DE2033625A1 - New, epoxy-containing adducts of polyepoxy compounds and acidic, linear polycsterdicarboxylic acids, Vcr, are used to produce and use them - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BAS E L (S C H WEIZ)

* Λ ^F · ^For · * ·· «» «· η. - Dr. E. Assmann Dr. R. Koenigsbcrger - Dipl. Phy ». R. Holzbauer

Dr. F. Zumstein jun. P o t η t ο η w β I t

8 Mönch η 2, Bräuhausstroß 4 / III

Germany

New adducts from polyepoxy compounds containing epoxy groups and acidic, linear polyester dicarboxylic acids their manufacture and use.

From the American patent no. 3 02J 279 it is known that curing polyadducts of acidic, linear or branched polyesters and epoxy compounds can produce plastic products ranging from flexible to rubbery elastic. The more flexible the polymers are obtained, the more flexible the polyester component and the greater the proportion of polyester in the cured product. '.

The cured polyadducts are either viscoelastic or rubber-elastic. The 'at room temperature viscoelastic products show a decent toughness, but exhibit in their physical properties show a strong temperature dependency, i.e. at low temperatures these products are brittle and at If the temperature is slightly increased, these viscoelastic products change to the rubber-elastic state with little mechanical Strength over. In the transition area, or in the viscoelastic state, the polymers are not elastic Deformation, i.e. the deformation is strongly time-dependent. The rubber-elastic products at room temperature are consistently very soft and have a low strength and an extraordinary low notch strength.

It has now been found that by advancing polyepoxide compounds, in particular certain cycloaliphatic and heterocyclic polyepoxides with acidic, linear polyesters of succinic acid or succinic anhydride and 1,4-butanediol, in certain stoichiometric proportions, novel flexibilized, curable epoxy resins are obtained containing ¹ crystalline, elastomeric molded materials can be converted by curing with customary hardeners for epoxy resins, such as carboxylic acid anhydrides, polycarboxylic acids, polyamines or curing catalysts »i *, which is a substantially ..höhere hardness and toughness as well as a

0098 * 372126

have surprisingly high crystallization transition point of 70 to 10O ⁰ C. They have exceptionally high tensile strength, especially after they have been stretched in the heat

2
up to 2000 kg / cm, values that apply to the molding materials.

The basis of the curable epoxy resin systems known to date can hardly be achieved.

The polyesters which have terminal carboxyl groups and are used for the advancement of polyepoxide compounds from succinic acid and butanediol (1,4) must be proportionate be long chain, i.e. the repeating structural element the formula

must appear at least six times in the chain.

Usually the average molecular weight is of the polyester at least 1.150 to about 14,000. Furthermore, you have to pay for the pre-extension for 1 equivalent Use epoxy groups of the polyepoxy compound 0.1 to at most 0.65 carboxyl group equivalents of the acidic polyester. The best results are achieved when using 0.4 to a maximum of 0.6 carboxyl group equivalents of the acidic polyester.

The present invention thus relates to new, Adducts containing epoxy groups from polyepoxy compounds and ■.: .--:

acidic, linear polyesters, characterized in that one

009883/2126 ORIGINALINSPECTED

(a) Linear polyesters having terminal carboxyl groups of the average formula

HO-C- (CH

2'2

2.

-OH (I)

° -z

wherein ζ is a fourth number of at least 6, generally in the value from 6 to 80, but preferably in the value from 9 to 40, means with

(b) Diepoxide compounds, preferably diglycidyl or di- (ß-methylglycidyl) compounds, the glycidyl or ß-methylglycidyl groups of which are bonded to heteroatoms, such as, in particular, oxygen, sulfur or nitrogen, are converted under heat with the formation of adducts , 0.1 to at most 0.65, preferably 0.2 to at most 0.6, equivalents of carboxyl groups being used per 1 equivalent of epoxide groups.

The linear succinic acid-butane-1,4-diol polyester (a) containing carboxyl end groups is usually prepared after the melting process by placing the starting materials in the appropriate proportions and for so long allowed to react under a nitrogen atmosphere to about 150 to 160 ° C, bid the theoretical acid equivalent weight is reached.

The production of the succinic acid-butane-1,4-diol-polyester with carboxyl end groups takes place according to the following equation:

U09883 / 2126

(z + 1) .HOOC - '(CJH ₂ -JpOOOH + ζ.HO- (CH ₂ ) -OH

OC- (CHrJ-T-C -) - OH + 2 ζ.

Instead of succinic acid, succinic anhydride can also be used according to the following equation

(z + l).

pt 2.HO- (OH ₂ ) -OH '.

ζ.η ο

The succinic acid-butane-1,4-diol polyester of the formula (I) have an average molecular weight of at least approx. 1150 and preferably from approx. 160 to approx. 7OOO. The technical products still contain small amounts of polyesters with both terminal carboxyl and terminal en hydroxyl groups.

A small proportion of one can also be present in the polyesters other dicarboxylic acids, such as glutaric acid or adipic acid * and / or another diol such as propanediol or hexanediol , be condensed, however, such Modification of the technical characteristics of the krä & allinen

009883/2126

Plastic products usually deteriorate or theirs Crystallization transition point decreased.

It has been found to be advantageous when using succinic anhydride to produce the polyester add basic catalyst to the reaction mixture. This creates a uniform addition of the butanediol to which causes anhydride.

Tertiary amines are preferably used as catalysts, which again largely in the vacuum treatment can be removed. Pyridine in particular has proven to be advantageous here.

For the preparation of adducts containing epoxy groups from polyepoxy compounds and acidic, linear polyesters, 0.1 to 0.65, preferably 0.4 to 0.6, equivalents of carboxyl groups of the acidic polyester are used per 1 equivalent of epoxy groups. As a rule, this is done by simply melting the polyepoxide compound together with the acidic polyesters of the formula (I) Xn in the prescribed stoichiometric proportions. As a rule, one works in the temperature range of 100 to 200 C, preferably from Γ50 ^b * ^s l80 ° C.

The diepoxide compounds (b) for the production of the new adducts containing epoxide groups are primarily those with an average of two to one heteroatom each (e.g. sulfur,

preferably oxygen or nitrogen) bound glycidyl groups, ß-methylglycidyl groups or 2,> - epoxycyclopentyl groups in question. They are also suitable for manufacture of the new adducts containing epoxide groups also include cycloaliphatic polyepoxide compounds which have at least one on a carbocyclic Five or six ring seated 1,2-epoxy group exhibit. .

Examples of suitable diepoxide compounds are: bis (2,3-epoxycyclopentyl) ether; Diglycidyl ethers of dihydric aliphatic alcohols such as 1,4-butanediol or polyalkylene glycols such as polypropylene glycols; Diglycidyl ethers of cycloaliphatic diols, such as 2,2-BiS- (V-hydroxycyclohexyl) propane, or of the diols, such as l, l-bis (hydroxymethyl) cyclohexene-5, l, l-bis-hydroxyinethyl / cyclohexane, 1 , 4-bis (hydroxymethyl) cyclohexane, cis and trans quinite; Diglycidyl ethers of dihydric phenols, such as resorcinol, bis (p-hydroxyphenyl) methane, 2,2-bis (p-hydroxyphenyl) propane (= diomethane), m 2,2-bis (4'-hydroxy-3 ', 5'-dibromophenyl) propane; Di- (ß-methylglycidyl) ethers of the above-mentioned dihydric alcohols or dihydric phenols; Diglycidyl esters of dibasic carboxylic acids, such as adipic acid, sebacic acid, phthalic acid, terephthalic . L · acid, Δ -tetrahydrophthalic acid, 4-methyl-A -tetrahydrophthalic acid, hexahydrophthalic acid, 4-methyl-hexahydrophthalic acid,

Yy.

3,6-endomethylene-Ä -tetrahydrophthalic acid, 4-methyl-3,6-endo-

0.0 9883 / 21.26

methylene-Δ-tetrahydrophthalic acid; N-glycidyl derivatives of Amines, amides and heterocyclic nitrogen bases, such as Ν, Ν-diglycidyl-aniline, Ν, Ν-diglycidyl-toluidine.

The following are particularly mentioned as diglycidyl compounds of the N-heterocyclic series:

N, N'-diglycidyl compounds of the formula

O
II
C.

CH ₂ -CH-CH ₂ -Ir N-CH ₂ -CH-CH ₂ (II)

VI | _{/ Rl} V

O = Cr-C

where R, and R "each represent a hydrogen atom or a lower one . Denote an alkyl radical having 1 to 4 carbon atoms. Representatives of this class of compounds are e.g.!, JJ-diglycidyl-hydantoin, 1,3-Dlglycidyl-5-methyl-5-ethyl-hydantoin and in particular 1,3-diglycidyl-5,5-dimethylhydantoin and 1, j5-diglycidyl-5-isopropylhydantoin.

N, N'-diglycidyl compounds of the formula 0 0

ri ) f

H ₂ C - C -CH ₂ -NN CH ₂ N N-CH ₂ -C ^ CH ₂ (III)

^{Nq //} II /! ^R 3x I °

C C C C

H ^x / H

0 ^R 2 4 0

wherein R., R ₂ , R, and R ^ each represent a hydrogen atom or a lower alkyl radical having 1 to 4 carbon atoms, and wherein R ¹ and R "each represent a hydrogen atom or a

OOQ> g2.3i

. I.

Methyl group; Representatives of this class of compounds 'are ζ.B. Bis-O-glycidyl-5,5-dimethylhydantoinyl-1) methane, Bis (3- [ß-methylglyeidyl] -5,5-dimethylhydantoinyl-1) methane.

, N'-J diglyeidyl compounds of the formula

GH - CH-GH-IT C = O

O =

H-CH ₂ -CH -

(IV)

GN-

^R 2 G

-R-

r c

σ R.

H ⁴

O O

where R is an aliphatic, cycloaliphatic or araliphatic radical and R ₁ , Rg, R, and R ^ each represent a hydrogen atom or a lower alkyl radical having 1 to 4 carbon atoms. Representatives of this class of compounds are, for example, bis (l-glycidyl-5,5-dimethylhydantoinyl-3) -methane, 1,4-bis- (1'-glycidyl-5 ', 5'-dimethylhydantoinyl-3 ¹ ) -butane, ß, ß'-bis (l-glycidyl-5,5-dimethylhydantoinyl-3) -diethyl ether.

N, N'-diglyeidyl compounds of the formula

Il C

R "

C = O

⁵ V

^R 6

wherein R ^ and R ^ are each independently a hydrogen atom or a lower alkyl radical having 1 to 4 carbon.

009883/2126

mean atoms and where R ¹ and R "each stand for a hydrogen atom or a methyl group; representatives of this class of compounds are, for example, 1,3-diglycidyluracil, l,> di- (§-methylglycidyl) -6-methyluracll.

Ν, Ν'-diglycidyl compounds of the formula

OO

U U

OC CO

CH ^ -C-CH ₀ -NN CH H N-CH-C- CH ₀ '(VI)

₀
2

O = C HC-R ₅ ^Α 8 ~ ° ^{Η C = 0}

CC R ₇ R ₆ R _g R ₁₀

wherein R ₁ -, Rg, R ₇ , Rg, Rg and R. _Q each independently represent a hydrogen atom or a lower alkyl radical having 1 to carbon atoms and wherein R ¹ and R ″ each represent a hydrogen atom or a methyl group; representatives of this class of compounds are, for example, 1,1'-methylene-bis- (3-glycidyl-5,6-dihydrouracil), 1,1'-methylene-bis (3-lβ-methylglycidyl] -5,6-dihydrouracil).

Among the likewise suitable cycloaliphatic epoxy resins, the one seated on a carbocyclic "ring 1,2-epoxy groups are, for example, those of the formulas

009883/2128

- ■■ 11 -

CH HC-C

- O-

CH

CH,

CH,

CH,

CH,

3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate),

CH,

CH,

HC

CH HC-CH ₃
CH ₂

CO-CH ₂ -0

CH

HC

CE

CH ₂

(= 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4-epoxy-6-methylcyclohexanecarboxylate)

CH C CH - CH HC

- 0

CH,

CH ₂

CH

(= 3,4-epoxyhexahydrobenzal-3 ' _l 4 ^l -epoxycyclohexane-l ^l , l ^l dimethanol)

called.

Mixtures of the above can of course also be used listed epoxy resins can be used.

The adducts according to the invention containing epoxy groups react with the customary hardeners for polyepoxy compounds.

(109883/2126

They can therefore be crosslinked in the same way as other polyfunctional epoxy compounds by adding such hardeners. as such well-known hardeners come, for example, aliphatic, cycloaliphatic and aromatic polyamines, aliphatic ^, hydroaromatic and aromatic polycarboxylic acid anhydrides,. also curing catalysts, such as tertiary amines or boron trifluoride complexes in question.

Preferred hardeners are, for example, cyclo-

aliphatic polycarboxylic anhydrides, such as Δ -Tetrahydrophthal-

4th
anhydride, 4-methyl-A -tetrahydrophthalsaureanhydrid, Hexahydrophthaisäureanhydrid ·, 4-methylhexahydrophthalic anhydride, 3,6-endomethylene-A -tetrahydrophthalsaureanhydrid, 4-methyl-3> S- endomethylene-Δ -tetrahydrophthalsaureanhydrid (= methylnadic) and the Diels-Aider- Adduct of 2 moles of maleic anhydride and 1 mole of!, ^ - bis-cyclopentadienylJ-S-butene, trimellitic anhydride or pyromellitic anhydride, phthalic anhydride, 3 / ^ j5> 6 * 7> Y-hexachloro- ^ j6-endomethylene-A-tetrahydrophthalic anhydride, Succinic anhydride, adipic anhydride, azelalic anhydride, sebacic anhydride, maleic anhydride, dodecenyl succinic anhydride; also mixtures of the above anhydrides.

Another preferred class of hardeners are cycloaliphatic polyamines; Such suitable polyamines are: 1,2-diamino-cyclohexane, 1,4-diaminocyclohexane, 1,> - diaminocyclohexane, 1,2-diamino-4-ethylcyclohexane, l, 4-diamino-3> 6-

009883/2126

2033111

diethylcyclohexane, 1,4-bis (methylamino) cyclohexane, dodecahydrobenzidine, N-cyclohexyr-propylenediamine-l, ^, N-cyclohexylethylenediamine, N, N'-dicyclohexyl-propylenediamine-l, 3 * Ν, Ν'-dicyclohexyl- diethylenetriamine, 1,8-diamino-p-menthane and in particular 4,4'-diaminodicyclohexylmethane, 5j3'-dimethyl-4,4 ^l - ■ diaminodicyclohexylmethane, 2,2-bis (4'-aminocyclohexyl) propane, l-amino 2-aminomethyl-cyelopentane and especially 3- (aminomethyl) -

(= Isophoronediamine).

The following are also suitable as hardeners:

aliphatic amines, such as monoethanolamine, ethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N, N-dimethylpropylenediamine-l, 3i N, N-diethylpropylenediamine-1,3; aromatic or araliphatic amines, such as benzidine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4-diaminodiphenylmethane ^I, 4,4'-diaminodiphenylamine, 4,4'-Diaminodiphenyldimethylmethan, 4,4'-diaminodiphenylsulfone or oxide, 4,4 ^I -diaminodiphenylurea, 2,2'-diaminodiphenylmethane, N-phenylpropylenediamine, bis (ß-amino-r ethyl) -durol, 1,4-bis (ß-aminoethyl) benzene, o-xylylenediamine, p -Xylylenediamine, m-xylylenediamine. Mannich bases such as 2,4,6-tris (dimethylaminomethyl) phenol; ß-Aminoäthyl-piperazinj adducts of acrylonitrile or monoepoxides, such as ethylene oxide or propylene oxide, with polyalkylenepolyamines, such as diethylenetriamine or triethylenetetramine; Adducts of polyamines, such as diethylenetriamine or triethylenetetramine, in excess, and polyepoxides, such as bisphenol A polyglycidyl ethers; Ketimines, for example from acetone or

009Ö83 / 212Ö

Methyl ethyl ketone and bis (p-aminophenyl) methane; Adducts Monophenols or polyphenols and polyamines; Polyamides, especially those made from aliphatic polyamines, such as diethylenetriamine or triethylenetetramine, and dimerized or trimerized unsaturated fatty acids such as dimerized linseed oil fatty acid (VERSAMID); polymeric polysulfides (THIOKOL); Dicyandiamide, Aniline-formaldehyde resins; polyhydric phenols such as resorcinol, 2,2-bis (4-hydrophenyl) propane or phenol-formaldehyde resins; Boron trifluoride and its complexes and ΒΡ -, - amine complexes, e.g. BF monoethylamine complex; Acetoacetanilide-BF ^ complex; Phosphoric acid, triphenyl phosphite.

Hardening accelerators can also be used for hardening, in particular when using polyamides, polymeric polysulfides, dicyandiamide or polycarboxylic acid anhydrides as a hardener; such accelerators are e.g. tertiary amines, their salts or quaternary ammonium compounds, e.g. 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, 2-ethyl-4-methyl-imidazole, triamylammonium phenolate, tin acylate, such as tin octoate; or alkali metal alcoholates such as sodium hexanetriolate. .

During the curing of the epoxy-containing compounds according to the invention Adducts with carboxylic anhydrides are expediently used for 1 gram equivalent of epoxide groups 0.5 to 1.2 gram equiva- " lent anhydride groups.

009893 / 312Q

- 15 - ■■ ·. ·

The term "hardening" as used herein means the conversion of the above diepoxides to insoluble and infusible, crosslinked products, usually with simultaneous shaping into molded bodies, such as castings, Pressed bodies or laminates or flat structures, such as paint films or adhesions.

The present invention therefore also relates to

curable mixtures for the production of moldings including Sheet-like structures are suitable and which optionally contain the adducts according to the invention containing epoxy groups together with a non-flexibilized polyepoxide, and a hardener for epoxy resins such as a polyamine or a polycarboxylic acid anhydride.

The adducts according to the invention, as well as most of them Adduct resin / hardener mixtures are crystalline at room temperature and have a surprisingly high crystallization transition temperature. The adducts are therefore particularly suitable for applications such as molding compounds, fluidized bed powder, and laminating resins for the production of storage-stable pre-impregnated fabrics ("prepregs") or binders, as the resin / hardener mixtures have a surprisingly high storage stability due to the crystallinity of the adducts. The resin / hardener mixtures however, they can also be processed using the pouring and impregnation method. For example, metal objects can be cast around the rubber-like coating adheres well to the metal.

009883/2126

The adducts according to the invention or their mixtures with other polyepoxide compounds and / or hardeners can also be used before curing in any phase with customary modifiers, such as extenders, fillers and reinforcing agents, pigments, Dyes, solvents, leveling agents, thixotropic agents, flame-retardant substances, farm additives • will.

Suitable organic solvents for the modification are the curable mixtures e.g. toluene, xylene, butyl acetate, acetone, methyl ethyl ketone, ethylene glycol mono-butyl ether.

Extenders, reinforcing agents, fillers and pigments which can be used in the curable mixtures according to the invention include, for example: glass fibers, boron fibers, Carbon fibers, cellulose, polyethylene powder, polypropylene powder, Mica, asbestos, quartz flour, slate flour, burnt kaolin, aluminum oxide trihydrate, chalk flour, gypsum, antimony trioxide, Bentone, silicic acid airgel (AEROSIL), lithopone ', barite, titanium dioxide, carbon black, graphite, iron oxide or metal powder, like aluminum powder or iron powder.

Z-Ie Vrttaren. "Emisc ** e '-" nren im urce *!' Ll *: r? R 'Cc- longed

Condition, especially as lamination resins, dipping resins, impregnating resins, Casting resins or embedding and insulation compounds are used for electrical engineering. You can also for everyone else technical areas where common epoxy resins are used, are used successfully, e.g. as binders, adhesives, Paints, varnishes, molding compounds and sinter powders.

BATH ORIGINAL

In the following examples, percentages are percentages by weight.

For the preparation of The following acidic polyesters were adducts containing epoxy groups used:

Polyester A

1100.8 g (11 mol) of succinic anhydride, 901.2 g (10 mol) of butane-1,4-diol and 0.8 ml of pyridine were mixed and heated, a weak exothermic reaction occurring at 130.degree. The reaction mixture was heated further by additional heating at 15O ⁰ C and under nitrogen atmosphere and stirring for 10 hours at unte'r I5O-I6O C allowed to react. The reaction was then continued for 10 hours at the same temperature under a water jet vacuum (10-12 mmHg). The result was a crystalline polyester with an acid equivalent weight of 884 (theory 911) and a melting temperature of 107 ° C. (measured in a differential scanning calorimeter [DSC]).

Polyester B

434.3 g (4.34 mol) of succinic anhydride and 384.3 g (4.2.0 mol + ~ L% excess) butane-1,4-diol (corresponding to a ratio of anhydride to butanediol such as 31 * 30) are mixed, 0.5 ml of pyridine was added and the mixture was heated to 140.degree. Then. The temperature will rise to 160-165 ° C in 3 hours

009883/2126

and allowed to react for 8 hours under a nitrogen atmosphere and a further 36 hours under a water jet vacuum (12 Torr). The polyester is a crystalline product having an acid equivalent weight of 2645 (theoretical 2632.9) and a melting point of 117 ⁰ C is (measured in DSC).

Polyester C

^ 20.3 g (4.20 mol) of succinic anhydride and 360.5 g (4.0 mol) of butane-1,4-diol (corresponding to an anhydride to diol ratio of 21:20) are mixed, 0.5 ml of pyridine are added and for 8 hours under nitrogen atmosphere to l4o-l6O ° C and 25 hours under a water jet vacuum (12 mm Hg) to I60 - 165 ⁰ C heated. The product obtained then has an acid equivalent weight of 1714 (theory 1771 * 9) and a melting point (measured in DSC) of 116.degree.

Polyester D

765 g (7 * 65 mol) of succinic anhydride and 695 g (7 * 49 mol + 3 % excess) butane-1,4-diol (corresponding to a ratio of succinic acid to butanediol of 51 * 50) were mixed and 2 g of methylimidazole were added . The mixture was then heated to I60 170 ⁰ C, with a rapid elimination of water began. The reaction mixture was continued at 170 ⁰ C allowed to react until the acid equivalent weight no longer increased. After 96 hours, 138 ml of water had been split off and the acid equivalent weight was 4650 (theory: 4341). After cooling, the product was a crystalline mass with a melting point of 114 ° C.

Manufacture of moldings

To determine the tensile strength, either 1 mm thick plates were cast and test specimens no. 2 according to ISO R 527 punched and these tested according to ISO or directly 4 mm thick test specimens according to DIN 16 946 sheet 1, respectively. DIN 53 455 sample form 5, produced and with a tear speed of 50 mm / minute tested according to this standard.

009883/2126

The crystallization transition temperature (KUT) was from Perkin Elmer determined with a "Differential Scanning Calorimeter" (DSC 1) with a heating rate of 8 ⁰ C per minute. When a resin is heated at a constant rate, when the crystals melt, there is a strong energy absorption by the resin within a relatively small temperature range.The temperature at which the energy absorption is greatest (maximum of the endothermic deflection) is referred to as the crystallization transition temperature (KUT).

example 1

li 221 g of polyester A were mixed with 112.5 g of diglycidyl tetrahydrophthalate with an epoxy content of 6.45 epoxy equivalents / kg (Epoxy resin I)! Corresponding to 3.0 equivalents Epoxy group to 1.0 equivalent carboxyl group] while Stirred for 3 hours at 140 ° C. under a nitrogen atmosphere. It a crystalline reaction product with an epoxide content of 1.055 epoxide equivalents / kg and a KUT of 99 ° C. was obtained (Adduct I).

Hardening:,

9 ^, 8 g of adduct I were ^{heated to 120 °} C. and mixed with 14.8 g of phthalic anhydride (corresponding to 1.0 equivalent of epoxide group to 1.0 equivalent of anhydride group) and 0.95 g of a 6 strength solution of the sodium alcoholate of 3-hydroxymethyl -2,4-dihydroxypentane (hereinafter referred to as "sodium hexylate" for short)

009887/2128

draws) in 3-hydroxymethyl-2,4-dihydroxypen.tan (hereinafter briefly referred to as "hexanetriol") mixed well. The mixture was now briefly evacuated to remove the air bubbles and then in preheated and treated with a release agent Aluminum molds of dimension 135 x. 135 "x 1mm cast. After a heat treatment for 16 hours at 140 ° C resulted in crystalline, rubber-elastic molded bodies obtained with the following properties;

Tensile strength according to ISO R 527 = 150 kg / cm elongation at break according to ISO R 527 = 210 %.

Example 2

529 g of polyester B were stirred with 62 g of epoxy resin I (corresponding to 1 equivalent of carboxyl group for 2 equivalents of epoxy group) for 3 hours at 140 ° C. under a nitrogen atmosphere. A white adduct (adduct II) which was crystalline at room temperature and had the following properties was obtained:

Epoxy content = 0.334 epoxy equivalents / kg

Acid equivalent weight = 15000

KUT = 115 ° C (secondary maximum at 96 ⁰ C)

Hardening;

a) 100 g of adduct II were heated to 140 ° C. and mixed well with 4.9 g of phthalic anhydride (corresponding to 1 equivalent of anhydride to 1 equivalent of epoxide group). After a short evacuation, the mixture was in the preheated. to shape

009883/2126

Cast according to Example 1 and subjected to a heat treatment for 16 hours at 140.degree. It became crystalline Shaped body obtained with the following properties:

Tensile strength according to ISO R 527 (1 mm) = 330 kg / cm ²

Elongation at break according to ISO = ² I-OO % »

Tensile strength according to DIN 53 455 (4 mm) = 290 kg / cm ²

Elongation at break according to DIN = 250 %

KUT ■ = 109 ° C

b) When using 1.0 equivalent of methylnadic anhydride instead of 1.0 equivalents of phthalic anhydride and otherwise the same composition and processing as in example 2a) moldings were obtained with the following properties:

Tensile strength according to ISO R 527 (l mm) = 370 kg / cm elongation at break according to ISO = 400 %

Tensile strength according to DIN 53 455 (4 mm) = 290 kg / cm ² elongation at break according to DIN = 250 #

KUT = 108. ⁰ C

The hard rubber-like moldings have an exceptional Toughness and also have a surprisingly high crystallization transition temperature on.

009883/2126

Example j?

g of polyester C were mixed with 93 g of epoxy resin I (corresponding to 1.0 equivalent carboxyl group to 2.0 equivalent epoxy group) stirred at 140 ° C. for 3 hours. It became a White, crystalline adduct (adduct III) obtained at room temperature with the following properties:

Epoxy content. = 0.42 epoxy equivalents / kg KUT = 112 ° C (secondary maximum at 104 ° C)

Hardening:

a) 258 g of adduct III were ^{heated to 1 ^ 0 °} C. and mixed well with 14.8 g of phthalic anhydride (corresponding to 1.0 equivalent of anhydride to 1.0 equivalent of epoxy group). After a short vacuum treatment, the mixture was poured into the preheated molds according to Example 1 and subjected to a heat treatment for 16 hours at 140.degree. Hard rubber-like crystalline moldings were obtained with the following properties:

2 Tensile strength according to ISO R 527 (1 mm) = 262 kg / cm

* ..
Elongation at break according to ISO = 250 #

Some traction body were heated to 120 ⁰ C, stretched to 100 $ and slowly cooled in the stretched state "With the onset of crystallization was up stretched to 40Q $ elongation · and cooled under tension" The so stretched specimens had the following mechanical properties: ·:

009883/2126

- 23 -. = 1500 2033625 Tensile strength according to ISO R 527 = 50 2
kg / cm Elongation at break according to ISO R 527 = 240 Tensile strength according to DIN
(4 mm unstretched) 53 455 = 210 kg / cm Elongation at break according to DIN 53 455 = 97 % KUT ⁰ C

b) When using 1.0 equivalent of dodecenyl succinic anhydride instead of 1.0 equivalent of phthalic anhydride

and otherwise the same composition and processing as in Example 3 a) were molded articles with the following properties obtain:

Tensile strength according to ISO R 527 (1 mm) = 230 kg / cm ² elongation at break according to ISO R 527 = 210 % KUT = 98 ⁰ C

c) Using 4.95 g of diaminodiphenylmethane as hardener and otherwise the same processing as in Example 3 a), moldings were obtained with the following properties: λ tensile strength according to ISO R 527 (1 mm) = 300 kg / cm ² elongation at break according to ISO R 527 = '320 % tensile strength according to DIN 53 4 ^ 5 (4 mm) = 260 kg / cra ² elongation at break according to DIN 53 455 = 230 %

KUT = 107 ° C

Example 4

884 g (1.0 equivalent) of polyester A were mixed with J584 g (2.0 equivalent) the N, N'-diglycidyl compound of the following formula

r »

O = C C-CH-

OC CO

Il Il

0 0

with an epoxy content of 5.07 epoxy equivalents / kg (epoxy resin II) [corresponding to -1.0 equivalents of carboxyl group to 2.0 equivalents of epoxy group] for 3 hours at 140 ° C. under a nitrogen atmosphere. A crystalline at room temperature, the reaction product having an epoxy value of 0.669 Epoxidäquiv "l" nth / kg and a KUT of 105 ⁰ C. (adduct IV).

Hardening:.

a) 149.5 g of adduct IV were ^{heated to HO 0} C and 15.4 g of hexahydrophthalic anhydride (corresponding to 1.0 equivalent of epoxy group to 1.0 equivalent of anhydride group) and 1 * 5 g of a 6 # solution of "sodium hexoxide" in "Hexanetriol" mixed well, evacuated and poured into the molds according to Example 1. After a heat treatment, crystalline, rubber-elastic molded bodies with the following properties were obtained:

009883/2126

- 25 -. '■■ · ■

tensile strenght according to ISO R. 527 = 190 ρ
kg / cm Elongation according to ISO R 527 300 KUT 83 ⁰ C

b) When adduct IV is hardened with 1.0 equivalent of methylnadic acid anhydride (instead of 1.0 equivalents of flexahydrophthalic anhydride) and otherwise the same composition and processing as in Example 4 a) were molded articles with the following Properties obtained:

Tensile strength according to ISO R 527 = 220 kg / cm ² elongation at break according to ISO R 527 = 330 % KUT = 89 - ° C

C-) 149.5 g of adduct IV were ^{heated to HO 0} G and mixed well with 4.95 g of 4,4'-diaminodiphenylmethane (corresponding to 1.0 equivalent of epoxy group to 1.0 equivalent of nitrogen-bound active hydrogen atoms) and after a short time Vacuum treatment poured into the preheated molds according to Example 1 * '. After a heat treatment for 16 hours at l4o C moldings were obtained with the following properties: Tensile strength according to ISO R 527 = 25Ο kg / cm ² Elongation at break according to ISO R 527 = 100% KUT = 89 ⁰ C

d) 105 g of adduct IV were heated to l40 ° C and 120.2 g of an acidic, weakly branched polyester which consists of \ # 8 13 g of glycerol, 283.4 g 1,4-butanediol and 360.0 g succinic ; acid anhydride was added (corresponding to 1.0 aequir.

009883/2126

"valerite carboxyl group to 1.0 equivalents epoxide) and after cooling to 120 ⁰ C with 0.25 g of 1-methylimidazole mixed well. The mixture was then evacuated briefly and poured into the preheated molds according to Example 1. After a heat treatment for 16 hours Moldings with the following properties were obtained at 140 ° C:

Tensile strength according to ISO R 527 = 270 kg / em ² elongation at break according to ISO R 527 = 400 % KUT = 97 ° c

In a further experiment, the tensile bodies were heated to HO ⁰ C and at this temperature up to. $ 100 stretched. Under this stretch they were slowly cooled and, when crystallization began, they were further stretched to about 400 $. These stretched tensile bodies had the following properties at room temperature:

Tensile strength according to ISO R 527 = I800 kg / cra ² elongation at break according to ISO R 527 80 %

Example 5

221 g of polyester A were mixed with 88.1 g of the diepoxide compound of the formula, which is liquid at room temperature

CH η CH

, CH CH-CO-CH ₂ -CH

CH

CH ₂ CH ₂

CH

009883/2126

(3 ', 4'-Epoxoxycyclohexylmethyl- ^ »^ -epoxycyclohexanecarboxylate) with an epoxy content of 7.1 epoxy equivalents / kg (epoxy resin III) (corresponding to 2.5 equivalents of epoxide group to 1.0 equivalents of carboxyl group] at 140 ° C. for 3 hours warmed up. The reaction product was crystalline and had a Epoxy content of 0.845 epoxy equivalents / kc and a 'KUT of 99 ° C (adduct V).

. "λ % ß ■ i_ a ι j_ £ ■ * #x ™

Hardening:

a) 118.5 g of adduct V were heated to 150 "C and mixed with 61.9 g of polyester A, 4.62 g of hexahydrophthalic anhydride (corresponding to 0.> equivalent anhydride group + 0.7 equivalent carboxyl group to 1.0 equivalent epoxy group1 and 1, 2 g of a 6 # solution of "sodium hexylate ¹¹ in" hexanetriol "were mixed well, evacuated and poured into the preheated molds according to Example 1. After a heat treatment for 16 hours at 140 ° C., molded articles were obtained with the following properties;

Tensile strength according to ISO R 527 = 210 kg / cm ² elongation at break according to ISO R 527 = 80 | ί KUT ■ - 92 ° e

b) 118.3 g of adduct V were heated to 120 ⁰ C, with 5.96 g of bis (Juamino-JJ-methylcyclohexyl) methane (corresponding to 1.0 equivalents of nitrogen-bonded hydrogen atoms active to 1.0 equivalents of epoxide ) mixed well, evacuated and poured into the preheated molds according to Example 1. After a heat treatment during

009883/2126

200 2
kg / cm 80 * . 89 ⁰ C

Moldings with the following properties were obtained for 16 hours at 140 ° C:
Tensile strength according to ISO R 527
Elongation at break according to ISO R 527
KUT

Example 6

884 g of polyester A were mixed with 308 g of diglycidyl hexahydrophthalate with an epoxy content of 6.5 epoxy equivalents per kg (epoxy resin IV) [corresponding to 1.0 equivalents of carboxylic acid to 2.0 equivalents of epoxy group] and 1.8 g of an oily solution of "sodium hexoxide" in "Hexanetriol" was stirred for 5 hours under a nitrogen atmosphere. A white, crystalline product was obtained (adduct VI) with the following properties:
Acid equivalent weight => 20,000

Epoxy content = 0.567 epoxy equivalent

per kg

KUT = 101 ⁰ C

Hardening:

171 »5 g adduct VI was mixed with 15 * 4 g of hexahydrophthalic anhydride (corresponding to 1.0 equivalents of epoxide to 1.0 equivalents of anhydride to 130 ⁰ C. and well mixed, evacuated, and in accordance with the preheated forms after the addition of 0.17 g Dirnethylbenzylarain Example 1 cast.

009883/2126

After heat treatment for 16 hours at 140 ° C., moldings were obtained with the following properties: tensile strength according to ISO R 527 = 220 kg / cm ² elongation at break according to ISO R 527 = 210 %

KUT = 85 ⁰ C

(Secondary maximum at 64 C)

Example 7

921 g of polyester A were mixed with 185 g Diomethandiglycidyläther having an epoxide content of 5 * 4 epoxide equivalents per kg (epoxy V) (corresponding to 2 equivalents of epoxy to 1 equivalent of carboxyl group, etc. of the polyester) for 3 hours at 145 ⁰ C stirred under nitrogen atmosphere. After cooling, the adduct was crystalline and had a melting point of 104 ° C. and an epoxide content of 0.94 epoxide equivalents per kg (adduct VII).

Hardening; ; .

a) 106.4 g of adduct VII were heated to 130 ° C. and mixed well with 26.6 g of dodecenylsuccinic anhydride (corresponding to 1.0 equivalent of epoxy group to 1.0 mol of anhydride group). After a short vacuum treatment, the mixture was in the. preheated to l60 ° C forms corresponding to Example 1 M molded and subjected to heat treatment for 16 hours at l60 ° C. The moldings obtained in this way had the following properties
Tensile strength according to ISO R 527 = 88 kg / cm * elongation at break according to ISO R 527 = 200 %

KUT = 76 ⁰ C

O
ο b) When using 4.95 g of 4,4'-diamino diphenyl methane

instead of dodecenyl succinic anhydride and otherwise

ω the same processing as in Example 7 ² O, _{molded J 0} bodies with the following properties were obtained:

k> tensile strength according to ISO R 527 = 170 kg / cm elongation at break according to ISO R 527 = 50 %
KUT = 89 ° C '

Belsplel 8

46O g of polyester A were mixed with 128 g of the Ν, Ν'-diglycidyl compound the formula

WJ

HC-C C = O

CH-CH-CH ₂ -N N-CH ₂ -CH-

C.
Il
0

with an epoxy content of 7.8 epoxy equivalents of epoxy resin VI (corresponding to 2.0 equivalents of epoxy group to 1.0 equivalent of carboxyl group) for 3 hours at 145 ° C under a nitrogen atmosphere. The adduct was crystalline after cooling and had a melting point of 104 ⁰ C and an epoxide content of 0.63 equivalents of epoxy per kg (adduct VIII).

Hardening; :

a) 158.6 g of adduct VIII were ^{heated to 130 °} C. and mixed well with 15.4 g of hexahydrophthalic anhydride (corresponding to 1.0 equivalent of epoxy group to 1.0 mol of anhydride group). After a short vacuum treatment, the mixture was poured into the molds preheated to 160 ° C according to Example 1 and subjected to a heat treatment for 16 hours at 160 ° C; The moldings obtained in this way were rubber-elastic and had the following properties:

Tensile strength according to ISO R 527 = 148 kg / cm elongation at break according to ISO R 527 = 200 % KUT = 8l ° C

009883/2126

- 31-bj When using 4.95 6 4, V-diaminodiphenylmethane instead of hexahydrophthalic anhydride and otherwise the same processing as in Example 8 a) were molded articles with the following properties obtain:

Tensile strength according to ISO R 527 = 211 kg / cm ² elongation at break according to ISO R 527 = 130 % KUT = 97 ° C

Example 9

465 g of polyester D were treated with epoxy resin I (corresponding to 1.0. Equivalent carboxyl group of the polyester to 2 equivalents epoxy group) for 3 hours at 140 ° C. under a nitrogen atmosphere touched. After cooling, the adduct obtained was crystalline and had a melting point of 112 ° C. and a Epoxy content of 0.32 epoxy equivalents per kg (adduct IX).

Hardening :

31 »> g adduct IX were heated to 14O ° C and treated with 2.32 g of epoxy resin I, then with 6.65 g Dodecenylbernstelnsäureanhy drld = M (corresponding to 1.0 equivalent of epoxide group of the adduct * and 1.5 equivalents of epoxy group of the epoxy resin I to 2.5 equivalents of anhydride group) and finally mixed well with 0.031 g of dimethylbenzylamine. After a short vacuum treatment, the mixture was poured into the molds preheated to 160 ° C according to Example 1 and then subjected to a heat treatment at 160 ° C for 16 hours. The moldings obtained in this way had the following properties:

2 Tensile strength according to ISO R 527 = 175 kg / cm

Elongation at break according to ISO R 527 = 200 %

KUT = 103 ⁰ C 009883/2126

Claims (1)

Claims 1. Process for the production of new adducts containing epoxide groups from polyepoxide compounds and acidic, linear polyesters, characterized in that (a) linear polyesters which have terminal carboxyl groups average formula U O - ^ rCI-0 ^ CH _o -h-0-C- (CH -) ^ - CJ — OH (I) * - ^ Il ^ 4 I! ^^ Il Il 0 wherein ζ is a number of at least 6, reacts with (b) diepoxide compounds with adduct formation in the heat, 0.1 to at most 0.65, preferably 0.4 to 0.6 equivalents of carboxyl groups per 1 equivalent of epoxide groups begins. 2. The method according to claim 1, characterized in that that one uses linear, acidic polyester (a), in which the symbol ζ in the formula (I) is a number in the value from 6 to 80, preferably from 9 to 40, is. 3. The method according to claims 1 and 2, thereby characterized in that diepoxide compounds (b) are used, which in the molecule an average of two glycidyl or ß-methylglycidyl groups bound to an oxygen, sulfur or nitrogen atom each own. . 009883/2126 ■■ -; »■ .- 203362! 4. The method according to claims 1 and 2, thereby characterized in that the diepoxide compounds (b) used are cycloaliphatic polyepoxide compounds whose 1,2-epoxide group sit on carbocyclic five or six rings. 5. The method according to claim 3, characterized in that that diglycidyl esters of dicarboxylic acids are used as diepoxide compounds (b). 6. The method according to claim 5, characterized in that H
that as a diepoxide compound Δ -Tetrahydrophthalic acid or Hexahydrophthalic acid diglycidyl ester used. 7. The method according to claims 1 to 3, characterized characterized in that diglycidyl compounds are used as diepoxide compounds of the N-heterocyclic series used, their heterocyclic ring at least once the group -N-C- I Il having, and wherein the two glycidyl groups are linked directly to endocyclic nitrogen atoms. . 8. The method according to claim 7, characterized in that that the diepoxide compound is 1,1'-methylene-bis-O-glycidyl-S ^ -dimethylhydantoin) used. 9. The method according to claim 7, characterized in that the diepoxide compound N (I), N (3) -diglycidyl-5> 5-dimethylhydantoln used. 009883/2126 10. The method according to claim 4, characterized in that the polyepoxide compound is a diepoxide of the formula CH HC-CO-CH ₀ -CH HC "II ² I ^IN Io I CH HC-R 'R-CHp HC CH CH ₂ wherein R and R ¹ each represent a hydrogen atom or the methyl group, or a diepoxide of the formula ZV ITT 0 / V C. N OH ₂ / \ CH-CH HC 0 CH C N / \ / CH ₀ - 0 ο ' 2 CH C \ / CH ₂ used. 11. The method according to claim 3 * characterized in that that as diepoxide compounds (b) diglycidyl ether used by phenols or alcohols. 12. The method according to claim 11, characterized in that that diomethane diglyeidyl ether is used as the diepoxide compound. 009883/2126 1> · New adducts containing epoxy groups from (a) linear polyesters with terminal carboxyl groups the average formula I * 'I O O -O- (CH ₂ ^ -OC- (CH ₂ ^ -C - OH (I) OC wherein ζ denotes an integer of at least 6, and (b) diepoxide compounds, where in the adduct formation | 0.1 to at most 0.65, preferably 0.4 to 0.6, equivalents of carboxyl groups are used per 1 equivalent of epoxide groups will, 14. Adducts according to claim 13 »characterized in that that they are derived from linear, acidic polyesters (a) in which the symbol ζ in the formula (I) is a number in the range from 6 to 80, preferably in the range from 9 to 40, means. 15. Adducts according to claims 13 and 14, thereby characterized in that they are derived from diepoxide compounds (b), which in the molecule an average of two glycidyl groups bound to one oxygen, sulfur or nitrogen atom each or have ß-methylglycidyl groups. 16. Adducts according to claims 13 and 14, thereby characterized in that they are derived from, as diepoxide compounds (b), cycloaliphatic diepoxide compounds, their 1,2-epoxide groups sit on carbocyclic five or six rings. 009883/2126 17. Adducts according to claim 15, characterized in that that they are derived from the diglycidyl esters of dicarboxylic acids. 18. Adducts according to claim 17, characterized in that that they are derived from the diepoxide compounds Δ-tetrahydrophthalic acid or diglycidyl hexahydrophthalic acid. 19 · Adducts according to claim 15 »characterized in that they are derived from the diglycidyl compounds of the N-heterocyclic series, the heterocyclic ring of which has at least once the group -IiT-C-, and viotel the two" Glycidyl groups directly with endocyclic nitrogen atoms are linked. 20. Adducts according to claim 19? characterized, that they differ from the diepoxide compound 1,1 "'-Methylene-bis- (3-glycidyl-5,5-dimethylhydantoin) derive. 21. Adducts according to claim 19, characterized in that that they are derived from the diepoxide compound N (1), iT (3) -diglycidyl-5,5-dimethylhydantoin-. · 22. Adducts according to claim 16, characterized in that they differ from a diepoxide of the formula 009883 / 212S ORIGINAL INSPECTED CH CH CH HC C-O ^ CH_-CH HC <l Ii Ί l> CH HC-E ¹ E-CH HC CH ₂ CH ₂ wherein R and R ¹ each represent a hydrogen atom or the methyl group, or a diepoxide of the formula. CH ₂
GH V CH-CH HC CH _2-0 ^N PH CH ₀ CH _p HC CH ₂ CH ₂ . derive. 23. Adducts according to claim 1-5 »characterized in that that they are derived from diglycidyl ethers of phenols or alcohols. 24. Adducts according to claim 23 * characterized in that that they differ from the diepoxide compound Diomethandigiycidyläther derive. 25. Curable mixtures which are suitable as casting, impregnating and laminating resins, as binders and molding compounds, characterized in that they contain an epoxy-containing adduct according to claims 11 to 20, optionally together with a non-flexibilized polyepoxide and • a hardener for epoxy resins such as a polyamine or a polycarboxylic acid anhydride. 001 ·· 3/212 ·