CA1330143C - Modified epoxide resins - Google Patents

Abstract

Modified epoxide resins Abstract Compositions containing A) a copolymer based on at least one 1,3-dieneand at least one polar, ethylenically unsaturated comonomer and B) a com-pound of the formula I

(I) in which m is 1 or 2, n is Z to 6, R1 is the n-valent radical of an ela-stomeric prepolymer which is soluble or dispersible in epoxide resins, X
and Y independently of one another are -O- or -NR3-, it being necessary for one of these groups to be -NR3-, R2 is an m+1-valent radical of a polyphenol or aminophenol and R3 is hydrogen, C1-C6alkyl or phenyl, are described.

Compounds containing the components A) and B) as well as an epoxide resin C) are also described.

The cured products are distinguished by a high peel strength and high resistance to crack propagation. The curable compositions can be em-ployed, for example, as structural adhesives.

Description

K-16658/1+2/+

Modified epoxide resins . ., --The present lnvention relates to mixtures of specific diene copolymers and phenol-terminated polyurethanes or polyureas, to mixtures of this type containing epoxide resins and/or adducts of epoxide resins with the diene copolymer and/or the polyurethane or the polyurea, to the cross-linked products formed from these mixtures, to a process for curing the mixtures and to the use of the multi-component mixtures as adhesives, in particular as structural adhesives.
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Mixtures of epoxide resins and phenol-capped polyurethanes are known from DE-A 2,152,606. The polyurethanes are obtained by reacting prepolymer diisocyanates with substituted or unsubstituted monophenols. The pro-ducts no longer contain free, phenolic hydroxyl groups. They are com-bined with epoxide resins and polyamine curing agents to give curable coating agents which are distinguished by special elasticity. Water-soluble or partly water-soluble, phenol-terminated polyurethanes which are derived from water-soluble or partly water-soluble polyalkylene gly-cols, diisocyanates and bisphenols are known from US-A 4,423,201. mese compounds are reacted with epoxide resins and phenols to give water-dis-persible epoxide resins. me modified epoxide resins can be employed as coatlng agents. Epoxide compositlons whlch are stable on storage and whlch contain a polylsocyanate blocked by means of a monophenol or poly- -phenol are known from IIS-A 3,442,974. No phenol-capped polylsocyanates which possess elastomeric properties are described. Hydroxyphenylure-thanes which can be employed as antioxidants or as intermediates for the preparation of polycondensates or polyadducts are also known from EP-A
247,476.

It is also known that epoxide resins can be modified by adding copolymers based on butadiene and acrylonitrile or by adding adducts of such copoly-mers with epoxlde resins.
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In general, additives of this type effect an increase in the impact - -.
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.-.:. - -strength and the flexlbility of the cured product. However, the peel strength generally leaves something to be desired. As a rule, the ten-sile shear strength and the glass transition temperature are reduced by the incorporation of such polymers.

Combinations of lmpact strength modifiers which, when mixed wlth epoxide resins, effect a significant increase in peel strength, have a reduced tendency to crack propagation and make possible high peel strength with-out loss of tensile shear strength have now been found. -Furthermore, these modifiers make it possible, depending on the resin formulation, to prepare elastic products having a high peel strength and a low glass transition temperature or high-strength products having a ~ -high glass transition temperature and a high peel resistance; the high-strength products are distinguished by high values of toughness to cracklng, and the crack propagation is reduced markedly, even at very high impact load, similar to shock.
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-~ As a rule, the prevlously known products based on epoxide resins and , ~ .
~ butadiene copolymers do not contain a high proportion of the component --~ imparting flexibility, slnce mixtures having a high content of flexi- bilizer can only be cured inadequately or not at all.
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It has now been found that mixtures of epoxide resins and high propor-tions of butadlene copolymers in combinatlon with speclfic phenol-terminated polyurethanes or polyureas can be cured, and highly flexible products can thus be prepared.

The present invention relates to compositions containing A) a copolymer based on at least one 1,3-diene and at least one polar, ethylenically ~ -unsaturated comonomer, and B) a compound of the formula I

Rl ~ x ~ -y-R2-~oH)m ] (I) in which m ls 1 or 2, n is 2 to 6, Rl is the n-valent radical of an elas-to~eric prepolymer, after the removal of the terminal isocyanate, amino .

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-_ 3 _ 1330143 or hydroxyl groups, which is soluble or dispersible in epoxide resins, X and Y independently of one another are -O- or -NR3-, it being necessary for at least one of these groups to be -NR3-, R2 is an m+l-valent radi-cal of a polyphenol or aminophenol after the removal of the phenolic hydroxyl groups and optionally the amino group, and R is hydrogen, Cl-C6alkyl or phenol.

Examples of 1,3-dienes for the preparation of component A) are butadiene, isoprene and chloroprene. Copolymers based on butadiene are preferred.

Examples of polar, ethylenically unsaturated comonomers for the prepara-tion of component ~) are acrylic acid, methacrylic acid, esters of acry-lic or methacrylic acid, for example the methyl or ethyl esters, amides of acrylic or methacrylic acid, fumaric acid, itaconic acid, maleic acid or esters or half-esters thereof, for example the monomethyl or dimethyl ~
esters, or maleic anhydride or itaconic anhydride; vinyl esters, for ~-example vinyl acetate, polar styrenes, such as styrenes chlorinated or brominated in the nucleus, or, in particular, acrylonitrile or meth- -~
acrylonitrile. -~
,-:-; :: -,.:- .
Besides polar, ethylenically unsaturated comonomers, component A) can also contain other non-polar, ethylenically unsaturated comonomers.
Examples of these are ethylene, propylene or, in particular, styrene or substituted styrenes, such as vinyltoluene. ,j :
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Component A) can be statistical copolymers, block copolymers or graft ~;
copolymers.
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This component can be solid/ in particular pulverulent, or, preferably, can be liquid. It can also be thermoplastics, thermoplastic elastomers or elastomers.
-The proportion of the comonomers in component A) can vary within wide ranges. This component is so chosen that an elastomer phase i9 formed ~-in combination w1th component B) and, if appropriate, an epoxide resin --C). These can be homogeneous or heterogeneous systems. ! ' . ' '~.
. ~ ' , ~ ' n ~ 4 - 1 33 0 1 4 3 An elastomer phase can already be present in component A), for example if a polybutadiene graft copolymer is used; the elastomer phase can, however, only be formed by selecting suitable components A), B) and, if appropriate, C).

If heterogeneous systems are desired, the components are, as a rule, selected in such a way that the difference between the solubility para-meters of A) and/or B) and that of C) is between 0.2 and 1.0, preferably between 0.2 and 0.6. These selection criteria are described, for exam-ple, in C.B. Bucknall, "Toughened Plastics", Chapter 2, Applied Science Publishers Ltd., London 1977.

Preferred components A) are copolymers based on butadiene/acrylonitrile, butadiene/(meth)acrylic acid esters, butadiene/acrylonitrile/styrene graft copolymers (ABS), especially ABS powders, and butadiene/methyl methacrylate/styrene graft copolymers (MBS) .

Components A) which are particularly preferred are copolymers which can be obtalned by the graft copolymerization of polar, ethylenically un-saturated comonomers onto polybutadiene microgels.
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Components A) which are very particularly preferred are liquid butadiene -~
copolymers with polar, ethylenically unsaturated comonomers, in parti- ~-cular liquld butadlene/acrylonltrlle copolymers.
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The molecular weights of these preferred llquld butadiene copolymers are ~ preferably 500-5,000, in particular 1,000-3,000. ~ -.~ , Other components A) which are very particularly preferred are butadiene/
i~ acrylonitrile copolymers having functional groups which are reactive to-wards epoxide resins.

; Examples of such copolymers are acrylonitrile/butadiene rubbers contain-lng carboxyl or hydroxyl or amine groups, for example compounds of the type of Hyca ~ made by Goodrich.

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- 5 - 13301~3 Preferred types of such rubbers contain the structural elements of the following formulae IIa to lId and the end groups Q
-CHz-CH=CH-CH2- (IIa), -CH2-~H- (IIb), -CH2-~H- (IIc) -CHz- - (IId), ~H ~ ~b in whlch Ra is hydrogen or methyl, Rb is -COOH, -COORC or -CONH2, RC is ~ -~
an aliphatic radical, preferably methyl, and Q is selected from the group consisting of -R-COOH, -R-OH and -R-CO- ~ ~ H, in which R is an alkylene radical; the proportion of the radicals IIa and IIb is prefer-ably 5-50% by weight, the proportion of the radical lc is preferably 5-50% by weight, and the proportion of the radical IId is preferably 0-30%
by weight, in the case of radicals having free carboxyl groups preferably ~' 0-10% by weight, the quantity data referring to the total amount of the -radicals IIa, IIb, IIc and, if appropriate, IId.

Component A) can also be employed in the form of an adduct, onto an epoxide resin, of a butadiene/acrylonitrile copolymer having functional --groups which are reactive towards epoxide resins.
' '~'~' ' ' : ''' The preparatlon of such adducts is effected in a manner known per se by -heating the reactive acrylonitrile/butadiene rubber and the epoxide resln, if appropriate together with a catalyst, so that a fusible, but still curable, precondensate is formed. -The catalyst used is, for example, triphenylphosphine, tertiary smines, ~;
quaternary ammoniu~ or phosphoniu~ salts or chromium acetylacetonate.

The invention also relates to compositions containg A) an adduct, onto an epoxide resin, of an acrylonitrile/butadiene rubber having functional groups reactive towards epoxide resins, and B) a phenol-terminated comr pound of the formula I, as defined above.

Component B) is a selected polyurethane or a selected polyurea derived from ~ specific prepolymer. The term "elastomeric prepolymer radical ':
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i~- , - , . ,,. , ;, . ~ . ... ..

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133~1~3 is to be understood, within the scope of this description, as meaning a radical, terminated with n-isocyanate, n-amino or n-hydroxyl groups, of a prepolymer which, after these groups have been capped, results in a compound of the formula I uhich, in combination with the diene component A) and epoxide resins C), produces, after curing, an elastomer phase or a mixture of elastomer phases. These can be homogeneous or heterogeneous combinations of components A), B) and C). The elastomer phase(s) is(are), as a rule, characterized by a glass transition temperature below 0C. The term prepolymer which is soluble or dispersible in epoxide resins' is to be understood, within the scope of this description, as meaning a radical, terminated by n-isocyanate, n-amino or n-hydroxyl groups, of a prepolymer which, after these groups have been capped, -results in a compo-md of the formula I which is soluble, or is dis- -persible without further assistance, for example emulsifiers, in an epoxide resin C) or in a co~bination of an epoxide resin C) and a diene copolymer A); in the course of this, therefore, a homogeneous phase is formed or at least no macroscopic phase separation of one of the com-ponents A), B) or C) or of a mixture of the said components takes place.
In the case of heterogeneous systems, the difference described above in the solubility parameters of A) and/or B) and/or C) should, as a rule, be maintained.

The solubility or dispersibility of B) in the combination of A) and C) i8 effected primarily by the selection of suitable prepolymer radicals . Examples of suitable radicals are given later in the text in the preparation of the component B).
The compound of the formula I is preferably a compound insoluble in water. This is to be understood, within the scope of this description, as meaning a compound which dissolves in water to the extent of less than SX by weight, preferably less than 0.5% by weight, and which, when stored in water, absorbs only a small amount of water, preferably less than 5X by weigjht, in particular less than 0.5X by weight, or which, in the course thereof, exhiblts only a slight swelling.

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- 7 - 133~1~3 ~

The prepolymers on which Rl is based have, as a rule, molecular weights(n~mber average) of 150 to 10,000, preferably 1,800 to 3,000.

The average functionality of these prepolymers is at least two, prefer- -~
abiy 2 to 3 and particularly preferably 2 to 2.5. ;

The term "elastomeric polyurethane" of "elastomeric polyurea" is known per se to those skilled in the art (cf. C. Hepburn: "Polyurethane Elastomers", Applied Sclence Publishers, London 1982). ~ -~

In general, elastoneric polyurethanes or polyureas contain rigid and - -flexible components (hard and soft segments).

The component B) can be liquid or thermoplastic, phenol-terminated, poly-urethanes or polyureas of the formula I. Compounds having a softening point below 80C, preferably below 40C, are preferred. ~

Component B) can also be employed as an adduct of a phenol-terminated - -polyurethane or polyurea of the formula I onto an epoxide resin. Adducts of this type can be prepared in the manner described above. ~

For highly flexible systems, adducts of such polyurethanes or polyureas ~ - ' containing glycidyl ethers of aliphatic diols, such as 1,4-butanediol or ~ -1,6-hexanediol, are preferred. ~
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Suitable components B) can be essentially linear or are branched types. ~ ;
The degree of crosslinklng is so selected that the polymer does not form a macroscopic gel. This will, as a rule, be the case if component B) is soluble or at least dispersible in a polar organic solvent or in an epoxide resin. ~' The compounds of the formula I in which X is -NR3- and Y is -NR3- or, in particular, -0-, can be prepared by various routes depending on the nature of the prepolymer on which Rl i8 based.

In the case of prepolymer isocyanates, they can be prepared by reacting ':
' '' compounds of the formula IIIa with polyphenols or aminophenols of the formula IVa (process a) Rl-~NCO)n (IIIa), H-Y-R2-~OH)m (IVa);

polyureas of the formula I in which X is -NR3- and Y is -NR3- can also be prepared by reacting prepolymer amines of the formula IIIb with ure-thanes of the formula IVb (process b) Rl-~NR3H)n (IIIb), Rll ~ -NR3-R2-~oH)m (IVb);
compounds of the formula I ln whlch X is -NR3- and Y is -NR3- or -O- and which have ortho-phenols or peri-phenols or ortho-aminophenols or peri-aminophenols as end groups, can also b~ prepared by reacting compounds of the formula IIIb with cyclic carbonates or urethanes of the formula IVc (process c) - Rl-tNR3H)n (IIIb), ~ 12 (IVc);
in these formulae IIIa, IIIb, IVa, IVb and IVc the radicals Rl, R2, R3 and Y and also the indices m and n are as defined earlier in the text, Rll is a radical which acts as a detachable group, for example alkyl or aryl, especially cl-c6alkyl or phenyl, and R12 is a divalent, carbo-cyclic-aromatic radical which has one of the meanings defined for R2 and on which the groups -O- and -Y- are in each case located in the ortho- ~ -position or peri-position relative to one another.

The compounds of the formula I in which X is -O- and Y is -NR3- can be obtained analogously to the processes described in EP-A 247,467.
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This i8 effected, for example, by reacting an elastomeric and hydroxyl-i ~ terminated prepolymer of the formula V which is soluble or dispersible 1 - in epoxide resins with an amount, corresponding to the OH content of the prepolymer, of a carbamate of the formula IVb, as defined above, Rl-~OH)n (V), Rll ~ -NR3-R2-~oH)~ b); ~ ~;
;~ in these formulae the raticals Rl, a2, R3 and Rll and also the lndices and n are as defined above.
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9 1330143 - -~ ~

In another embodiment the prepolymer of the formula V can first be re-acted with an amount of phosgene corresponding to the OH content, and -the resulting chlorocarbonyloxy derivative can then be reacted with a phenol or aminophenol of the formula IVa. -:, . , , ~.:. '- -' The radical R2 is derived, in general, from phenols or aminophenols having a mononuclear or polynuclear, carbocyclic-aromatic radical. ~ -Phenol radicals or aminophenol radicals having several carbocyclic-aromatic radicals can be condensed or, preferably, attached via bridge members.
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Examples of phenols or aminophenols having condensed radicals are dihy-droxynaphthalenes or dihydroxyanthracenes or aminonaphthols.
. .
Preferred radicals R2 are derived from bisphenols of the formula VI
HO ~ ~ OH (VI) ~ -(~ )p (Rs )q in which Z is a direct C-C bond or a bridge member selected from the group consistlng of -CR6R7-, -O-, -S-, -SO2-, -CO-, -COO-, -Co~R3- and -SiR9R10-, R4 and R5 independently of one another are Cl-C20alkyl~
C2-C6alkenyl~ C2-C6alkinyl or halogen, p and q independently of one another are O, 1 or 2, R6, R7 and R8 independently of one another are hydrogen, -CF3 or Cl-C6alkyl, or R6 and R7, together with the common C atom, form a cycloaliphatic radical having 5-12 ring C atoms, and R9 ;;
and R10 are Cl-c6alkyl.

The radicals R2 which are particularly preferred are derived from bis-phenols of the formula VI in which the hydroxyl groups are attached in ~ -the 4,4'-position, especlally the derivatives in which p and q are 1 and R4 and R5 are allyl.

other radicalQ R2 which are particularly preferred are derived from bis-phenols of the formula VI in which Z i~ selected from the group consisting of -CH2-, -C(CF3)2-, -O-, -S02-, a direct C-C bond and, espe-clally, -C(CH3)2-, p and q are each O or 1 and R4 and R5 are Cl-C6alkyl, C2-C6alkenyl, particularly allyl, or C2-C6alkinyl, particularly pro-pargyl.
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Other preferred radlcals R2 are derived from mononuclear aminophenols, for example 2-, 3- or 4-aminophenol, or from mononuclear polyphenols, for example resorcinol, hydroquinone or pyrogallol.

Radicals R2 whlch are particularly preferred are derived from blsphe- -nols; examples of these are 4,4'-dihydroxybiphenyl, bis-(4-hydroxyphe-nyl) ether, bis-(4-hydroxyphenyl) sulfone, bis-(4-hydroxyphenyl)-methane, 2,2-bis-(4-hydroxyphenyl)-propane and the corresponding 3,3'-di~ethyl, 3,3'-dinonyl, 3,3'-diallyl, 3,3'-dichloro, 3,3'-dibomo and 3,3',5,5'-tetrabromo derivatlves of these compounds.

If R4 or R5 are Cl-C20alkyl, they are linear or branched radicals.

Examples of these are methyl, ethyl,-n-propyl, isopropyl, n-butyl, iso-butyl, tert.butyl, n-pentyl, n-hexyl, 2-ethylbutyl, n-heptyl, n-octyl, ~;
2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n- ; ~`
hexadecyl, n-octadecyl or n-eicosyl.

R4 and R5 are preferably Cl-c6alkyl~ partlcularly preferably linear `- -Cl-C6alkyl and very particularly pr-ferably ethyl.

If any radicals are C}-C6alkyl, they are preferably linear ratlcals, l.e. methyl, ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl, but very pattlcularly methyl.

Ex a ples of R4 and R5 a8 C2-c6alkenyl are vlnyl, allyl, l-propenyl, l-butenyl, l-pentenyl or l-hexenyl. Vlnyl, l-propenyl and allyl are preferred, 811yl beln~ very particularly preferred.

Exa~ple8 of R4 and R5 as C2-C6alklnyl are ethinyl, propargyl, 1-butinyl, l-pentinyl or l-hexinyl. Propargyl is preferred. ;~

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- 11 - 1~301~t~ ;

If R4 and R5 are halogen, they can be fluorine, chlorine, bromine or iodine. Chlorine or bromine is preferred, particularly bromine.
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¦ Compounds of the formula VI having alkyl or alkenyl substituents are pre-ferably used if the composition according to the invention is intended to have a high adhesion to oily steel.

Halogen-containing compounds of the formula VI generally increase the flame resistance.
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If R6 and R7, together with the common C atom, form a cycloaliphatic radical, this is, for example, a cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene or cyclododecylidene radical. Cyclo-hexylidene and cycLododecylidene are preferred.

R3 is preferably hydrogen.

The isocyanate of the formula IIIa is either a prepolymer al) derived from the addition of a polyisocyanate, preferably a diisocyanate Or tri-isocyanate and very particularly preferably a diisocyanate, onto a pre-polymer polyhydroxyl or polysulfhydryl component or onto a mixture of such prepolymer components, if appropriate in combination with chain lengtheners (short-chain polyhydroxyl, polysulfhydryl or polyamine com-pounds), or a prepolymer polyisocyanate a2) derived from a prepolymer polyamlne of the formula IIIb, especially from a prepolymer polyether-amine.

Prepolymer components for the preparation of al) can be condensation or addition polymers which can, if desired, contain grafted-on l-olefins, it being possible for the said l-olefins to contain not only non-polar ;
groups, but also polar groups, such as nitrile, ester or amide groups.
Examples of polymers are polyesters, polyethers, polythioethers, poly-acetals, polyamides, polyester-amides, polyurethanes, polyureas, alkyd resins, polycarbonates or polysiloxanes, provided that these compounds are hydroxyl-terminated oe sulfhydryl-termlnated, result in compounds of the formula I which are soluble or dispersible in epoxide resins, and -~

. ., .:.

- 12 ~ 3 0 1 3 impart elastomeric properties according to the above definition to these resins. ~

Polyethers or segmented prepolymers containing polyether segments, such as polyether-amides, polyether-urethanes and polyether-ureas, are pre-ferred.

These compounds are known to those skilled in the art in the field of polyurethane chemistry as components for the synthesis of polyurethanes.
They can be linear or branched; linear types are preferred. Preferred synthesis components for prepolymers al) are hydroxyl-terminated pre-polymers having average molecular weights (number average) of 150-lO,000, ~ -very particularly 500-3,000. -~

In addition to the hydroxyl-terminated or sulhydryl-terminated prepoly-mers, it is also possible for chain lengtheners to be present in the pre-paration of the prepolymer polyisocyanates al).

Monomers of this type are preferably difunctional or trifunctional.

If trifunctional or polyfunctional hydroxyl-terminated or sulfhydryl-terminated prepolymers or trifunctional or polyfunctional chain length~
eners are used for the preparation of the component al), the synthesis ~ ~ ;
components should be selected in such a way that an adtuct al) which is soluble or at least swellable in organic solvents is formed. ;- -When polyfunctional synthesis components are used, the degree of cross- -linking can be regulated in a manner known per se by means of the nature and,ratios of these components. It is also possib}e to vary the elasto- ;
mer properties in a manner known per se by means of the degree of cross-linklng.

us, lf difunctlonal prepolymers or trlfunctional or polyfunctional chaln lengtheners are employed, as a rule only a small proportlon of the polyfunctional component will be employed, whereas, if difunctional and trlfunctlonal or polyfunctlonal prepolymers are combined, as a rule a ~ ~
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1 ~ :-- 13 - 1 ~3O1~J3 . :;
larger amount of the polyfunctional chain lengthener can be present with-out excessive crosslinking taking place. m e degree of crosslinking will also depend on the functionality of the polyisocyanate. Thus, if tri-functional or polyfunctional, hydroxyl-terminated or sulfhydryl-terminated synthesis components are present, diisocyanates will, as a -rule, be employed, whereas, if difunctional, hydroxyl-terminated or sulf- ;
hydryl-terminated synthesis components are used, polyfunctional iso-cyanates will also be used. Examples of prepolymer synthesis components for the preparation of polyisocyanates al) are hydroxyl-terminated poly-ethers, in particular polyethers which result in water-insoluble com-pounds of the formula I.

These include, for example, the polyalkylene ether-polyols whlch are obtained by anionic polymerization, copolymerization or block copolymeri-zation of alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxlde, uslng difunctional or polyfunctional alcohols, such as 1,4-butanediol, l,l,l-trimethylolethane, 1,1,1-trimethylolpropane, 1,2,6-hexanetriol, glycerol, pentaerythritol or sorbitol, or using amines, such as methylamine, ethylenediamine or 1,6-hexylenediamine, as initlator com-ponents, or by cationic polymerization or copolymerization of cyclic ethers, such as tetrahydrofuran, ethylene oxide or propylene oxide, uslng ~ -acld catalysts, such as BF3.etherate, or by polycondensatlon of glycols whlch can be sub~ected to polycondensatlon with the elimlnation of water, such as 1,6-hexanedlol, ln the presence of acid etherification catalysts, ! ~'~
such as p-toluenesulfonlc acld. lt 18 also possible to use oxalkylatlon products of phosphorlc acid or phosphorous with ethylene oxide, propylene oxide, butylene oxide or styrene oxlde.

Other preferred hydroxyl-terminated polyethers contain grafted-on 1-ole- ~-flns, such as acrylonitrile, styrene or acrylic acid esters. In this case the proportlon by weight of the graft component ls, as a rule, 10- ~;
50%, particularly 10-30%, relative to the amount of polyether employed.
. -Other examples of prepolymer synthesis co~ponents for the preparatlon of polylsocyanates al) are hydroxyl-termlnated polyester-polyols derived from dicarboxyllc andlor polycarboxylic acids and diols and/or polyols, - 14 - 1 _! 301 ~t 3 preferably from dicarboxylic acids and diols.

Examples of s~ch polycondensates are the hydroxyl-terminated polyesterswhich can be obtained by polycondensation of adipic acid, sebacic acid, azelaic acid, dimeric and trimeric fatty acids, phthalic acid, iso-phthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydro-phthalic acid and endomethylenetetrahydrophthalic acid with propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene, triethylene and tetraethylene glycol, dipropylene, tripropylene and tetrapropylene ;
glycol, dibutylene, tributylene and tetrabutylene glycol, 2,2-dimethyl-propane-1,3-diol, l,l,l-trimethylolpropane, 1,1,1-trimethylolethane and 1,2,6-hexanetriol.

other suitable prepolymer synthesis components for the preparation of polyisocyanates al~ are hydroxyl-terminated polybutadienes, which are ~ ;
reacted, in particular, with hydroxyl-terminated polyethers in order to ~, form the component al).

ther examples of suitable prepolymer synthesis components for the pre-paration of polyisocyanates al) are polymerization products of lactones, for example ~-caprolactones; or polyalkylene thioether-polyols, for example the polycondensation products of thiodiglycol with itself and with diols and/or polyols, for example 1,6-hexanediol, triethylene gly-col, 2,2-dimethyl-1,3-propanediol or l,l,l-trimethylolpropane. ~ -,: , . :
- : :
e preferred prepolymer synthesis components for the preparatlon of polyisocyanates al) are hydroxyl-terminated polyethers or polyesters.

Other preferred prepolymer synthesis components for the preparation of polyisocyanates al) are mixtures of hydroxyl-terminated polybutadiene and hydroxyl-terminated polyalkylene glycol or hydroxyl-terminated polyalky-lene glycols containing grafted-on l-olefins, in particular styrene or acrylic acid derivatives, such as acrylic acid esters or acrylonitrlle.
:
Prepolymer synthesls components for the preparation of polyisocyanates al) which are very particularly preferred are hydroxyl-terminated poly-ethers, in particuLar dihydroxyl-terminated polyalkylene glycols.

Chain lengtheners for the preparation of the prepolymer polyisocyanate al) are known per se. Examples of these are the diols and polyols men-tioned earlier in the text for the preparation of the hydroxyl-terminated polyethers, in particular the diols and triols, such as 1,4-butanediol, l,l,l-trimethylolpropane or hydroquinone 2-hydroxyethyl ether, or dia-mines, such as diaminoethane, 1,6-diaminohexane, piperazine, 2,5-di-methylpiperazine, l-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4,4'-diaminocyclohexylmethane, 1,4-diaminocyclohexane and 1,2-propylene-diamine, or hydrazine, amlnoacid hydrazides, hydrazides of semicarbazido-carboxylic acids, bLs-hydrazides and bis-semicarbazides.

Short-chain diols or triols are preferably used as chain lengthening agents.

The prepolymer polyisocyanate a2) can be obtained in a manner known per se from amino-termlnated prepolymers of the formuLa IIIb, especially from amino-terminated polyethers, by reaction with phosgene or with polyiso-cyanates, preferably diisocyanates or triisocyanates and particularly preferably diisocyanates. In general, besides the amino groups, the amino-term1nated prepolymers do not contain any further radicals having active hydrogen atoms. Prepolymers having terminal amino groups are derived, in general, from the hydroxyl-terminated condensation or addi-tion polymers described earlier in the text as synthesls components for .. . . .
al), particularly from polyethers. -~

They can be obtained by reacting the said condensation or addition poly- ~ ;
mers containing secondary hydroxyl groups with ammonia or by reacting the said condensation or addition polymers containing primary hydroxyl groups, for example polybutylene glycol, with acrylonitrile, and subse-quently hydrogenating these products.

Prepolymer-amino-terminated poly-THF can also be obtained by the method of S. Smith et al. in Macromol. Sci. Chem., A7(7), 1399-1413 (1973) by terminating a difunctional, still active, cationic THF polymer with . , ~ 330 ~ 43 :~

potassium cyanate.

The polyisocyanates used for the preparation of the components al) or a2) are, as a rule, aliphatic, cycloaliphatic, aromatic or araliphatic di-isocyanates, triisocyanates or tetraisocyanates or precursors which can be converted into isocyanates of this type.

The aliphatic, cycloaliphatic or araliphatic diisocyanates or triiso-cyanates are preferred, very particularly the aliphatic or cycloaliphatic diisocyanates.

The preferred aliphatlc diisocyanates are, as a rule, linear or branched -,~-diiæocyanates. The alkylene chains can, if appropriate, be inter- ` -~
rupted by oxygen oc sulfur atoms and can, if appropriate, contain ethy- -~
lenically unsaturated bonds.

,~-Diisocyanates having linear, saturated C2-C20alkylene radicals are preferred. -Examples of such radicals are ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethy~
lene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadeca-methylene and eicosamethylene.

Examples of preferred aliphatic ~ diisocyanate radicals which are $nterrupted by hetero atoms are -(CH2-CH2-0~-CH2-CH2-, -(CH(CH3)-CH2-0 ~ CH(CH3)-CH2-~ -(CH2-cH2-cH2-cH2-o~-cH2-cH2-cH2-cH2 and -(CH2-CH2-S)o-CH2-CH2- in which o is 1 to 20. ;~

The preferred cycloaliphatic diisocyanates are, as a rule, derlvatives -which are derived from substituted or unsubstituted cyclopentanes, cyclo-hexanes or cycloheptanes. It is also possible for two such rings to be attached to one another via a bridge member.
.
Examples of radicsls of this type are 1,3-cyclohexylene, 1,4-cyclo-hexylene or dodecahydrodiphenylmethane-4,4'-diyl.
;.", ~:

~''''`'`,"``'',. . ~ ""`'.''' ''` ' ''-''' '`""' ' '' ,' ', " . "'' ''" .

. . ~ h; ' ~ " . ~ i ' , 1 3301 a3 It is also possible to use diisocyanates or triisocyanates derived fromdimeric or trimeric fatty acids. These compounds can be obtained in a manner known per se from the fatty acids by rearrangement to give the corresponding diisocyanates or triisocyanates (Hoffmann, Curtius or Lossen rearrangements).

Examples of preferred aromatic diisocyanates correspond to the examplesof divalent phenol radicals given earlier in the text, in which the -OH
groups have been replaced by -NCO groups.

Examples of araliphatic diisocyanate radicals are 1,2-xylylene and 1,4-xylylene.

Specific examples of suitable polyisocyanates are 2,4-diisocyanatotoluene and technical mixtures thereof with 2,6-diisocyanatotoluene, 2,6-diiso-cyanatotoluene, 1,5-diisocyanatonaphthalene, 4,4'-diisocyanatodiphenyl- ~ -~
methane and technical mixtures of various diisocyanatodiphenylmethanes (for example the 4,4'- and 2,4'-isomers), urethanized 4,4'-diisocyanato-diphenylmethane, carbodiimidized 4,4'-diisocyanatodiphenylmethane, the uretdione of 2,4-diisocyanatotoluane, triisocyanatotriphenylmethane, the adduct formed fro~ diisocyanatotoluene and trimethylolpropane, the trimer formed from diisocyanatotoluene, diisocyanato-m-xylylene, N,N'-di-(4-methyl-3-isocyanatophenyl)-urea, mixed trimerization products of diiso-cyanatotoluene and 1,6-diisocyanatohexa~ethylene, 1,6-diisocyanatohexane, 3,5,5-trimethyl-1-isocyano-3-isocyanatomethylcyclohexane (isophorene di-isocyanate), N,N',N"Ltri-(6-isocyanatohexyl)-biuret, 2,2,4-trimethyl-1,6-diisocyanatohexane, l-methyl-2,4-diisocyanatocyclohexane, dimeryl, diiso-cyanate, 4,4'-diisocyanatodicyclohexylmethane, trimeric isophorene, diiso-cyanate, trimeric hexane diisocyanate and methyl 2,6-diisocyanatohexanoate. ~ - ~
- ~:
The preparation of the component al) or a2) is effected in a manner known per se by reacting the hydroxyl-terminated, sulfhydryl-terminated or amlno-terminated elastomeric prepolymer co~ponent with a polyisocyanate or witb a mixture of these components. The reactions can, if appro- -priate, be carried out in the presence of a chain lengthener.

-13301~3 :

The preparation of the component al) or a2) is carried out without a solvent or in solvents which are inert towards lsocyanates.

Examples of inert solvents are esters, such as ethyl acetate, butyl ace- -tate, methylglycol acetate and ethylglycol acetate; ketones, such as methyl ethyl ketone or methyl isobutyl ketone; aromatic compounds, such as toluene or xylene, or halogenated hydrocarbons, such as trichloro-ethane or methylene dichloride.

If a certain additional chain lengthening reaction via urethanes or urea -groups is accepted, or is even desired, the prepolymers containing hy-droxyl, sulfhydryl or amino groups and the monomers which may be present ~
are reacted with the diisocyanate or polyisocyanate in an NCO/OH or NCO/ ;
SH or NCO/NH2 ratio, respect'vely, of 1.5-2.5, preferably 1.8-2.2, if appropriate first at 0-25C and with cooling, and subsequently, if appro-priate, for several hours by heating at, preferably 50-120C.

If a chain lengthening reaction is not desired, a substantially larger exces3 of diisocyanate or polyisocyanate, for example an NCO/OH, NCO/SN
or NCO/NN2, respectively, ratio of 3-5, and no chain lengthener, is, as a rule, used, and the procedure is otherwise as described for low NCO/ON, NCO/SH or NCO/NH2 ratios. After the reactlon the excess dllsocyanate -or polylsocyanate ls, lf appropriate, removed, for example by thln film ~ -dlstlllatlon or by solvent extraction.

The reactlon of the hydroxyl-terminated, sulfhydryl-terminated or amlno-termlnated prepolymers with polylsocyanates is carried out ln the pre- ~ ~
sence of catalysts known per se.

Examples of these are diazablcyclooctane, dlbutyltln dllaurate or tin-II
octoate. These catalysts are employed in the customary amounts, for example ln amounts of 0.001-2% by welght, relatlve to the amount of poly-lsocyanate.

m e reaction of the components al) or a2) (polylsocyanate IIIa) with the '''' ..'~ . . -: . .,: .
: ,. ~ , ............
::- . : , ~r~ ~

- 19 _ 1 ~30 1 ~3 phenol or aminophenol IVa is carried out analogously to the reaction, described above, of the hydroxyl-terminated, sulfhydryl-terminated or amino-terminated synthesis component with the polyisocyanate.

The polyphenol or aminophenol IVa is preferably initially taken in this reaction in an amount such that the free NCO groups are essentially con-suned by the reaction and that, in the main, one -OH or -NH2 group re-acts per polyphenol or aminophenol.

This will, as a rule, be the case if about two or three moles of OH
groups of the bisphenol or trisphenol or about one mole of NH2 groups of the aminophenol are initially taken for 1 mole of free isocyanate groups.

In the case of the polyphenols IVa the OH:NCO ratio is generally 1.5:1.0 to 3.0:1.0, preferably 1.8:1.0 to 2.5:1Ø

In the case of the aminophenols IVa the i1H2:NCO ratio is generally 0.8:
1.0 to 1.2:1.0, preferably 0.8:1.0 to 1.0:1Ø

It is, of course, also possible to employ excess amounts of the component IVa, in which case chain lengthening can take place via the phenol; how-ever, the end product should not contain more than 50% by weight, prefer- -ably less than 10% by weight, of unreacted component IVa, relative to the total mixture.

: . - , In the case of the aminophenols IVa, a stoichiometric amount is generally desirable.
~ /
It is also possible to employ mixtures of phenol and/or aminophenol IVa for masking the polyisocyanate IIIa. These mixtures can also contain small proportions of monophenols. In this variant, the proportion of monophenol i~ so chosen that the reaction product consists mainly of com-pounds of the formula I havlng free phenolic OH groups.

1 ')30 1 ~ 3 The amino-terminated prepolymers IIIb in process b) or c) are, as a rule, the prepolymer polyamines which have already been described in process a) and which were employed in that process for the preparation of the prepolymer polyisocyanate components IIIa. Preferred compounds IIIb are amino-terminated polyethers as defined above.

The urethanes IVb are derived from aminophenols HR3N-R2-(o~)m in which R2, R3 and m are as defined above. Urethanes IVb are prepared by masking these aminophenols with R11-0-C0-Cl in a manner known per se. In this formula Rll is as defined earlier in the test. The reaction of the comr ponents IIIb and IVb (process b) is generally carried out by initially taking the two components in a stoichiometric ratio or a slight excess of component IVb and by heating the mixture so that virtually all the free amino groups of IIIb are masked.

The reaction is preferably carried out in an inert solvent. Examples of these have been listed earlier in the text. ~

The cyclic carbonates or urethanes IVc are derived from ortho- or peri- ~ -bisphenols or ortho- or peri-aminophenols of formula H0-R12-OH or HR3 R12-OH, respectively. In these formulae R3 and R12 are as defined ^~earlier in the text. The compounds IVc can be obtained therefrom by re-action with phosgene. The reaction of the components IIIb and IVc (pro- ~
cess c) is generally carried out by initially taking the two components - ~- -in a stolchiometric ratio or a slight excess of component IVc. In other respects the reaction is carried out as described in process a).

The molecular weight (number average) of the polyurethanes or polyureas B) is usually within the range from 500 to 50,000, preferably within the ~ :
range from 500 to 10,000 and very particularly preferably within the range from 500 to 3,000.

The viscosity of these compounds is, as a rule, less than 150,000 mPa s, -~
preferably less than lO0,000 mPa s (measured at 80C by means of the Epprecht viscometer).
.;

~ . - . ;; . . . . ~ . .. , ~, .

13301~

The structures of the phenol-terminated polyurethanes or polyureas of the formula I which are derived from the reaction according to process a), b) or c) dlffer, depending on the functionality of the prepolymer radical Rl .

In process a) this functionality is determined, for example, by the functionality of the hydroxyl-terminated, sulfhydryl-terminated or amino-terminated prepolymers, by the chain lengtheners which may be employed, by the functionality of the isocyanate used for the preparation of IIIa and by the ratios between the individual reactants. Preferred components B) are compounds of the formula I in which X is -NH- and Y is -~1-, but very particularly preferably -0-.

Components B) which are also preferred are compounds of the formula I
which are essentially free from isocyanate groups and contain at least two free phenolic hydroxyl groups and can be obtained by reacting a) a prepolymer polyisocyanate which al) is an adduct of a polyisocyanate onto a prepolymer polyhydroxy or polysulfhydryl compound or onto a mixture of such compounds, if appropriate in combination with a chain lengthener, or a2) is derived from a prepolymer polyether-amine, with b) at least one phenol having two or three phenolic hydroxyl groups or an a~inophenol having one or two phenolic hydroxyl groups.

Compounds of the formula I which are particularly preferred are derived from prepolymer polyisocyanates a) which have an average isocyanate functionality of 2 to 3.
1 , t Compounds of the formula I which are particularly preferred are those in , which component al) is an adduct of a polyisocyanate onto a hydrdxyl-terminated prepolymer having an average molecular weight of 150 to 10,000. Compounds of the formula I which are very particularly preferred are those in which the synthesis component for the preparation of compo-nent al) is a hydroxyl-terminated polyether or polyester.

This synthesls component for the preparation of component al) is prefer-ably employed in combination with chain lengtheners.

:
. ~

Compounds of the formula I which are very particularly preferred are those in which the polyisocyanate for the preparation of component al) is an aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanate or triisocyanate, In a preferred embodiment, the preparation of the component al) is carried out using a hydroxyl-terminated polyether or polyester, in the absence of a chain lengthener and using an amount of polyisocyanate equivalent to the OH content or in excess; this gives, after masking with the polyphenol or aminophenol, polyurethanes of the formula VII .-~
0~
~ l(HO-~-mR2-X-~-NH ~ a~3-NH-~-o ~ Rl~ (VII) in which R2, m and n are as defined above, r i9 an integer between 1 and 3, X is -O- or -NH-, R13 is the r+l-valent radical of an aliphatic, cycloaliphatic, aromatic or araliphatic polyisocyanate after the removal of the isocyanate groups, and R14 is an n-valent, hydroxy-terminated polyester or polyether radical after the removal of the terminal OH
groups, sub~ect to the proviso that the index m and the radicals R2 and R13 can be different within a given molecule. ~ ~
.' "~ :,' ' Compositions containing compounds of the formula VII as component B) are preferred. ;~ ;

The lndex m is preferably 1. m e index n is preferably 2 or 3, very par-ticularly preferably 2. The index r is preferably 1. Preferred com-ponents B) are compounds of the formula VII in which m is 1, n is 2 or 3, r is 1, X is -O-, R13 is derived from an aliphatic, cycloaliphatic or aromatic diisocyanate and R14 is a divalent or trivalent radical of a hydroxyl-terminated polyester or polyether having a molecular weight of 150 to 10,000 after the removal of the terminal hydroxyl groups.

Components B) which are very particularly preferred are compounds of the formula VII in which m is 1, n is 2 or 3, r is 1, X is -O-, R13 i9 derived fro~ an aliphatic or cycloaliphatic diisocyanate and R14 is a divalent or tri~alent radical of a polyalkylene ether-polyol having a molecular weight of 150 to 3,000 after the removal of the terminal , ` ; '':

:~ :

1 33~1 43 hydroxyl groups.

The particularly preferred components B) of this last-defined type include those in which n is 2 and R14 is a structural element of the formula VIII
-(C9H2s-0-)x-csH2s (VIII) in which s is 3 or 4, x is an integer from 5 to 40 and the units -Cs-H2s-o- can be different within a given structural element of the for-mula VIII, within the scope of the definitions given.

The following are examples of structural elements of the formula VIII:

and copolymers containing these structural elements.

The components B) of this invention which are also preferred include com-pounds which can be obtained by reacting al) an adduct of an essentially equivalent amount of a diisocyanate with a mixture of a dihydroxyl-ter-minated or trihydroxyl-terminated polyether or polyester and less than 1 mol Z, relative to the hydroxyl-terminated prepolymer, of a short-chain diol or triol and b) an amount of a blsphenol or trlsphenol whlch i8 essentially equivalent to the NC0 content.

In another preferred embodiment, the preparation of the component a2) is ~
carried out using an amino-terminated polyalkylene ether, reacting the ~--latter ln the absence of a chaln lengthener with an amount of dllsocyan- ~ -ate which is equivalent to the NH2 content or in excess, or with phos- ~ -gene, and masking the resulting polyisocyanate with a polyphenol or aminophenol IIIa. miS gives a compound of the formula IX

[(H -t-mR Y ~ -NH-RIs ~ -NH ~ Rls (IX) in whlch R3, Y, m and n are as deflned above, t ls 0 or 1, RlS ls the divalent radlcal of an allphatic, cycloallphatic, aromatic or araliphatic dllsocyanate after the removal of the lsoCyanate groups, and R16 ls the ~ -n-valent radical of an amino-terminated polyalkylene ether after the removal of the termlnal NH2 groups.

r` :
- 24 - ~ 3 3 0 1 ~

Compositions containing compounds of the formula IX as the component B) are preferred.
"', .'' ',,~,, Particularly preferred compositions contain, as the component B), com- ;
pounds of the formula IX in which m is 1, n is 2 or 3, Y is -O-, R15 is derived from an aliphatic, cycloaliphatic or aromatic diisocyanate and R16 is a divalent or trivalent radical of an amino-terminated polyalky-lene ether having a molecular weight of 150 to 10,000 after the removal ~ -of the terminal amino groups. -.: . .
Compositions which are very particularly preferred contain, as the com-ponent B), compounds of the formula IX in which m is 1, n is 2, t is 0, Y is -O- and R16 is derived from a divalPnt, amino-terminated poly- ~; alkylene ether havlng a molecular weight of 150 to 6,000.

, .
Compositions which are very particularly preferred contain, as the com-ponent B), compounds of the formula IX in which m and t are 1, n is 2, R15 is the divalent radical of an aliphatic or cycloaliphatic diiso- :
cyanate after the removal of the isocyanate groups, and R16 is derived from a divalent, amino-terminated polyalkylene ether having a molecular ;~
welght of 150 to 6,000.
.
The particularly preferred components B) of these last-defined types include those in which R16 is a structural element of the formulae X, XI, XIIj XIII or XIV
HH-CH2-~-O-CH2 CH ~ (X), R~7 ~ CH2 ~ H2-CH ~ (XI), R ~ CH2-8NN ~ H2 ~cH ~ (XII), -tCH2 ~ CH2 ~ z (XIII), CO ~ NH~~CH-CH2~0ty~RI7~~0~CH2~ N ~ (XIV), in which y is 5 to 90, preferably 10 to 70, z is 10 to 40, R is a radical of an aliphatic diol after the removal of the two OH groups, and R is a radical of an aliphatic triol after the removal of the three OH groups.

~G;

:~ .

The compositions, according to the invention, formed from A) and B) csn be processed with epoxide resins to give cured products having the advan-;ageous properties described earlier in the text.

The invention therefore also relates to compositions containing compo-nents A) and B) as defined above and C), an epoxide resin havin8 at least two 1,2-epoxide groups per molecule; or containing an adduct formed from component A) and an epoxide resin, and also component B) and, if appro-priate, component C); or containing component A), an adduct formed from component B) and an epoxide resin and, if appropriate, component C); or containing an adduct formed from component A) and an epoxide resin, an adtuct formed from component B) and an epoxide resin, and, if appro-priate, component C).

The preparation of the compositions according to the invention can be ~ effected in a customary manner by mixing the components by means of known I mixing units (stirrers and rolls).
,, : .
In principle, any compound which is customary in the technology of epox- `
~ ide resins can be employed as the component C) or for the preparation of n~ ~ the adducts.

~ The following are examples of epoxide resin ,~ . , }) polyglycidyl and poly-(B-~ethylglycidyl)esters which can be obtained by reacting a compound having at least two carboxyl groups in the mole~
cule and epichlorohydrln or B-2ethylepichlorohydrin. The reaction is advantageously carried out in the presence of bases.

Aliphatic polycarboxylic acids can be used as the compound having at least two carboxyl groups in its molecule. Examples of these polycar-boxylic acids are oxalic acid, succinic acid, glutaric acit, adipic acid, pi~elic acld, suberic acld, azelaic acid and dimerized or trimerized linolelc acid.

It 18 also possible, however, to employ cycloaliphatic polycarboxylic - 26 - 13301~3 acids, for example tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.

It is also possible to use aromatic polycarboxylic acids, for example phthalic acid, isophthalic acid or terephthalic acid.

II) Polyglycidyl or poly-(R-methylglycidyl) ethers which can be obtained by reacting a compound having at least two free alcoholic hydroxyl groups -;
and/or phenolic hydroxyl groups and a suitably substituted epichloro-hydrin under alkaline conditions, or in the presence of an acid catalyst, with subsequent treatment with alkali.
,:
Ethers oE this type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly-(oxyethylene) glycols, propane-1,2-diol or 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-tri-methylolpropane, pentaerythritol, sorbitol and polyepichlorohydrins.

They are, however, also derived, for example, from cycloaliphatic alco-hols, such as 1,4-cyclohexanedimethanol, bis-(4-hydroxycyclohexyl)-methane or 2,2-bis-(4-hydroxy-cyclohexyl)-propane, or they possess aromatic nuclei, such as N,N-bis-(2-hydroxyethyl)-aniline or p,p'-bis-(2-hydroxyethylamino)-diphenylmethane.

The epoxide compounds can also be derived from mono-nuclear phenols, for example resorcinol or hydroquinone; or they are based on polynuclear phenols, for example bis-(4-hydroxyphenyl)-methane, 4,4'-dihydroxybi- ;
phenyl, bis-(4-hydroxyphenyl) sulfone, 1,1,2,2-tetrakis-(4-hydroxy- -phenyl)-ethane, 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-di-bromo-4-hydroxyphenyl)-propane and novolaks which can be obtained by sub~ecting aldehydes, such as formaldehyde, acetaldehyde, chloral or furfuraldehyde, to a condensation reaction with phenols, such as phenol, or with phenols which are substltuted in the nucleus by chlorine atoms or Cl-Cgalkyl gro~ps, for example 4-chlorophcnol, 2-methylphenol or 4-tert.-butyl-phenol, or by a condensation reaction with bis-phenol~, as descrlbed : .
: :

above.

III) Poly-(N-glycidyl) compounds which can be obtained by dehydro- -chlorinating the reaction products of epichlorohydrin with amines which contain at least two amino hydrogen atoms. These amines are, for example, aniline, n-butylamine, bis-(4-aminophenyl)-methane, m-xylenedi-amine or bis-(4-methyl-aminophenyl)-methane.

The poly-~N-glycidyl) compounds also include, however, triglycidyl isocyanurate, N,N'-diglycldyl derivatives of cycloalkyleneureas, such as ethyleneurea or 1,3-propyleneurea, and diglycidyl derivatives of hydan-.-toins, such as 5,5-dimethylhydantoin. ~-:' IY) Poly-(S-glycidyl) compounds, for example di-S-glycidyl derivatives derived from dithiols, for example ethane-1,2-dithiol or bis-(4-~`~ mercaptomethylphenyl) ether.
- - . :
V) Cycloaliphatic epoxide resins, for example bis-(2,3-epoxy cyclo-pentyl) ether, 2,3-epoxycyclopentyl glycidyl ether, 1,2-bis-(2,3-epoxycyclopentyloxy)-ethane or 3,4-epoxycyclohexylmethyl 3',4'-epoxy- ~ ;
cyclohexanecarboxylate.

It i8 also possible, however, to use epoxide resins in whieh the 1,2~
~ epoxide groups are attached to varlous heteroatoms or functional groups;
these~compounds inelude, for example, the N,N,O-triglyeidyl derivatlve of ~ ` -4-aminophe 1, the glyeidyl~ ether/glycityl ester of sallcylic acid, N~
glycityl-N~'-(2-glycidyloxypropyl)-5,5-timethylhydantoin or 2-glycidyloxy-i~ 1,3-bls-(5,5-dlmethyl-1-glycidylhydantoln-3-yl)-propane.

Polyglycidyl ethers of bisphenols, for example 2,2-bis-(4-hydroxyphenyl)-propane or bis-(4-hydroxyphenyl)-methane, of novolaks formed by reacting ~`
formaldehyte with a phenol, or of the aliphatie diols mentionet above, espeeially butane-1,4-dlol, and adducts of blsphenol A and glycldylized allphatlc dlols are particularly preferret as epoxlde resins.

he curable compositlono aceordl~ to the lnvention also eontaln, as a ~:

- 28 - I 330 1 ~3 -rule, additional curing agents D) which are known to those skilled in the art, if appropriate in combination with an accelerator E).

Examples of curing agents are D) aliphatic, cycloaliphatic, aromatic and heterocyclic amines, such as bis-(4-aminophenyl)-methane, aniline/
formaldehyde resins, bis-(4-aminophenyl) sulfone, propane-1,3-diamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, 2,2,4-trimethylhexane-1,6-diamine, m-xylylenediamine, bis-(4-aminocyclohexyl)-methane, 2,2-bis-(4-aminocyclohexyl)-propane and 3-aminomethyl-3, 5,5- - -trimethylcyclohexylamine (isophoronediamine); polyaminoamides, for example those formed from aliphatic polyamines and dimerized or trimerized fatty acids; polyphenols, such as resorcinol, hydroquinone, 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A) and phenol/aldehyde resins; polythiols, such as the polythiols obtainable commercially under :the name Thiokole~; polycarboxylic acids and anhydrides thereof, for example phthalic anhydride, tetrahydrophthalic anhydride, hexahydro-phthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride, pyromellitic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic di-anhydride, the acids of the abovementioned anhydrides and also iso-phthalic acid and terephthalic acid. It i9 also possible to use curing agents having a catalytic action, for example tertiary amines Ifor example 2,4,6-tris-(dimethylaminoethyl)-phenol~; imidazoles or Mannich ~ .
bases; alkali metal alcoholates (for example the Na alcoholate of 2,4-dihydroxy-3-hydroxymethylpentane); tin salts of alkanoic acids (for example tin octanoate); Friedel-Crafts catalysts, such as boron tri-fluoride and boron trichloride and complexes and chelates thereof which ;~
are obtained by reacting boron trifluoride with, for example, 1,3-diketones; and amidines, preferably dicyandiamide.
.
Examples of accelerators E) are tertiary amines and salts or quaternary ammonium compounds thereof, such as benzyldimethylamine, 2,4,6-tris-(dimethylaminomethyl)-phenol, l-methylimidazole, 2-ethyl-4-methylimid-azole, 4-aminopyridine, tripentylammoniu~ phenolate or tetramethyl- : .
ammonium chloride; or alkali n~etal alcoholates, such as Na alcoholates of - :
2,4-dihydroxy-3-hydroxymethylpentane; or substituted ureas, such as N-(4- . : .:
chlorophenyl)-N',N'-dimethylurea or N-(3-chloro-4-methylphenyl)-N',N'-- 29 _ 1 330 1 ~3 dimethylurea (chlortoluron).

The properties of the cured end product can be varied, in accordance wlth the proportion of the components A) and B). -The followlng percentages relate in each case to the total weight of the ~ -components A), B) and C).

If products havlng a high strength, high glass transition temperature, high peeling resistance, high impact strength and high resistance to crack propagation (toughness to cracking) are desired, the proportion of -the components A) and B) should, as a rule, not exceed 60Z by weight.
Systems of this type are heterogeneous, as a rule. m e lower limit depends on the properties desired, for example the peeling resistance.
As a rule, components A) and B) should amount to more than 5X by weight, preferably more than lOX by weight.

If, on the other hand, products having the highest possible flexibility are desired, at least 40Z by weight, preferably more than 60X by weight, of the co~ponents A) and B) shoult be present.
:.
If component A) and/or B) has been modified by the formatlon of an adduct `~ wlth an epoxlde resln, a separate component C) 18 not absolutely neces~
sary.

In the case of hlghly flexlble sy9tems, lt is preferable to modify c03r ponent A) by the formatlon of an adduct wlth epoxide reslnsj adducts of llquid acrylonltrlle/butadlene copolymçrs havlng groups whlch are r ~
reactlve towards epoxlde reslns, with glycldyl ethers of allphatic ~ -dlols, such as 1,4-butanedlol or 1,6-hexanedlol, are partlcularly ~ pre'erred.

`~ Glycldyllzed novolaks derived from phenols having long-chain aliphatlc substituents in the nucleus, such as nonylphenol or cashew nut oil, are l i~ particularly suitable as the component C) in this case.
1`~ `
I

1~3ol43 The ratio by weight of A) to B) can be varied within wide limits. The preferred range of A) to B) is 50:1 to 1:50, 20:1 to 1:10 is particularly preferred and 5:1 to 1:5 is very particularly preferred.
..
The proportion of the epoxide resin C) to the total amount of A), s) and C) can also be varied within wide limits. For cured products having an increased flexibility, fairly small amounts of C), for example 10 to 30X
by weight, will, in general, be employed, it being also possible for component C) to be in the form of an adduct with A), whereas for cured products having a high strength, fairly large amounts of C), for example 50 to 95Z by weight, preferably 60-80% by weight, will, in general, be employed.
.
Surprisingly, it is possible to cure a composition containing a high proportion of components A) and B), for example more than 50X by weight, relative to the amounts of A), B) and C).

The invention therefore also relates to a process for curin~ composltions containing components A), B) and C), as deflned above, by adding a curing agent D) which i8 active at room temperature or at an elevated tempera-ture, and, if appropriate, a curing accelerator E) for C) and, if appro-priate, by heating, wherein the proportion of A) amounts to more than 50X
by weight, relative to the weight of A), B) and C).

The amount of curing agent D) or accelerator E) depends on the type of curing agent and is selected by those skilled in the art in a manner known per se.
Preferred are heat curable systems comprising components A), B) and C) in combination with primary und/or secondary aromatic amines or with -~
amidines as curing agent D).

m e preferred curing agent is dicyandiamide. In this case, it is prefer~
able to employ 0.1 - 0.5 mole of the curing agent per mole of epoxide groups.
, ~ '--:
me curing of the compositions according to the invention can be carried out at room temperature or at higher temperatures.
:
~ .

e ~ -31 1330143 : ~:

In general, the curing temperatures in the case of hot curing are between .
80 and 250C, preferably between 100 and 180C. The curing can, if i -desired, also be carried out in two stages, for example by interrupting ~-the curing process or, if a curing agent is employed for fairly high -temperatures, by allowing the curable mixture to cure partially at lower temperatures. The products obtained thereby are precondensates which are -still fusible and soluble (so-called "B-stage resins") and are suitable, for example, for compression moulding materials, sintered powders or prepregs.

If desired, reactive thinners, for example styrene oxide, butyl glycidyl ether, 2,2,4-trimethylpentyl glycidyl ether, phenyl glycidyl ether, --cresyl glycidyl ether or glycidyl esters of synthetic, highly branched, mainly tertiary, aliphatic monocarboxylic acids, can be added to the curable mixtures to reduce their viscosity further.

Other customary additives which the mixtures according to the invention ~ - ~
can contain are plasticizers, extenders, fillers and reinforcing agents, ~-for example coal tar, bitumen, textile fibres, glass fibres, asbestos ~-fibres, boron fibres, carbon fibres, mineral silicates, mica, powdered quartz, hydrated aluminiu~ oxide, bentonite, wollastonite, kaolin, silica -aerogel or metal powders, for example aluminium powder or iron powder, and also pigments and dyes, such as carbon black, oxide colours and titaniun dioxide, fire-retarding agents, thixotropic agents, flow control agents, such as silicones, waxes and stearates, which can, in part, also be used as mould release agents, adhesion promoters, antioxidants and llght stabilizers.

The cured products are distinguished by the advantageous properties described initially.

The invention therefore also relates to the products which can be obtai-ned by curing compositions containing A), B) and C); in this regard it is also possible to employ components A) andtor B) as adducts to epoxide resins.

The mixtures accorting to the invention can be used, for example, as ~ -, -: ~'",':~':~:-i,:,: :.~:

3nl~3 .: ' adhesives, adhesive films,patches, matrix resins, lacquers or sealing compositions or very generally for the preparation of cured products.
They can be used in a formulation adapted to suit the particular field of use in each case, in an unfilled or filled state, for example as paints, coating compositions, lacquers, compression moulding materials, dipping resins, casting resins, impregnating resins, laminating resins, matrix resins and adhesives.

The invention also relates to the use of the mixtures according to the invention for the purposes mentioned above.
The following examples illustrate the invention. Quantities refer to parts by weight unless specified otherwise.
Examples 1-6:
A. Preparation of the components Phenol-terminated pre~olymer lA ~ -354 g of anhydrous polypropylene glycol (Mw ~ 2,000), 1.8 g of tri-methylolpropane and 0.1 ml of dibutyltin dilaurate are added at 100C
and under nitrogen to 54.4 g of hexamethylene dlisocyanate. After the mixture has been stirred at 100C for two hours and the isocyanate con-tent has fallen below 4X, this prepolymer is run at 80C into 135 g of anhydrous 3,3'-diallylbisphenol A, and the mixture is stirred for 2.5 hours at 80C and for 30 minutes at 100C uneil free isocyanate can no longer be detected. This gives a viscous resin having the following analytical data: -viscosity n40 ~ 128,600 mPa s; ~ --phenol content: 2.5 equivalents/kg;
molecular weight (GPC): Mn ~ 1260, MW/Mn ~ 11.4.
Butadiene/acrylonitrile copolymer - epoxide resin adduct lB
730 g of bisphenol A diglycidyl ether (epoxide content 5.4 equivalents/
kg), 200 g of carboxyl-terminated acrylonitrile/butadiene copolymer -(acrylonitrile content 26%, acid nu~ber 32 mg of KOH/g), 64 g of bisphenol A and 5 g of triphenylphosphine are heated, in a flask with ground ~oints equipped with a stirrer, a nitrogen inlet and a reflux con-denser, for 3 hours at 130C until a viscous resin is formed having an epoxide content of 3.3 equivalents/kg ant an Epprecht viscosity of 130,000 ~Pa s (40C).

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_ 33 _ l 3 3 0 ~

B. The preparation and testing of adhesive formulations General working instructions:
The mixtures described in Table I are prepared on a triple-roll mill and are employed to bond degreased, sand-blasted aluminium l.S mm thick and ~- -degreased steel 1.5 mm thick, the test specimens being cured for 1 hour ~:
at 180C and having an overlap of 1.25 cm2. The T-peel on degreased steel 0.8 mm thick is also measured, curing also being carried out for 1 hour at 180C. The glass transition tempe-rature is determined by dynamic mechanical spectroscopy on a glassfibre prepreg which has been impregnated with the adhesive and cured for 1 hour at 180C, using a Du Pont 9000 thermoanalysis instrument.

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:"'' ,, '. ., - :,' ' ~ 34 ~ 1330143 Table I: Adhesive formul~tions tested Example No. 2 3 4 5 6 Diglycidyl ether based on 70 70 70 70 70 70 bisphenol A
(epoxide content 5.4 equiva-lents/kg) .
Butanediol diglycidyl ether (epoxide content 9.2 equiva- 5 5 5 5 5 5 lents/kg) Glycidyloxypropyltrimethoxy- 0.1 0.1 0.1 0.1 0.1 0.1 silane _ Wollastonite Pl 30 30 30 30 30 30 Dicyandiamide 9.8 9.8 9. 8 9 .8 9.8 9. 8 Chlortoluronl 0.5 0 .5 0 .5 0 .5 0. 5 0- 5 Pyrogenic silica (Aerosil 380) 0.1 0.1 0~1 0.1 0-1 0-1 Adduct lB 30 30 30 30 30 30 _ Phenol-terminated polyurethane lA 5 15 20 30 50 70 (X by ~eight of polyurethane 11A) t3-3) (9-3) (12.3) (17-1) (25-6) (32.5) _ ~
,Lap shear strength on Al (N/mm2) 29.2 29.5 31.5 28.4 28.7 20.3 Lap shear strength on :
,,~teel (N/mm2) 2 3 .92 6 .02 5 . 8 2 6 . ~ 2 2. 9 18 ~ 2 T-peçl (N/mm) <0 .5 2 J 4 .0 7. 8 6~3 $~0 : :
I !
.r` ~: l Fracture t% cohesion failure) 0 0 0100 I100 100 . ~: ',-Glass transition temperature(C~104 97 91 8~ ~2 61 :: ' ;~:
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~ 35 ~ 13301~
Examples 7-8:
Production of castings and determinatlon of their toughness to cracking GTr A mixture of 200 g of epoxide resin based on bisphenol A (epoxide con-tent 5.4 equivalents/kg), lO g of butanediol diglycidyl ether (epoxide content 9.2 equivalents/kg), 22.8 g of dicyandiamide, l.O g of chlor-toluron, 2.0 g of pyrogenic silica and the amounts described in Table II
of the components from Examples Al are and cast to form a sheet measuring lSO x 60 x 4 mm, which is cured for 2 hours at 140C and for l hour at 160C. The glass temperature (Tg) is determined by means of thermo-mechanical analysis (TMA). The toughness to cracking GIC is measured at a variable measuring speed on polished, notched samples measuring 4 x lO
x 60 mm by the 3-point bending test method, crack formation being initi-ated by means of razor-blade notching. m e results are shown in Table II.
Table II: Toughness to cracking values GIC of mouldings and toughness to cracking as a function of the speed of rupture Ex. Phenol- Acrylo- Tg Toughness to cracking G (kJ/m ) ,~ -No. terminated nitrile/ Ic polyure- butadiene as a function of the speed of rupture ~
thane lA epoxide (m/s) ¦ a(de)ct L6 ¦~ c) Z-SY10-S ¦2.5X11-4¦9.7X10-2¦0.52 ¦l.a4 720 20 104 2.76 _ 1.52 0.53 0.48 `
81 40 1 40 1 941 5-9~ 1 5.80 1 5.20 12.56 11.22 ! Example 9: A mixture of 30 g of a carboxyl-terminated acrylonitrile/ -~
butadiene copolymer (acrylonitrile content 26Z, acid number 32 mg of ROH/g), 70 g of butanediol diglycidyl ether and 1.2 g of triphenylphos- ~ -phine i9 heated at 150C for 2 hours until an adduct having an Epprecht ~ -viscosity of 560 mPa s and an epoxide content of 6.0 equivalents/kg has been formed. 15 g of this adduct are mixed on a triple-roll mill with ~-15 8 Of the phenol-terminated polyurethane lA and 5 g of epoxide resin ': '-' ;

f~ ~
- 36 _ 1 ~30 1 ~3 based on bisphenol A (epoxide content 5.4 equivalents/kg), 3 g of aro-matic thinner (Actrel 400), 8 g of wollastonite Pl, 4 g of talc and 0.6 g of pyrogenic silica (Aerosil)380 and also 0.7 g of dicyandiamide and 0.2 g of chlorotoluron. A flexible composition which, when bonded, gives the following values is obtained after curing for 30 minutes at 180C:

Lap shear strength on sand-blasted aluminium sheet 1.5 mm thick which has been degreased with acetone: 3.8 N/mm, T-peel on steel 0.8 mm thick s~hich has been degreased with acetone: 1.6 N/mm.

Example 10: A mixture of 70 g of epoxide resin based on bisphenol A
(epoxide content 5.4 equivalents/kg), S g of butanediol diglycidyl ether (epoxide content 9.2 equivalents/ kg), 0.1 g of glycidyloxypropyltri-methoxysilane, 7 g of pyrogenic silica, 9.8 g of dicyandiamide, 0.5 g of chlortoluron, 30 g of wollastonite Pl, 30 g of a graft polymer of styrenetacrylonitrlle on a polybutadiene microgel (ABS powder, Novodur ~ ;~
A90 made by 8ayer) and 30 g of the phenol-terminated polyurethane lA is used to bond aluminium sheets 1.5 mm thick which have been degreased with acetone. The T-peel is determined by bonding steel sheets 0.8 mm thick which have been degreased with acetone.
Lap shear strength on aluminium: 25.2 N~mm T-peel on steel: 3.0 N/mm Examples 11-15 A. Preparatlon of the components Phenol-termlnatet prepolymer for Example 11 84 g o$ hexamethylene dllsocyanate are lnitially placed, under nitrogen, in a dry flask with ground ~olnts, and 500 g of anhydrous polypropylene glycol ~Mw 2000) are added at 85C ln the course of one hour, and the mlxture is stirred for 2 hours at 100C and for 1 hour at 135C until an ~ -lsocyanate content of 3.2% has been reached. mis prepolymer is added at 100C to a mlxture of 155 g of 3,3'-dlallylbisphenol A and 0.1 ml of dibutyltln dllaurate. After Rtlrrlng for 3 hours at 100C, lt ls no longer possible to detect frec~ lsocyanate, and S00 g of a vlscous resin havin8 the followlng analytical data are obtained:
' :-:..
., viscositynL40 = 390,000 mPa s;
phenol content: 1.4 equivalents/kg;
molecular weight (GPC): Mn = 2285, MW/Mn - 24.
Phenol-terminated prepolymer for Exa~ple 12:
54.4 g of hexamethylene diisocyanate are initially placed under nitrogen in a dry flask with ground joints, 354 g of anhydrous polypropyleneglycol (Mw = 2000), 1.8 g of trimethylolpropane and 0.1 ml of dibutyltin dilaurate are added successively at 100C, and the mixture is stirred for 2 hours at 100C until an isocyanate content of 3.5% has been reached. -~
This prepolymer is added to a solution of 100 g of bisphenol A in 300 ml -of anhydrous dioxane, and the mixture is boiled under reflux for 5 hours.
The dloxane is then removed at 100C/1.33 Pa torr and a viscous resin having the following analytical data is obtained: ~ - -viscosity n 80 = 60,160 mPa s;
molecular weight (GPC): Mw ~ 31,500;
phenol content: 1.8 equivalents/kg.

Phenol-terminated prepolymer for Example 13:
. ., . :., .:
40.8 g of hexamethylene diisocyanate are initially placed under nitrogen in a dry flask with ground joints and 265.5 g of anhydrous polybutylene glycol (Mw ~ 2000), 1.35 g of trimethylolpropane and 0.1 ml of dibutyltin dilaurate are added, and the mixture is stirred for 2 hours at 100C.
The resulting prepolymer is added at 80C to 101.3 g of anhydrous 3,3'- ~ ;dlallylbisphenol A, and the mixture is stirred for 4 hours at 100C and for 3 hours at 110 until free isocyanate could no longer be detected.
This gives aviscous resin having the following analytical data:
viscosity n80 - 56,000 mPa s; ~ ~ ;
molecular weight (GPC): Mn ~ 1250, ~W/Mn = 17;
phehol content: 1.55 equivalents/kg. -Phenol-termlnated prepolymer for Example 14: ~
67.2 g of hexamethylene diisocyanate are initially placed under nitrogen ~--in a dry flask with ground ~oints and 354 g of anhydrous polypropylene-glycol (Mw ~ 2000), 1.8 g of trimethylolpropane and 0.1 ml of dibutyltin dilaurate are added at 85C in the course of 15 minutes, and the mixture Is l~tirrod for 2 hotrs at 100C. Thlo prepoly-er Is added ar 100C to :`
- 38 _ 1 ;~30 1 ~3 135 g of anhydrous 3,3'-diallylbisphenol A, and the mixture is stirred for S hours at 100C and for 2 hours at 130C. This gives a vlscous resin having the following analytical data:
viscosity ~0 = 133,000 mPa s;
molecular weight (GPC): Mn ' 1420, MW/Mn = 11.5;
phenol content: 1.6 equivalents/kg .

Phenol-terminated prepolymer for Example 15:
54.4 g of hexamethylene diisocyanate are initially placed under nitrogen in a dry flask with ground joints, 354 g of anhydrous polypropylene glycol (Mw = 2000), 1.8 g of trimethylolpropane and 0.1 ml of dibutyltin dilaurate are added successively at 100C, and the mixture is stirred for 2 hours at 100C until an isocyanate content of 2.5X has been reached.
This prepolymer is then run into a solution of 100 g of bisphenol A in 300 ml of anhydrous dioxane, and the mixture is boiled under reflux for 5 hours. The dioxane is removed in vacuo at 100C/1.33 Pa, and a viscous resin having the following analytical data is obtained:
viscosity T180 = 92,160 mPa s;
molecular weight (GPC): Mw = 25,260; Mn 3 840, MW/Mn = 30;
phenol content: 1.8 equivalents/kg.

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B. The preparation and testing of adhesive formulations General working 1nstructions as in Examples 1-6 Table III: Adhesive fonmulations tested ~ . :
:~' " '' ~' Example No. 11 12 13 14 lS
Diglycidyl ether based on bisphenol ~
A (epoxide content 5.4 equivalents/ 70 70 70 J0 J0 ~ : -Butanediol diglycidyl ether - __ :
(epoxide content 9.2 equivalents/kg) 5 5 5 S 5 Glycidyloxypropyltrimethoxy- _ :
silane 0.1 0.1 0.1 0.1 oLl Wollastonite P1 30 30 30 30 30 -Dicyandiamide 9.8 9.8 9.8 9.8 9.8 Chlortoluron O.S O.S O.S 0.5 C- 5 .
Pyrogenic silica : ;:
(Aerosil 380) J.0 7.0 7.0 J.0 ~.0 Adduct lB 30 30 30 30 30 Phenol-terminated polyurethane 30 30 30 30 30 ` :
(% by weight of polyurethane) 16 16 16 16 16` -_ . . - ... ~
~ap sh2ear strength on Al 32.0 30.3 32.632.4 32.1 ~ap shear strength on steel (~I/mm2) 24.0 23.4 23.6 2S-2 2 Angle peeling resistance --on steel (N/mm) 8.~ 4-S ~4 4~9 5~ - :
~racture (% cohesion failure) 90 80 90 ~0 40 Glass transition temperature (C) . ~ ~
I ~2 9~ 8~ 84 94 : . :
~ . "" . :' Examples 16-20:
A. Preparation of the phenol-terminated polyurethanes Prepolymee for Exa~ple 16:
76 g of isophorone diisocyanate are initially placed under nitrogen in a dry flask with ground joints and 303 g of polybutylene glycol (Mw ~
2000), 1.5 g of trimethylolpropane and 0.1 ml of dibutyltin dilaurate are added successively at 100C, and the mixture is stirred for 2 hours at 100C until an isocyanate content of 3.3% has been reached. This prepolymer is added to 115 g of anhydrous 3,3'-diallylbisphenol A, and the mixture is stirred for 3 hours at 80C and for 30 minutes at 105C
until free isocyanate can no longer be detected. This gives a viscous resin having the following analytical data:
viscosity n80 ~ 64,000 mPa s;
molecular weight (GPC): Mn = 1740, MW/Mn - 8.8;
phenol content: 1.56 equivalents/kg.

Prepolymer for Exa~ple 17: -88.8 g of isophorone diisocyanate are initially placed under nitrogen in a dry flask with ground Joints and 354 g of polypropylene glycol (Nw 2000), 1.8 g of teimethylolpropane and 0.1 ml of dibutyltin dilaurate are added successively at 100C in the course of 15 minutes, and the -mixture ls stirred for 2 hours at 100C until an isocyanate content of 4.0% has been reached. This prepoly~er is added to 135 g of anhydrous 3,3'-dlallylbisphenol A, and the mixture is stirred for 3 hours at 80C
and for 30 minutes at 100C until free isocyanate can no longer be detected. This gives a viscous resin having the following analytical -~
data:
viscosltyn 80 ~ 12,640 mPa s;
molecular weight (GPC): Mn ' 1630, NW/Mn ~ 7.2; ~ -phenol content: 1.5 equivalents/kg.
1'` :
Prepolymer for Example 18:
88.8 g of isophorone dilsocyanate are inltially placed under nitrogen in a dry flask with ground ~oints and 354 g of polypropylene glycol (Mw 2000), 1.8 g of trimethylolpropane and 0.1 ml of tibutyltin dilaurate are ~ ~-added successively at 100C in the course of lS minutes, and the mixture ;~
,: .. , .~

. .. .
is stirred for 2 hours at 100C until an isocyanate content of 4.0% has been reached. 44 g of p-aminophenol are then added and the mixture is stirred for 3 hours at 120C. This gives a viscous resin having the following analytical data:
viscosity n80 = 42,800 mPa s;
molecular weight (GPC): Mn = 1090, MW/Mn = 5.8;
phenol content: 0.83 equivalents¦kg.

Prepolymer Eor Example 19:
88.8 g of isophorone diisocyanate are initially placed under nitrogen in a dry flask with ground jolnts and 354 g of polypropylene glycol tMW ~
2000), 1.8 g of trimethylolpropane and 0.1 ml of dibutyltin dilaurate are added successively at 100C in the course of 15 minutes, and the mlxture is stirred for 2 hours at 100C until an isocyanate content of 4.0% has been reached. 118 g of bisphenol A are then added, and the mixture is stirred for 3 hours at 120C until free isocyanate can no longer be detected. This gives a viscous resin having the following analytical data:
viscosity n80 = 11,360 mPa s;
molecular weight (GPC): Mn = 620, MW/Mn = 9.3;
phenol content: 2.4 equivalents/kg.

Prepolymer for Example 20:
70 g of a mixture of toluylene diisocyanate isomers is initially placed under nitrogen in a dry flask with ground ~oints and 354 g of poly-propylene glycol (Mw 2000), 1.8 g of trimethylolpropane and 0.1 ml of dibutyltin dilaurate are added successively at 100C, and the mixture i8 stirred for 2 hours at 100C until an isocyanate content of 4.0% has been -reached. This prepolymer is run at 100C into 135 g of diallylbisphenol A, and the mixture is stirred for 3 hours at 100C until free isocyanate ~ -can no longer be detected. This gives a viscous resin having the following analytical data:
viscosity n80 ~ 17,920 mPa s;
molecular weight (GPC): Mn ~ 2000, MW/Mn ~ 6.4;
phenol content; 2.2 equivalents/kg.

B. The preparation and testlng of adhesives The procedure described in Example l i8 followed. In measuring the T-peel on oily steel, the steel specimens 0.8 mm thick are cleanset with acetone, dried at 80C in a circulating air oven, then immersed in a mixture of 10 parts of anti-corrosion oil (P80 made by Pfinders Nachf. GmbH & Co. D-7030 B'oblingen) and 90 parts of n-heptane, and dried for 10 minutes at 80C in a circulating air oven. m e results are shown in Table IV.
:, Table IV: Adhesive formulations tested Example No. 16 17 18 19 20 _ _ "', ':-Diglycidyl ether based on bisphenol A 70 70 70 70 70 (epoxide content 5.4 equivalents/kg) Butanedlol glycidyl ether (epoxide5 5 5 S 5 content 9.2 equivalents/kg) _ --~
Glycidyloxypropyltrimethoxysllane0.1 0.1 0.1 0.1 0.1 Wollastonite Pl 30 30 30 30 30 - - -Dicyandiamide 9.8 9.8 9.8 9.8 9.8 ; Chlortoluron 0.5 0.5 0.5 0.5 O.S
~ Pyrogenic si}ica (Aerosil 380) 7.0 7.0 7.0 7.0 7.0 a}~ Adduct lB 30 30 30 30 30 ; Phenol-termlnated polyurethane 30 30 30 30 30 (Gew. % Polyurethane 16 16 16 16 16 . : :: - , --.
,Lap ~hear strength on A} (N~m )27.0 25.3 26.9 25.3 24.6 ;- ;

Lap shear trength on stee1 (N/mm2) 23.4 24.6 26.4 23.~9 24.0 T-peel on degreased steel (N/mm)5.0 8.1 5.8 5.3 6.0 ~Z cohesion failure)(30)(90)(70) (50) (30) ¦T-peel on oily steel (N/mm)4.96.9 4.9 6.5 5.4 (% cohe8ion failure)~0)(80)(30)(80) (30) ~`-1 330 1 ~3 - 43 - . ::

Examples 21-26: :

A. Preparation of prepolymers Adduct 23 680 g of the diglycidyl ether of bis-(4-hydroxyphenyl)-methane (epoxide content 5.8 equivalents/kg), 319 g of carboxyl-terminated acrylonitrile/
butadiene copolymer (acrylonitrile content 26~, acid number 32 mg of KOH/g) and 1 g of triphenylphosphine are heated for 2 hours at 150C in a flask with ground joints equipped with a stirrer, a nitrogen inlet and a reflux condenser until a viscous resin having an epoxide content of 3.5 equivalents/kg has been fonmed.

Polyurethane adduct 25 750 g of the phenol-terminated prepolymer lA are heated, together with 248 g of butanediol diglycidyl ether (epoxide content 8.0 equivalents/kg) and 2 g of triphenylphosphine, in a flask with ground ~oints equipped with a stirrer, a nitrogen inlet and a reflux condenser, for 2 hours at 150C until a viscous resin having an epoxide content of 1.26 equiva-lents/kg has been formed. ~
'~',, ' '.' B. The preparation and testing of the adhesive mixtures ~^

The mixtures described in Table V are prepared on a triple-roll mill and ~ :
are e~ployed for bonding oily steel.
: , -:
~ : Lap shear strength values on oil-treated steel 1403 (thickness 1.5 mm) are determined as specified in DIN 53,283.
~ , .
T-peel values on oil-treated steel 1403 (thickness -0.6 mm) are determined as specified in DIN 53,282.

~: Values of eloogation at break are determined on standard test specimens of the materlal by the tensile test ISO R 527.

- In all cases curing is carried out for 30 minutes at 180C.
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1 330 1 ~3 The energy absorption i8 determined in a modlfied falling bolt test (impact peel test), a steel sheet 2 mm thick (150 x 20 mm) bein8 glued (curing 30 minutes/180C) to a perforated steel plate (150 x 60 x 20 mm, diameter of perforation 25 mm). The steel sheet is knocked away through this drilled hole by means of a bolt (10.7 kg, diameter 12.6 mm), falling from a height of 2 m, ant the absorption of energy is measured at the same time by means of the CEAST falling bolt device.

Table V: Adheslve formulations tested xample No. Zl 22 23 24 25 Z6 L ~ ~ -Epoxide resin based on bisphenol - ~ ~
A (epoxide content 5.3 equiva- 25 9 25 25 25 25 ~ - ;Y
lents/kg) Epoxide resin based on bis-(4- ~
hydroxyphenyl)-methane (epoxide _ 16 _ l _ _ ~ -u-~ -content 5.8 equivalents/kg) _ Adduct lB `32 32 Adduct 23 _ _ 30 30 30 30 Phenol-terminated polyure- -thane lA 8 8 8 _ _ _ - -~ ~ -Phenol-terminated polyure-thane 16 _ _ _ 8 _ _ Adduct 25 _ _ _ _ 15 25 7 ,.
Dlcyandiamide 4.7 4.7 4.7 4.7 4.7 4.7 Wollaatonite 10 10 10 10 10 10 Pyrogenlc silica (Aerosil~ R 202) 3 3 3 3 3 3 .': .' ~
Lap shear strength on oily ` - ;--steel (N/mm2) - 25 26 26 27 25 26 T~peel on oily - ~ -steel (N/mm) 5.0 6.0 4.8 5.5 5.2 7.0 -Energy absorption in the impact peel test (J) 10.5 13.012.3 12.C12.9 15.0 Elongation at break in the tensile test (X) 9.0 9.0lO.C ll.C10.0 15.0 `~

Example 27: A mixture of 35 parts of epoxide resin based on bisphenol A
(epoxide content 5.3 equivalents/kg), 2.5 parts of butanediol diglycidyl ether (epoxide content 8.0 equivalents/kg), 15 parts of adduct lB, 0.1 part of glycidyloxypropyltrimethoxysilane, 15 parts of wollastonite, 4.9 parts of dicyandiamide, 0.25 part of chlortoluron, 3.5 parts of pyrogenic silica (Aerosil~9380) and 15 parts of the phenol-terminated polyurethane lA is prepared on a triple-roll mlll. Curing 1s carried out for 1 hour at 180C. The values of T-peel on degreased steel (thickness 0.6 mm) [DIN 53,282] and the tensile elongation charac-teristics [ISO R 527] are determined.
Angle peel strength: 6.7 N/mm;-Elongation at break: (23C) 13.8%;
(-30C) 5.0%;
Modulus of elasticity: (23C) 2.85 GPa;
(-30C) 3.83 GPa. :

The effect-of the speed of measurement is also investigated in the case of the angle peel strength values:

,~ .
Drawin~ speed (m/s) T-peel (N/mm) 0.0025 8 1.99 13 5.01 15 10.0 19.3 . ' '.
, .
Examples 28-41:
' ,~
A. Preparation of prepolymers Adduct 28 : :' 438 g of epoxide resin based on bisphenol A (5.3 equivalents/kg), 38.2 g ~ ~ -of bisphenol A, ll9 g of carboxyl-terminated acrylonitrile/butadiene co-polymer (acrylonitrile content 18X, acid n~mber 29 mg of ROH/g) and 4.8 g ~r , r ,~

of triphenylphosphlne are heated at 140C for 2 hours under nitrogen until a viscous resin having an epoxide content of 3.3 equivalents/kg and a viscosity by Epprecht's method of n40 ' 74,240 ~Pa s has been formed.

Phenol-terminated prepolymer for Example 29 54.4 g of hexamethylene diisocyanate are initially placed, under nitro- -gen, ln a dry flask with ground joints, and a mixture of 200 g of anhy- -drous dihydroxyl-terminated polypropylene glycol (Mn - 2,000) and 0.1 ml -of dibutyltin dilaurate is added at 100C in the course of 60 minutes.
11.0 g of 1,4-cyclohexanedimethanol are then added to this reaction mix-ture and the latter is stirred for 60 minutes at 100C and the prepolymer M
thus obtained is added, under nitrogen, to 135 g of 3,3'-diallylbisphenol A at 100c in the course of 30 minutes. After stirring for three hours at looC free isocyanate can no longer be detected and a viscous resin having the followil~ analytical data is obtained:
viscosity n80 ~ 9,600 ~Pa s.
Phenol-terminated prepolymer for Example 30 33.9 g of isophorone diisocyanate and 0.1 ml of dibutyltin dilaurate are initially placed, under nitrogen, in a flask with ground ~oints, and a mixture of 137 g of anhydrous dihydroxyl-terminated polypropylene glycol `~ ~ -(Mn ~ 2,000) and 68.5 g of trihydroxyl-terminated polypropylene glycol tMn - 4,000) is added at 100C in the course of 1 hour. After the mix-ture has been stirred at 100C for 2 hours, this prepolymer is added to `
50 g of 3,3'-dlallylblsphenol A, and the mixture is stirred for 3 hours .~, -: ~ :
untll free lsocyanate can no longer be detected. This glves a vlscous resin having the following analytlcal data~
vlscoslty n40 ~ 24,600 ~Pa s; `-pheno} content: 1.15 equivalents/kg;
molecular weight (GPC): Nn ~ 1,830, MW/Nn - 16.
~"~
Phenol-terminated prepolymer for Example 31 ~ ;
71.8 g of lsophorone dilsocyanate are initially placed, under nitrogen, -in a dry flask with ground ~oints, a mixture of 354 g of anhydrous dihy- ;~
troxyl-termlnated polytetrahydrofuran (Mn ~ 2,000), 1.8 g of tri~ethylol-propane and 0.1 ml of dibutyltin dilaurate is added and the mixture is ~ ~ :
' .: :.
. ` ' ' `'`'~
:.' '''~ `~"'~' 1~30143 stirred for 2 hours at 100C until an isocyanate content of 2.3% has been reached. The prepolymer thus obtained is run into 134 g of 3,3'-diallyl-bisphenol A at 80C. After stirring for 3 hours at 80C, free isocyanate can no longer be detected and a viscous resin having the following analy-tical data is obtained: ;
viscosity n80 ' 37,760 mPa s;
molecular weight (GPC): Mn = 1,520, MW/Mn - 13.1.

Phenol-terminated prepolymer for Example 32 ô8.8 g of isophorone diisocyanate are initially placed, under nitrogen, in a dry flask with ground ~oints and a mixture of 354 g of anhydrous di-hydroxyl-terminated polycaprolactone (Mn - 2,000), 1.8 g of tri~ethylol-propane and 0.1 ml of dibutyltin dilaurate is added, with stirring, at 80C in the course of 30 minutes. After two hours the prepolymer obtained is added to 150 g of 3,3'-diallylbisphenol A, and the mixture i8 stirred for a further 3 hours at 80C until free isocyanate can no longer be detected. This gives a semi-solid resin having the following analytical data:
viscosity n80 ~ 5,760 mPa s.

Phenol-terminated prepolymer for Example 33 .
95.4 g of isophorone diisocyanate are initially placed, under nitrogen, in a flask with ground ~oints and 1.8 g of trimethylolpropane and 0.1 ml ~ -of dibutyltin dilaurate are added at 80C. A mixture of 354 g of dihy-droxyl-terminated polypropylene glycol (Mn - 2,000) and 80 g of bis-~aminopropyl)-polytetrahydrofuran (Mn - 750) læ then added at 80C ln the ~- course of 2 hours, the mixture is allowed to react for 2 hours and,finally, 150 g of 3,3'-diallylbisphenol A are added. After a reaction i time of 3 hours at 80C free isocyanate can no longer be detected and a viscous resin having the followin analytical data iæ obtained:
viscosity n80 ~ 40,9~0 mPa s;
molecular weight Mn - 1,200, NW/Mn ' 18-~
Phenol-terminated prepolymer for Example 34 30 g of bis-(isocyanatopropyl)-polytetrahydrofuran (prepared by phos-genating a bis-(aminopropyl)-tetrahydrofuran of molecular weight 750 and . ' ....

- 48 - 1 3 3 0 1 ~ 3 isocyanate content 8.5X which has been neutralized with anhydrous HCl) are added, under nitrogen, to a mixture of 24.6 g of 3,3'-dlallylbis~
phenol A and 0.1 ml of dibutyltin dilaurate in a dry flask with ground ~oints. Stirring for three hours at 100C gives a viscous resln having the following analytical data:
viscosity n 25 = 122,880 mPa s;
phenol content: 2.88 equivalents/k~.
:
Phenol-terminated prepolymer for Example 35 10 g of p-aminophenol are added, under nitrogen, to 50 g of bis-(iso- - ;
cyanatopropyl)-polytetrahydrofuran (prepared by phosgenatlng a bis-(aminopropyl)-polytetrahydrofuran of molecular weight 1,100 and isocyan-ate content 3.1% which has been neutralized with anhydrous HCl) in a dry flask, and the mixture is stirred for 5 hours at 100C. miS gives a viscous resin having the following analytical data:
viscosity: n 25 ~ 67,840 mPa s; ~ -phenol content: 2.03 equivalents/kg.
. : .
Phenol-terminated prepolymer for Example 36 29.2 g of a diisocyanate-terminated polypropylene glycol (isocyanate con-tent 3.6%, prepared by phosgenating a bisamino-terminated polypropylene ~ ~ -glycol of molecular weight 2,000, obtainable as Jeffamine~D D 2000 from Texaco, which has been neutralized with anhydrous HCl) are added, under - -nitrogen, to a mixture of 10.8 g of 3,3'-tiallylbisphenol A and 0.1 ml of dibutyltin dilaurate in a dry flask. Stirring for 6 hours at 100C ~ -gives a viscous, isocyanate-free resin having the following analytical ~ ~:data:
viscosity: n 25 ~ 44,160 mPa s;
phenol content: 1.73 equivalents/kg.

Phenol-terminated prepolymer for Example 37 4.9 g of p-aminophenol are added, under nitrogen, to 44.6 g of diiso-cyanate-terminated polypropylene glycol (isocyanate content 3.6X, pre- ; ~ ;
paret by phosgenating a bisal~ino-terminated polypropylene glycol of mole- ~ ;cular weight 2,000, obtainable as Jeffamin~ D 2000 from Texaco, which has been neutralized with anhydrous HCl) in a dry flask. Stirring for . ,-. ~".;~,...
. . ..
,'-,' :,"'.

'.':,'.,'. . ';:,, .~

1 3301 ~3 5 hours at 100C gives an isocyanate-free, viscous resin having the following analytical data:
viscosity n25 ' 63,360 mPa s;
phenol content: 0.96 equivalent/kg.

Mixture of phenol-terminated prepolymers for Example 38 A mixture of 56.5 g of 3,3'-diallylbisphenol A and 0.1 ml of dibutyltin dilaurate is added, under nitrogen, to 20 g of diisocyanate-terminated polypropylene glycol (isocyanate content 20%, prepared by phosgenating Jeffamin~ D 230 made by Texaco) in a dry flask. Stirring for four hours at 100C gives a waxy resin havlng the following analytical data:
vlscosity n80 = 1,520 mPa s; -phenol content: 4.76 e~uivalents/kg.
This prepolymer is employed as a mixture (1:3 parts by weight~ with the prepolymer described under Example 36.

Phenol-terminated prepolymer for Example 39 5.5 g of p-aminophenol are added, under nltrogen, to 50 g of trllsocyan-ate-termlnated polypropylene glycol (lsocyanate content 1.6%, prepared by phosgenatlng the polypropylene glycol triamine of molecular weight 3,000 which can be obtained commercially as Jeffs~ine~3T 3000), and the mixture ls boiled for 5 hours at 100C. This gives a viscous resin having the following analytical data:
vi~cosity n 25 ~ 89,600 mPa 8;
phenol content: 1.0 equivalents/kg.
. ' ;~ Phenol-terminated prepolymer for Example 40 ~ .
A mixture of 15.4 g of 3,3'-diallylbisphenol A and 0.1 ml of dlbutyltin dilaurate i8 added, under nitrogen, to 50 g of triisocyanate-terminated polypropylene glycol (isocyanate content 1.6X, prepared by phosgenating the polypropylene glycol triamine of molecular weight 3,000 whlch can be obtained commercially as JeffamineR T 3000, which has been neutralized -with anhydrous HCl), and the ~ixture is heated for 6 hours at 100C and for 2 hours at 140C to give sn isocyanate-free resin having the follo~-lng analytlcal data:
viscoslty: n 25 ' 87,040 mPa 8;

,,,', ` '. ' ' , ' . `, ,"' ' ,' ~ ,~:' ' . ',:. ' ' :. ' '',' .:.. ' .' ' ' 1 ~30143 phenol content: 1.53 equivaleQts/kg.

Phenol-terminated prepolymer for Example 41 A mixture of 68.2 g of 3,3'-diallylbisphenol A and 200 g of bisamino-termlnated polypropylene glycol (~n ' 2,000; obtainable as Jeffamine~3 D 2000 from Texaco) is added, under nitrogen, to 33.6 g of isophorone diisocyanate at room temperature, with stirring. 'When the exothermic reaction has subsided, 0.1 ml of dibutyltin dilaurate is added and the mixture is stirred for 3 hours at 100C. This gives an isocyanate-free, high-viscosity resin having tbe following analytical data:
viscosity: ~120 8 5,120 mPa s;
phenol content: 1.45 equivalents/kg. - -Phenol-terminated prepolymer for Example 42 ~ --A mixture of 313 g of hydroxyl-terminated polyalkylene ether, grafted with styrene/acrylonitrile (Niax0 24-32 made by Union Carbide), 0.1 ml of dibutyltin dilaurate and 0.9 g of trimethylolpropane is added, under -~
nitrogen, to 27.2 g of hexamethylene diisocyanate at looC in the course of one hour. After a further two hours, this isocyanate-terminated pre- -polymer is added to 68.0 g of diallylbisphenol A, and the mixture is stirred for 3 hours at 100C until free isocyanate can no longer be detected. This gives a phenol-terminated graft polymer having the following analytical data: -vlscosity (Epprecht): 40,900 mPa s (80C).

Phenol-terminated prepolymer for Example 43 ~ `
A ~ixture of 12.5 g of acrylonitrlle, 37.S g of styrene and 0.5 8 of azo- ; ~ -;
isobutyronltrile is added, under nitrogen, to 354 g of dihydroxyl-ter-minated polypropylene glycol (Mw - 2,000) at 75C in the course of 2 hours, and the mixture is allowed to react for four hours at an internal `~
temperature of 80-85C. After 0.1 ml of dibutyltin dilaurate has been added, the graft polymer is run, at 100C and in the course of 1 hour, ; ~
into 54.4 g of hexamethylene diisocyanate. After the mixture has been ~ ;
stirred for 3 hours at 100C, the isocyanate-terminated graft polymer thu8 obtained ls added to 135 g of o,o'-diallylbisphenol A, and the mlx-ture is allowed to react for two hours at 100C. mls gives a resin - 51 ~ 1 ~/)30 1 43 having the following analytical data:
viscosity (Epprecht): 158,720 mPa s (40C);
phenol content: 1.7 equivalents/kg.

Phenol-terminated prepolymer for Example 44 The procedure of Example 43 is repeated, except that a mixture of 50 g of styrene and 0.5 g of azoisobutyronitrile is added in the grafting Operation, and a phenol-contalning resin having the following analytical data is obtained:
viscosity (Epprecht): 143,360 mPa s (40C);
phenol content: 1.6 equivalents/kg.

Phenol-terminated prepolymer for Example 45 88 g of isophorone diisocyanate are initially placed, under nitrogen, in a dry flask with ~round joints, and a mixture of 25 g of hydroxyl-termi-nated poly~utadiene (ARC0 RD45HT) and 0.1 ml of dibutyltin dilaurate is added, with stirring, at 100C in the course of 1 hour. After the mix-ture has been stirred for 1 hour, 300 g of anhydrous dihydroxyl-termi-nated polybutylene glycol (Mn - 2,000) are added ln the c`ourse of 1 hour, and the mixture is then stirred for 2 hours at 100C. The isocyanate-terminated prepolymer thus obtained is added, with the exclusion of mois-ture, to 150 g of 3,3'-diallylbisphenol A. Stirring for 3 hours at 100C -gives a viscous, isocyanate-free resin having the following analytical data:
viscosity (Epprecht): n 80 ' 56,320 mPa s;
phenol content: 1.68 equivalents/kg;
molecular weight (CPC): Mn ' 1,700, ~/Mn - 90.
, Phenol-terminated prepolymer for Example 46 The preparation of the prepolymer is carried out analogously to Example 45, but using 50 g of hydroxyl-terminated polybutadiene (ARCO RD45HT) and -250 g of polybutylene glycol. This gives a viscous, isocyanate-free resin having the following analytical data:
viscosity (Epprecht): n 80 ' 84,480 mPa s;
phenol content: 1.76 equivalents/kg;
molecular weight (GPC): Mn ' 1,890, MW/Mn - 9.1.

'. .' - 52 ~ 1 330 1 ~3 B. The preparatlon and testlng of adheslves The procedure descrlbed in Example 1 is followed. The results, and the ~
compositions of the indlvldual adhesive mlxtures, are shown ln Table VI :
below.
D ~ ~ 0 ~ 5 ~ C ~ 5 9~ 'q X -3 C ~ O o ~ ~ X ~ ~ O 'e D~ ~ g ~ X 3 _ 3 ~- ~ ~ O~ 0 C~ ~ . ~
q 0 3 ' ~ 3~ O ~ 0 O : :
a.
~,~ ¦ rv __ ~n O r~ v~ rv 0, vl I ~,~ r~ ~O ~n ~ vl W O

vl I W V ~0 Vl _ vl W W 3 _ V~ I W U7 ~ V~ _ Vl W W I , ~
l vl I W vl ~0 Ul O vl vl rv .:

_ vl I W : r vl O ~ W W 0 .,, _ Ul ~ W O ~ vl O Vl vW~ V~ ., v~ ~ W v~~0 v~ O v~ v~ W .' -; . ~.

V~ V~ O ~0 v~ O v~ W W . . . -_ _ __ ~ W r~ ~O v~ O rv vW~ W ~
__ vl ~ W ~~n O v~ W O ' ~ ;;

_ v~ ~ W v~ .v~ O v~ vW~ : ' l vn I W O ~~n O rv ~ ~ ~
_ vl ry ~O ~ Vl Vl ~_, ~ ' l W O ~O W O Vl O N ., '.', o o Foo o o ~o- -w -::
o ~ o~ ,o~ o o o _ . v I W r~ ._ vn W
Vl vl ivY ~O Vl l rv W O~ , _ _ v~ _. '.'. ~

., 1 330 1 ~3 ? ? ? D) ~`? I~? ¦ _ ¦ 1.. ¦

`? _ w _ W ~ _ W . ' .
W U~_ -- W
- ~W ~ W _ ~ ; ~ ' ," ~? ~-? _ ~

'` ~ Cr~ W - - ~ . , ~ ~ .
. ~ C~l 0 _. _ _ , ~ ,~, r w ~ S ~A O

~''i,'`'~;'`: L.~ ~ W _ ~
~ o o ~ ~ ', ~, O W
,o~ O~ ~? O

. ~ : ~ `O o~ ~?
,~ I ~O 'w ` U- ~
` ~ ,: .: :

Claims (22)

1. A composition containing A) a copolymer based on at least one 1,3-diene and at least one polar, ethylenically unsaturated comonomer, and B) a compound of the formula I

(I) in which m is 1 or 2, n is 2 to 6, R1 is the n-valent radical of an elas-tomeric prepolymer, after the removal of the terminal isocyanate, amino or hydroxyl groups, which is soluble or dispersible in epoxide resins, X
and Y independently of one another are -O- or -NR3-, it being necessary for at least one of these groups to be -NR3-, R2 is an m+1-valent radi-cal of a polyphenol or aminophenol after the removal of the phenolic hydroxyl groups and optionally the amino group, and R3 is hydrogen, C1-C6alkyl or phenol.

2. A composition according to claim 1, wherein component A) is a copoly-mer based on butadiene.

3. A composition according to claim 1, wherein component A) is a copoly-mer based on butadiene/acrylonitrile, butadiene/(meth)acrylic acid esters, a butadiene/acrylonitrile/styrene graft copolymer (ABS) or a butadiene/ methyl methacrylate/styrene graft copolymer (MBS).

4. A composition according to claim 1, wherein component A) is a liquid butadiene/acrylonitrile copolymer.

5. A composition according to claim 1, wherein component A) is employed in the form of an adduct, of a butadiene/acrylonitrile copolymer having functional groups which are reactive towards epoxide resins, onto an epoxide resin.

6. A composition according to claim 1, in which the radical R2 is derived from a bisphenol of the formula VI

(VI) in which Z is a direct C-C bond or a bridge member selected from the group consisting of -CR6R7, -O-, -S-, -SO2-, -CO-, -COO-, -CONR8- and -SiR9R10-, R4 and R5 independently of one another are C1-C20alkyl, C2-C6alkenyl, C2-C6alkinyl or halogen, p and q independently of one another are 0, 1 or 2, R6, R7 and R8 independently of one another are hydrogen, -CF3 or C1-C6alkyl, or R6 and R7, together with the common C atom, form a cycloaliphatic radical having 5-12 ring C atoms, and R9 and R10 are C1-C6alkyl.

7. A composition according to claim 1, wherein X is -NH- and Y is -NH-or -O-.

8. A composition according to claim 1, wherein component B) is a com-pound of the formula I which is essentially free from isocyanate groups, contains at least two free phenolic hydroxyl groups and can be obtained by reacting a) a prepolymer polyisocyanate which a1) is an adduct of a polyisocyanate onto a prepolymer polyhydroxyl or polysulfhydryl compound or a mixture of such compounds, if appropriate, in combination with a chain lengthener, or a2) is derived from a prepolymer polyether amine, with b) at least one phenol having two or three phenolic hydroxyl groups or an aminophenol having one or two phenolic hydroxyl groups.

9. A composition according to claim 8, wherein the synthesis component for the preparation of component a1) is a hydroxyl-terminated polyether or polyester.

10. A composition according to claim 8, wherein the synthesis component for the preparation of component a1) is a mixture of a hydroxyl-terminated polybutadiene and a hydroxyl-terminated polyalkylene glycol, or is a hydroxyl-terminated polyalkylene glycol having grafted-on 1-olefins.

11. A composition according to claim 8, wherein the polyisocyanate for the preparation of the component a1) is an aliphatic or cycloaliphatic diisocyanate.

12. A composition according to claim 1, wherein component B) is a com-pound of the formula VII

(VII) in which R2, m and n are as defined in claim 1, r is an integer between 1 and 3, X is -O- or -NH-, R13 is the r+1-valent radical of an aliphatic, cycloaliphatic, aromatic or araliphatic polyisocyanate after the removal of the isocyanate groups, R14 is an n-valent, hydroxyl-terminated poly-ester or polyether radical after the removal of the terminal OH groups, subject to the proviso that the index m and the radicals R2 and R13 can be different within a given molecule.

13. A composition according to claim 12, in which m is 1, n is 2 or 3, r is 1, X is -O-, R13 is derived from an aliphatic or cycloaliphatic diisocyanate and R14 is a divalent or trivalent radical of a polyalky-lene ether-polyol having a molecular weight of 150 to 3,000, after the removal of the terminal hydroxyl groups.

14. A composition according to claim 8, wherein component B) can be obtained by reacting a1) an adduct of an essentially equivalent amount of a diisocyanate with a mixture of a dihydroxyl-terminated or trihy-droxyl-terminated polyether or polyester and less than 1%, relative to the hydroxyl-terminated prepolymer, of a diol or triol, and b1) an amount of a bisphenol or trisphenol which is essentially equivalent to the NCO
content.

15. A composition according to claim 1, containing, as the component B), compounds of the formula IX

(IX) in which R3, m and n are as defined in claim 1, Y is -O- or -NH-, t is 0 or 1, R15 is the divalent radical of an aliphatic, cycloaliphatic, aro-matic or araliphatic diisocyanate, after the removal of the isocyanate groups, and R16 is the n-valent radical of an amino-terminated poly-alkylene ether, after the removal of the terminal NH2 group.

16. A composition according to claim 15, wherein m is 1, n 1, 2 or 3, Y
is -O-, R15 is derived from an aliphatic, cycloaliphatic or aromatic di-isocyanate and R16 is a divalent or trivalent radical of an amino-ter-minated polyalkylene ether having a molecular weight of 150 to 10,000, after the removal of the terminal amino groups.

17. A composition according to claim 15, wherein m is 1, n is 2, t is 0, Y is -O- and R16 is derived from a divalent, amino-terminated polyalky-lene ether having a molecular weight of 150 to 6,000.

18. A composition according to claim 15, wherein m and t are 1, n is 2, R15 is the divalent radical of an aliphatic or cycloaliphatic diiso-cyanate, after the removal of the isocyanate groups, and R16 is derived from a divalent, amino-terminated polyalkylene ether having a molecular weight of 150 to 6,000.

19. A composition containing components A) and B) according to claim 1 and C) an epoxide resin having at least two 1,2-epoxide groups per mole-cule; or containing an adduct formed from component A) and an epoxide resin and also component B) and, if appropriate, component C); or con-taining component A), an adduct formed from component B) and an epoxide resin and, if appropriate component C); or containing an adduct formed from component A) and an epoxide resin, an adduct formed from component B) and an epoxide resin, and, if appropriate, component C).

20. A composition according to claim 19, wherein component C) is a poly-glycidyl ether of bisphenols, of novolaks formed by reacting formaldehyde with a phenol, or of aliphatic diols, and is also an adduct of bisphenol A and glycidylized aliphatic diols.

21. A process for curing compositions containing components A), B) and C) according to claim 19 by adding a curing agent D) which is active at room temperature or at elevated temperatures and, if appropriate, a curing accelerator E) and, if appropriate, by heating, wherein the proportion of A) amounts to more than 50% by weight, relative to the weight of A), B) and C).

22. A cured product which can be obtained by curing the compositions according to claim 19.