diamine, diethyl.ene triamine, 1,2-diamino-propane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, 3-(n-isopropylamino)propylamine, hexapropyleneheptamine, l-cyclohexylamino-3-aminopropane, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, ~z~
2,~-diaminocyclohexane, 1,3-di(aminocyclohexyl)propane, N,N'-diethyl-1,3-diaminopropane, N,N'-diethyl-1,4-diaminOCyclOheX
ane, N-aminoethylpiperazine, N-aminopropylpiperazine, N-aminobutylpiperazine, 1,3-dipiperazinylpropane, 1,3-dipiperidylpropane, 3-(2-aminoe-thyl)-aminopropylamine, N,N'-bis-(3-aminopropyl)-ethylenediamine, a commercially available primary aliphatic polyoxypropylene diami.ne or triamine, phenlyenediamine, 4,4'-diaminodiphenylmethane, and other diamines such as 1,7-diamino-4-oxaheptane, 1,7-diamino-3,5-dioxaheptane, 1,10-diamino-4,7-dioxadecane, 1,10-diamino-4,7-dioxa-~-methyldecane, l,ll-diamino-6-oxaundecane, 1,11-diamino-4,8-dioxaundecance, 1,11-diamino-4,8-dioxa-5-methyl-undecane, l,ll-diamino-4,8-dioxa-5,6-dimethyl-7-propionyl-undecane, l-12-diamino-4,9-dioxadodecane, 1,13-diamino-4,10-dioxatridecane, 1,13-diamino-4,7,10-trioxa 5,8-dimethyltride-cane, 1,14-diamino-4,11-dioxatetradecane, 1,14-diamino-4,7,10-trioxate-tradecane, l,l6-diamino-4,7,10,13-tetrahexadecane, 1,20-diamino-4,17-dioxaeicosane, and especially hexa-methylenediamine, 2,2,~(2,4,4)-trimethyl-hexamethylenediamine and 3,3'dimethyl-4,4'-diaminodicyclohexylmethane, and particu-larly isophoronediamine (l-amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane), N-aminoethylpiperazine, 1,2-diaminopropane, methylpentamethylenediamine, xylylenediamine, or mixtures of these amines.
The polyaminoamides also used in accordance with the invention are condensation products o~ dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylenedicar-boxylic acid, decamethylenedicarboxylic acid, and -the dicar-boxylic acids obtained b~ carbonylation of unsaturated fattyacids and excess amines, such as the compo~nds recited above.
Polyaminoamides, and polyaminoamides containing imi-dazoline groups and based on monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid and the naturally occurring animal and vege-table fatty acids or thelr es-ters and the polyamines recited above, but especially polyalkylene polyamines such as diethylenetriamine, triethylene-tetramine, and tetraethylenepentamine, may also be used, either alone or in mixture.

iO The amines which are preferred in accordance with the invention are polyaminoamides and polyaminoamides contain-ing imidazoline groups comprising dimerized fatty acids and excess polyalkylene polyamines, which are used in ,7 the prior art as curing agents in the field of ~poxy resins, or their mixtures with the amines recited above.
Along with the hardening or curing agents recited above, which in accordance with the invention are preferred, the amine curing agents for epoxy resins commonly employed in this field may be used for modification.
The epoxy resins or glycidyl compounds ~B) which are also used in accordance with the invention are curable with these curing agents or with mixtures thereof when either hot or cold. They contain an average of more than one epoxy group in the molecule and are preferable glycidyl ethers of polyhydric alcohols, for example of glycerol or of neopentylglycol; of hydrogenated diphenylolpropane; or of polyhydric phenols for example of resorcinol; of diphenylolpropane; or of phenol-formaldehyde condensation products. The glycidyl esters of polyhydric carboxylic acids such as hexahydrophthalic acid or dimerized fatty acids may also be used. The epoxy values of these compounds are approximately between 0.2 and 0.7; preferably between about 0.4 and 0.7.
The use of liquid epoxy resins comprising epichlorohydrin and diphenylpropane having a molecular weight from 340 to 450 is particularly preferred.
Optionally, monofunctional epoxy compounds may be used to reduce the visco6ity of the mixtures and thus to improve their processability. Examples of these are ~2~ 6 aliphatic and aromatic glycidyl ethers such as butylglycidyl ether and phenylglycidyl ether, or glycidyl esters such as glycidyl acrylate, or epoxides such as styrene oxide.
In the formulation of a reaction mass for coating, adhesive or castin~ applications, the usual mineral and organic fillers, pigments, plasticizers, accelerators, other solvents commonly employed in the epoxy-resin ~ield, and still other additives may be used.
The curable r.nixtures in accoraance with the invention are ~uitable for coatings, adhesives, sheetlike articles, caulking and sealing compounds, and molded articles in all fields of application where good a~hesion, chemical resistance, high impact strength and shock resistance as well as improved flexibility and elasticitv are required, as in the filling ~f cracks and joints in the construction field, for example.
A better understandin~ of the present invention and of its many advantages will be had from the fol.lowing examples, giv~n by way of illustration~

A. PREPARATION OF P~I.YETHER llRET~ANF.
CARBAMIC ACID ARYL ESTERS
Exampl _ Preparation of a ~ifunctional polyether havin~ terminal carbamate (4-nonylphenyl ester~ groups ` (?

1000 g of a linear polypropylene glycol of OH
number 56.1 iMW=2000) were mixed with 222.3 g of isophoronediisocyanate. After the addition of 1.2 g of dibutyltin dilaurate, the ~ixture was heated to 75~C with vigorous stirring and held at tha~ temperature for 2.5 hours.
The reaction product had an isocyanate CnnteJIt of 3.4~.
0.3 g of zinc acetylacetonate and 215.7 ~ of a technical 4-nonylphenol mixture with branched nonyl radicals were added to the isocyanate prepolymer, cooled to 20 to 25 C. The mixture was then heated in two hours to 50 C
with stirring. ~he product then contained practically no isocyanate and had about 2.87% blocked NCO groups.
Example 2 P aration of a trifunctional olyether havinq terminal rep p carbamate 14-nonylphenyl ester) groups 1000 g o a branched trifunctional polypropylene glycol of OH number 35.6 (~=4700~ were mixed with 141 g of isophoronediisocyanate. After the addition of 1.2 g of dibutyltin dilaurate, the procedure of Example 1 was followed and a reaction product having an isocyanate content of 2.2% was obtaine~.
~~ 0.3 g zinc acetylacetonate and 131.1,g of a technical 4-nonylphenol mixture with branched nonyl radicals were added to the isocyanate prepolymer, cooled to 20 -to 25C.
The further procedure was as in Example 1, a product containing 1.95% blocked NCO groups and practically no isocyanate thus being obtained.

Preparation of a carbamate (p-tert. butylphenol) ester - Example 1 was repeated with the difference that 147.1 g of p-tert.-butyl-phenol were used as -the capping agent. The product then con-tained practically no isocyanate and had abou-t 3% blocked NCO
groups.

Preparation of a prepolymer with a difunc-tional poly-ether and TMDI - A prepolymer was formed between a difunctional polyether and 2,4,4 -(2,2,4)-trimethylhexamethylenediisocyanate ('~`M~L) by reacting 1,000 g of a linear polypropylene glycol hav-ing an O~ number o~ 56.1 with 210 g of TMDI as ln Example Atl).
The reaction product has an isocyanate content of 3.47 percent.
Following Example A(l), the corresponding carbamic acid ester was prepared with 215.7 g of 4-nonylphenol. The product shows practically no unreacted isocyana-te and has about 2.9 per-O~llt oE bLocked NCO groups.

., ~2~ 6 Example 5 Preparation of a prepolymer of polytetrahydrofuran and IPDI
250 g of polytetrahydrofuran having a molecular weight of about 2,000 and an OH number of 55.5 were reacted according to Example A~ 1) with 5~.35 g of isophorone diiso-cyanate IPDI. The reaction product has an isocyanate number of 38.8.
300 g of this reaction product were reacted for 2 hours at 50C. with 45.6 g of a technical 4-nonylphenol isomer mixture. Thereafter, the product contained practically no free isocyanate and contains about 2.52 percent of blocked NCO
groups.
Example 6 Preparation of a prepolymer of a linear polyglycol and IPD
1,000 g of a linear polyglycol, prepared by the copolymerization of propylene glycol with propylene oxide and ethylene oxide and having a molecular weight of about 2,000 and a OH number of 55, were reacted with 22.3 g of isophorone diisocyanate. After the addition of 1.2 g of dibutyltin dllaurate, the mixture was warmed to 75C with vigorous stir-rln~ and maintained at this temperature for 2.5 hours. The reaction has an isocyanate content of 3.4 percent.
0.3 g of zinc acetylacetonate and 215.7 g of a tech-nical 4-nonylphenol isomer mixture having branched nonyl groups were added to the isocyanate prepolymer after cooling the latter to 20-25C. Subsequently, the mixture was stirred for 2 hours at 50C. The product thereaf-ter contained practi-cally no isocyanate and contained about 2.87 percent of blocked NCO groups.
Example 7 Preparation of a prepolymer of polypropyle,ne ~lycol and XDI

1,000 g of a linear polypropylena glycol having a OH

~.

lZ~ 36 number of 56.1 were reacted with 188 g of xylylene diiso-cyanate (XDI) as in Example A(l). The reaction product has an isocyanate content of 3.53 percent.
By reaction with 215.7 g of 4-nonylphenol, the cor-responding carbamic acid ester was prepared. The product shows practically no isocyanate and contains about 2.98 per-cent of blocked NCO groups.
B. PREPARATION OF POLYETHER URETHANE UREA AMINES
Example 1 25.3 g of 1,2-diaminopropane were heated to 70C and 250 g of the product obtained under A, Example 1, were added through a dropping funnel over a period of 6 hours, the tem-perature being maintained at 70C. Excess 1,2-diaminopropane was then drawn off at 70C under a vacuum of 0.1 mm Hg. The reaction product had an amino group content corresponding to 35 mg KOH/g (theoretically 36.5).

Example 2 59.~ g of 1,2-diaminopropane were mixed with 1175 g of the product obtained under A, Example 1, and the mixture wa~ heated to 80C with vigorous stirring and held at that temperature for 3.5 hour~.
The reaction product had an amino group content corresponding to 34.7 mg KOH/g.
Example 3 26.9 g of trimethylhexamethylenediamine ~T~D) were reacted with 250 g of the product obtained under A, Example 1, as in Example 2~ The reaction product had an amino group content corresponding to 38 mg KOH/g.
Example 4 23.2 g of m xylylenediamine (XDA) were reacted with 250 g of the product obtained under A, Example 1, as in Example 2. The reaction product had an amino group con~ent corresponding to 39 mg KOH/g.
Example 5 29 g of isophoronediamine (IPD) were reacted with 250 g of the product obtained under A, Example 1, as in Exa~ple 2. The reaction product had an amino group content ~orresponding to 39 mg KOH/g.
F.xample h 33.7 g of p,p'-diaminodiphenylmeth~ne (~SDA) were mixed with 250 g of the product obtained under A, Example 1, and the mixture was heated to 100 C with vigorous stirring and held at that temperature for lÇ hours. The reaction product had an amino group corresponding to 37 mg KOH/g.
Example 7 23.4 9 of 1,2-diaminopropane were reacted with 340 g of the product obtained under A, Example 2, as in Example 1. The reaction product had an amino group content corresponding to 22 mg KOH/g.
Example 8 7.19 g of piperazine were reacted with 180 g of the product obtained undex A, Example ~, as in Example 2.
The reaction product had an amino group content corresponding to 26 mg KOH/g.
Example 9 30 y of 1,2-diaminopropane were reacted according to Example B(l) with 250 g of the product prepared above according to A(4).
The reaction product has a content of amino groups corresponding to 37.0 mg KOH/g Itheory = 37.3).
Example 10 35 g of 1,2-diaminopropane were reacted according to B(l) with 250 g of the product prepared under A(7~.
The reaction product has a content of amino groups corresponding to 38.0 mg of KOI~/g (theory = 37.~).

~2~
Example 11 3~5.6 g of the product prepared according to A(5) were reacted with 30.6 g of 1,2-diaminopropane according to Example B(1).
The reaction product has a content of amino groups corresponding with 26.9 mg KOH/g.
Example 12 293.4 g of the product prepared according to A(l) were reacted with 80 g of an aminoamide containing imidazoline groups, comprising fatty acid and triethylenetetramine and having an amine number of 420.
The reaction product has a content of amino groups corresponding with 58 mg of XOH/g.
C. PREPARATION OF ELASTICIZED EPOXY-RESIN MASSES
Example 1 85 parts by weight of an epoxy resin based on bisphenol A and epichlorohydrin and having an epoxy value of 0.53 and a viscosity of about Pa.s at 25C were diluted with 15 parts by weight of a glycidyl ether based on C12 to C14 f~tty alcohols and epichlorohydrin and having an epoxy value of about 0.35 and a viscosity of about mPa.s at 25C. The latter is a reagent and also functions as a diluent viscosity regulator.

~ ! `

420 parts by weight of a polyether urethane urea amine according to B, Example 1, as w~ll as 28 parts by weight of 2,4,6-tris-(dimethylaminomethyl)phenol (DMP) and 1.6 parts by weight of 4 nonylphenol lNP) were added. The DMP functions as an accelerator. The NP is both a viscosity regulator and an accelerator.
This epoxy resin mass was cast into plates 4 mm thick and allowed to cure at 23C. The increase in hardness was determined (Shore hardness in conformity with DIN 53505) and, after 7 days' curing at 23~C, also the tensile strength, the elongation ~DIN 53455), and the crack propagation resistance ~DIN 53505).
The fully cured mass was clear/transparent and nearly nontacky on the surface.
The following resins were prepared and tests thereon were conducted as described in Example 1. The m~surements presented in the following Table are average values from three tests.
Example 2 100 parts by weight of the epoxy mixture of Example 1 were mixed with 372 parts by weight of the amine of B, Example 3, and with 16 parts by weight of DMP and 29 parts by weight of NP.

t ~%~

Example 3 100 parts by weight of the epoxy resin mixture of Example 1 were mixed with 359 parts by weight of the amine of B, Example 4, and with 24 parts of DMP and 28 parts of NP.
Example 4 30 parts by weight of an epoxy resin based on bisphenol A and bisphenol F in a weiyht ratio of 70:30 and epichlorohydrin of an epoxy value of 0.54 and a viscosity of 7 mPa.S at 25C were diluted with 20 parts by weight of dibutylphthalate (as a so-called "plasticizer") and then mixed with 300 parts by weight of the amine of Example B6, as well as with 20 parts of DMP and 32 parts of NP.
Example 5 85 parts by weight of the epoxy resin of Example 1 were diluted with 15 parts of the glycidyl ether formed from neopentyl glycol and epichlorohydrin, said ether having an epoxy value of 0.68 and a viscosity of 20 mPa.s at 25C~
This was then mixed with 356 parts by weight of the amine of B, Example 5, and with 24 parts of DMP and 29 parts of NP.
Example _ 100 parts by weight of the epoxy resin mixture of Example 1 were cured with 539 parts o the amine of B, Example 7, and with 43 parts of DMP and 63 parts of NP.

Example 7 lO0 parts by weight of the epoxy resin mixtur~ of Example 5 were reacted with 1062 parts by weight of the amine of B, Example 8, and with 71 parts of DMP and 90 part-of NP.
Example 8 lO0 parts by weight of the epoxy resin of Example C(l) were combined with 272 parts by weight of the amine from Example B(l~, 4.7 parts by weight of isophorone diamine, 18.3 parts by weight of DMP, and 11.4 parts by weight of NP. After dilution with 44 parts by weight of methylene chloride/i-propanol, (l/l), the mixture was homogenously combined with 110 parts by weight of calcite filler having an average particle size of approximately 20 microns.
Example 9 100 parts b~ weight of the epoxy resin mixture of Example C(l) were mixed with 155 parts by weight of the amine from Example B(l~, 30.5 parts by weight of NP, and 7 parts by weight of DMP~ 58 parts by weight of an aminoamide imidazoline curing agent comprising a dimerized tall oil fatty acid and diethylene triamine ~having an amine number about 280, an amine equivalent weight of about 170, and a viscosity of 25C of about 28~9 mPa.s) were added thereto.

The mixture was diluted with 49 parts by weigh-t o:E
methylene chloride/i-propanol (1/1) and then filled with 90 parts by weight o~ calcite (around 20 microns average par-ticle size) and 10 parts by weight oE tl-tanium dioxide-ru-tile.
Example 10 100 parts be weight of a plgmented synthetic resin mass as in Example C 8) were combined with 1 part by weight of pyrogenic silicic acid subsequent to thixotrpping.
Comparative Example 100 parts by weight of the epoxy mixture of Example 1 were mixed with 400 parts by weight of an aryl carbamate ester according to A, Example 1. A mixture of 20 parts by weight of 1,2-diaminopropane, 28 parts of DMP and 1.6 parts NP
was added to this as a curing-agent component.
The fully cured material had a milky opacity and was very tacky on the surface.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. The method of hardening a glycidyl compound having more than one epoxy group per molecule, which method comprises admixing with said glycidyl compound an approximately stoichio-metric amount of an amino hardener which is a polyether urethane urea amine prepared by the reaction of (1) a prepolymer having blocked isocyanate groups, prepared by reacting a phenol or alkyl-phenol with the reaction product of a polyether polyol or poly-thioether polyol with an excess of a polyisocyanate, with (2) a polyfunctional amino compound having (a) at least two reactive amino hydrogen atoms per molecule or (b) at least one reactive amino hydrogen atom and at least one azomethine group per mole-cule, the amine then being liberated from the reaction product formed between (1) and 2(b) by hydrolysis of the azomethine group.

2. The method as in claim 1, wherein said mixture additionally comprises at least one member selected from the group consisting of fillers, pigments, accelerators, viscosity regulators, and other additives.

3. The method as in claim 1, wherein said blocked pre-polymer ester is the reaction product of (A) a polalkylene polyether polyol having an average molecular weight between 150 to 10,000 with an excess of (B) a polyfunctional aliphatic or cycloalipha-tic isocyanate, the ratio of NCO groups to OH groups being be-tween 1.5 and 2.5, followed by further reaction of the resulting prepolymer containing NCO groups with (C) a phenol, the phenol/
NCO ratio being between about 1.0 and about 1.5.

4. The method as in claim 3, wherein said polyol has an average molecular weight between 400 and 5000.

5. The method as in claim 3, wherein said polyol has an average molecular weight of about 2000.

6. The method as in claim 3, wherein said isocyanate is isophorone diisocyanate.

7. The method as in claim 3, wherein said phenol is a para-noylphenol or a para-butylphenol.

8. The method as in claim 1, wherein said polyfunc-tional amino compound is selected from the group consisting of (A) amines of the formula wherein R is linear or branched alkyl having from 1 to 4 carbon atoms, or is hydrogen, and R1 is linear or branched aliphatic, cycloaliphatic, or araliphatic hydrocarbon, which may be substi-tuted, having from 2 -to 20 carbon atoms, or is the alkyl portion of a dimeric fatty diamine which may be interrupted by hereto atoms; (B) amines of -the formula R2 - (R3 - NH -)m - R3 - R2 wherein R2 is -N=C(R4)(R'4), R3 is -CH2-CH2- or -CH2-CH2-CH2-, R4 and R'4 are the same or different and are -CH3, -CH2CH3, or -C(CH3)3, and m is 1 or 2; (C) amines of the formula wherein R5 is H, or wherein R5 is -(CH2)k -R2 and k is 2 or 3, or wherein R5 is (-CH2)h - (CH2)k -R6, R6 is -NHR or -R2, h is 0, 1, 2 or 3, and X is C or N; (D) con-densation products of an amine (A) - (C) with a carboxylic acid wherein, when an amine (B) is used with m = 1 or an amine (C) is used with R6 = R2, the ratio of amino hydrogen atoms to carbamate aryl ester groups is 1:1, and wherein, when an amine (A) or (B) is used with m = 2, or an amine (C) is used with R6 = NHR, the ratio of amino groups to carbamate aryl ester groups is from 1.8:1 to 2:1, an amino group being liberated by hydrolysis from compounds containing a group R2.

9. A method for making a polyether urethane urea amine having two or more reactive amino hydrogen atoms per molecule, which method comprises reacting (1) a prepolymer having blocked isocyanate groups, prepared by reacting a phenol or alkylphenol with the reaction product of a polyether polyol or polythioether polyol with an excess of a polyisocyanate, with (2) a polyfunc-tional amino compound having (a) at least two reactive amino hydrogen atoms per molecule or (b) at least one reactive amino hydrogen atom and at least one azomethine group per molecule, the amine then being liberated from the reaction product formed between (1) and 2(b) by hydrolysis of the azomethine group.

10. A method as in claim 9, wherein said amino com-pound is present in an excess such that the ratio of reactive amino hydrogen atoms to blocked isocyanate groups is from about 2:1 to about 4:1.

11. A method as in claim 9, wherein said amino com-pound is present in an excess such that the ratio of reactive amino hydrogen atoms to blocked isocyanate groups is about 2:1.

12. A polyether urethane urea amine made by the method of claim 9.