DE2132683C3 - Process for the production of internally plasticized epoxy resins - Google Patents

Description

C) HO
CH ₂ OOC-R ₂ -CH R ₁ R ₁ -CH -R ₂ CC) OCH
OH O

CH ₁ OOCR ₁ -CH-- R ₁

CH ₁ -CH-CH ₁ -O ^ f Vj- <f VO-CH ₁ -CH-CH ₂

° CH ₃

CH ₃

OH O

CH ₂ -CH -CH ₂ -O- <_> -Hf ^> - O-CH ₂ -CH CH ₂

R, = - (CH ₂ ) J-CH ₃ ,
R ₂ = - (CH ₂ J ₇ -CH = CH-CH ₂ -

6. A modified and internally plasticized epoxy resin with the following formula

CH ₂
-O- ^ ~~ H ^ , -C) -CHy-CH-CH ₂

CH ₇ -CH -CH, -O

CH ₂ -CH-CH ₁ -O
O

OH O

CH ₂ OOC-R ₂ -CHR ₁ R ₁ -CH -R ₂ -COOCH
OH O CH, 0 OC - R ₁ -CH - R,

0-CH ₁ -CH-CH ₁

O
CH ₁ -CH-CH ₁ -O -

CH ₂ OH 0

¥ ~ * VO-CH ₁ -CH - CH,

R ₁ = - (CH ₂ J ₅ -CH ₃ ,

R ₁ = - (CH ₂ ), - CH = CH-CH ₂ -

7. Use of the internally plaslified epoxy resins prepared according to claim 1 as casting resins in the Electrical industry.

It is known from OE-I'S 2 47 006 that Mono- or polyepoxides with mono- or polyhydric alcohols or compounds containing SH groups / weeks hardening to convert to plastics. Implementation of an epoxy group z. B. with an alcoholic hydroxyl group with dilution proceeds in the absence of a suitable one acidic or basic catalyst extremely slowly. Implementation of epoxides with SH groups containing compounds is faster than that with alcohols, but usually also has to be higher temperatures can be made.

Quaternary ammonium salts b / w were used to accelerate these reactions. -Bases. Alkali salts of higher fatty acids. Thiourea. Proposed salts of hydrofluoric acid or its amine complexes and BF ₃ in the form of its etherate or alcohol complexes.

With these known accelerators for implementation of mono- and or polyepoxides !! containing mil - OH - and or SIl groups Compounds for the purpose of hardening to plastics that are insoluble in organic solvents are Implementation, however, is not unambiguous, because one occurs to a greater or lesser extent Self-polymerization of the epoxy groups. so that some of the OH and / or SH groups are uncrosslinked remains. In the case of the compounds containing SH groups, there is also a strong darkening of the reaction products (plastics).

In U.S. Pat. No. 28 90 195, for example, epoxy resin preparations are described which consist of a Di-oxide compound and a polyol. preferably a phenol. These preparations are by mixing the components at a temperature that is about the melting point of the components corresponds, produced (column 3, lines 40 to 46) and can at temperatures between 25 and 250 C. preferably between HX) to ISO C (column S. lines 35, 36 and 49) are cured. To speed up acidic and basic catalysts, including boron trifluoride amine complexc, are used during the hardening process mentioned (column 9, lines 7 to 2s 19) and a possible polymerization of the Hpoxide groups pointed one below the other (column 4, lines 17 to 27).

of the present invention always adheres to the conditions of implementation in the United States patent 7U cured plastics, whereas the 11 produced by the process of the present invention Connections, as can be seen from part b of comparative experiment I. at high temperatures have excellent storage stability.

Also through the book: Epoxy Resins by Henry L c e and Kris Neville. McGraw Hill Book Company. Inc. New York. Toronto. Eondon 1957. pp. 164 to 182. known, the commercial ones To give epoxy compounds a greater or lesser degree of elasticity in various ways, namely:

E by external plastination. ie by adding ₄ s long-term molecules, e.g. B. plasticizers such as dibutyl phosphate. which remain irreparably after hardening.

2. by adding long molecules, e.g. B. Glycidyl ether longer glycols which are also crosslinked during curing, or

3. by incorporating long molecules into the epoxy compounds themselves.

Comparative experiment 1
shows in part a. that
28 90195 senenten

Since in the procedure according to item 3, the plasticizing component is part of the resin is. one speaks here of internal plasticization. This has various advantages, since there is no exudation of the plasticizer takes place and greater homogeneity is achieved because the plasticizing Component is part of the resin.

Known ways of making internally plasticizers Epoxy resins are z. B. the implementation of di- or irimerized fatty acids with di- or polyepoxide compounds in a ratio that 1 mole of di- or polyepoxide compounds per mole of carboxylic acid group implemented.

With higher-condensing epoxy resins based on bisphenol A. which already contain a larger amount of hydroxyl groups can plasticize them Fatty acid molecules through a catalylic transesterification, z. B. their Mclhylcstcr are built into the molecular structure.

These types of internal plasticization play a certain role in the industry, but they are internally plasticize resins in solvent-free form, highly viscous to solid, so that they can be used as casting resins. Adhesive resins and self-leveling coating compounds are not possible.

In British patent specification 1100187 and in the German patent 12 82 970 Schlcifgewebc are described, which inter alia with a internally plasticize with castor oil epoxy resin based on bisphenol A as a finishing and impregnation massc were provided. The internally plasticized epoxy resin used for impregnation was by using the diglycidyl ether of bisphenol A with castor oil in a molar ratio of 1: 0.25 to 1: 0.3 in the presence of Lewis acids, such as boron trite fluoride and its attachment compounds. for example acetic acid. Ethyl ether. Phenol. Cresol. Piperidine produced (DT-PS 12 82 970. Column 2. Lines 22 to 33) Γ

As in comparison 2 de: present patent description shows, leads to the conversion of castor oil and an epoxy resin based on bisphenol A (epoxy equivalent of 190) in the presence of the boron trifluoride piperidine complex even at increased Temperature only leads to slight polymerisation of the epoxy groups. An implementation to a defined Reaction product does not take place.

The invention relates to a process for the preparation of modify, in organic solvents soluble internally plasticizing epoxy resins of the general formula

with A =

CH ₂ -CH-CH ₂ -OA-Xj _n B

or

0-CH ₇ -CH-CH, -

609 618/185

CH, OH

A = -CH ₂ -C-CH ₂ -O-CH ₂ -CH-CH, -CH,

CH,] CH ₁ OH

-CH ₁ -CH -o4 CH, -CH- O -CH ₁ -CH-CH, -

J - III "-

, OH

CH,

hCH, -CH-CH, -0-

OH HO— ^ -CH-CH, -

and X = —O— or —S—, where Be condition holds that

wherein

D =

CH,

CH, -CH-O

CH ₃ -CH, -CH-

or

CH,

^ V-C- ,; ^ V

CH,
-CH ₂ -, ^x

CH,

CH ₂ -CCH ₂ -CH,

CH ₂ - _χ ; - CH, -

for / ι = 2 and

B = -CH, -CH-CH ₂ -for »i = 3.

R ₁

CH ₂ -OOC R ₂ -CH-O-CH ₂ -CH-CH ₂ B = CH-OOC R ₂ -CHO CH ₂ CH-CH ₂

^{! R} :

CH ₂ -OOC-R ₂ -CH - O -CH ₂ -CH-CH,

for π = 3 and

R ₁ = - (CH ₂ I ₅ -CH,

R ₂ = - (CH ₂ ), - CH = CH-CH, -

by reacting polyepoxides of the general formula

O O

CH ₂ -CH-CH ₂ -ODO-CH ₂ -CH-Ch ₂

- CH, - + -—

CH,

CH,

CH ₁ -CH-Ο - + - CH, -CH

] - ίο

represents or the connection

O
ρ CH- CH,

with compounds of the general formula [HX] Jl.

where X. B and π have the obice Bcdeutun », reacts in the presence of BF, complexes, which is characterized by this. that such BF, amine complexes are used which are soluble in the reaction mixture and in which the f \ ^mm _ ^cmcn PK _h value in aqueous solution of 15 t> is 4.3 and per g equivalent one with one equivalent e. ner Epoxidgruppc to be reacted hydroxyl group 1 to 100mmol BF complex are used and that per equivalent of an epoxy

group OJ to 0.9 equivalents of hydroxyl groups Continuous connection must be used:

The excess amounts of mono- and polyepoxides or _fo are selected such that per Aqui-

vulcni of an epoxy group preferably 0.4 to 0.6 equivalents the compounds containing OH groups and / or SH groups.

According to the process according to the invention, relatively low-viscosity teachings can be learned in a simple manner Manufacture plasticized epoxy resins. In addition, however, modifications of the epoxy resins can also be used through the incorporation of ionic groups, such as hydroxyl and mercapto groups, into the molecular structure be carried out according to the method according to the invention.

Suitable BF ₃ amine complexes are, for example

Tejcnigen, which are formed from the following amines (pK _h values in brackets) and BF ₃ :

'5

n-amylamine (10.63),
Aniline (4.63),

// - Phenylalanine = 2-aminoethylbenzene (9.S4). 2-ethylbenzimidazole (6.18),

Benzylamine (9.33), trans-bornylamine (10.17),
1-amino-3-methylbulane (10.60), 1,4-diaminobutane (11.15).
n-butylamine (10.77),

t-butylamine (10.83).

n-Butylcycloxylamine (11.23), cyclohexylamine (10.66).
n-decylamine (10.64),
Diethylamine (10.49).

Diisobutylamine (10.91), jo

Diisopropylamine (10.96).
Dimethylamine (10.73).
n-dodccanamine = laurylamine (10.63). 2-aminoethanol (9.50).

Ethylamine (10.81).

Hcxadccanamine (10.63).
1-aminoheptane (10.66).
2-aminoheptane (10.88).
n -xylamine (10.56).

2,4-dimethylimidazole (8.36).

Morpholine (8.33),
Methylamine (10.66).
n-nonylamine (10.64).
Octadecanamine (10.60).

Octylamine (10.65).

3-aminopentane (10:59).
3-Amino-3-methylpcntane (11.01). n-peniadecylamine (10.61).
Piperazine (9.83).

Propylamine (10.71).

Pyrrolidine (11.27 |,

Tctradecanamine = myristylamine (10.62). Tridecanamine (10.63).
Triethylamine (11.01).
Trimethylamine (9.81).

BFrBcnzylamine are preferred. BF, monoethylamine. BF ₃ propylamine and BF ₃ n-butylamine are used.

For one equivalent of a hydroxyl or sulfhydryl group to be reacted with one equivalent of an epoxide group, 100 to 1, preferably 15 to mmol. of the BF ₃ amine complex used. The reaction of the hydroxyl groups with the epoxy groups can be carried out in the temperature range from 20 to 200.degree. The implementation temperature depends on the respective BFj-Ammkomplex. For example, the conversion temperature when using BF, monoalkylamine or BF ₃ -ben / \ lamin is around 130 C. It is therefore expedient to heat the mixtures of hydroxyl groups or compounds containing sulfhydryl groups and compounds containing Hpoxide groups to be converted up to the temperature at which the reaction takes place Adequate companionship expires in 30 minutes to 15 hours. The reaction is expediently monitored via the increase in the epoxide equivalent. which indicates a decrease in the epoxy groups.

The reaction can be terminated by cooling below the reaction temperature.

Part of the BFj-amine complex is consumed during the reaction through the incorporation of the fluoride ions into the reaction product. Any excess of the BF ^ amine complex can be removed after the reaction has elapsed by adding basic substances such as fuller's earth. Calcium oxide. Calcium hydroxide. Barium oxide and barium hydroxide in excess can be rendered harmless to the complex. The basic substances are removed by filtration together with the products formed from them and the BF _{3 amine complexes.}

To facilitate the addition of the BF ₃ amine complexes, these can be dissolved by suitable solvents before addition to the mixture to be reacted of hydroxyl groups or sulfhydryl groups and a mixture containing epoxide groups.

Suitable solvents are, for. B. benzaldehyde. Toluic aldehyde. Salicylaldehyde, lactones such as; »'- propiolactone. , .'-butyrolaclone. - butyrolactone. Λ-valerolaclone and, ■ -caprolactone and esters of mono- and dicarboxylic acids known as monomeric plasticizers with monoalcohols such as tetrahydrofurfuryl adipate. Phthalic acid esters of monoalcohols, e.g. B. of n-butanol, amyl alcohol, 2-ethylhexanol. Nonanol. Benzyl alcohol individually or as a mixture. Furfuryl alcohol, lower and higher molecular weight polyols. z. B. glycerine, methylol propane, ethylene glycol as well as oxäthylicrte or oxpropylicrtc polyols or esters of phosphoric acid such as Trikrcsylphosphat useful.

From the large number of epoxy compounds that contain more than one 1,2-epoxy group in the molecule and which are reacted with the compounds containing hydroxyl groups or sulfhydryl groups The following may be mentioned: The epoxides of polyunsaturated hydrocarbons such as Vinylcyclohcxcn. Dicycloptintadicn. Cyclohexadiene. Cyclododecadiene, Cyclododccatriene, isoprene, 1,5-hexadicn. Butadiene, polybutadiene, divinylbenzene, oligomers of epichlorohydrin, polyvalent glycidyl ether Alcohols such as ethylene, propylene and butylene glycols. Polyglycemia. TTiiodiglycols, glycerine, penta erythritol. Sorbitol, polyvinyl alcohol, polyallyl alcohol and their reaction products with ethylene oxide andor propylene oxide, epoxy ethers, polyhydric phenols such as resorcinol. Hydroquinone, 2,2'-, 2,4'- and or 4,4'-dihydroxydiphenyl-melhan, bis- (4-hydroxy-3-methylphenyl) -methane. Bis - (4 - hydroxy - 3,5 - di chlorophenyl) methane, bis (4 - hydroxy - 3,5 - dibromo phenyl) methane. Bis - (4 - hydroxyphenyl) - ether 2,2 - bis - (4 - hydroxyphenyl) - propane, 2,2 - bis - (4 - hy hydroxy-3-methylphenyl) propane, 2-2-bis- (4-hydroxy-3-chlorophenyl) -prop> an, 2,2-bis- (4-hydroxy-3,5-d] chlorophenyl) propane. Bis - (4 - hydroxyphenyl) - phc nylmethane, bis- (4-hydroxyphenyl) -diphenylmethai

Bis - (4 - hydroxyphenyl) - 4 '- methylphenyl methylane. 1,1 -Bis- (4-hydroxyphenyl) -2,2-irichloroethane, bis- (4 - hydroxyphenyl) - 4 - chlorophenylmcthan, 1,1-bis (4 - hydroxyphenyl) cyclohexane. Bis - (4 - hydroxyphenyl) - cyclohexylmethane, 4,4'-dihydroxydiphynyl. 2,2'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl sulfone as well as their hydroxyethyl ether, phenol-formaldehyde condensation products, such as phenol alcohol, phenol aldehyde resins, S- and N-containing epoxides (N, N - Diglycidylaniline, N, N '- Dimethyldiglycidyl-4,4-Diaminodiphenylmcthan) and epoxides, which are obtained by conventional processes from polyunsaturated carboxylic acids or . polyunsaturated carboxylic acid esters of unsaturated alcohols have been produced, Glycidyl esters, polyglycidyl esters, obtained by polymerization or interpolymerization of glycidyl esters Unsaturated acids can be obtained or from other acidic compounds, for example Cyanuric acid, cyclic trimethylene trisulfone or their derivatives and others are available.

Just as well as the above di- or polyepoxides, their mixtures and also mixtures with monoepoxides, optionally in the presence of solvents or plasticizers, can be reacted in the process of the invention. Thus kön- ₂ $ NEN, for example, be used the following Monocpoxidc in admixture with the aforementioned di- or Polyepoxidverbindungcn: cpoxidierte easy-ungesältiglc hydrocarbons (Butylcn-, Cyelohexen-, styrene oxide), halogcnhalligc epoxides such. B. Epichlorohydrin, Epoxidäthcr monohydric alcohols (methyl, ethyl, butyl, 2-Äihylhcxyl-Dodccylalkohol). Epoxy ethers of monohydric phenols (phenol. Krcsol and other phenols substituted in the o- or p-position), glycidyl esters of unsaturated carboxylic acids. cpoxidized esters of unsaturated alcohols or unsaturated carboxylic acids and the acetals of glycidaldehyde.

The glycidyl ethers of 4,4'-dihydroxydiphenylpropane, the isomers of dihydroxydiphenylmethane, and polyhydric alcohols such as ethylene, propylene and butylene glycols are preferred. Thiodiglycols. Glycerin. Pentaerythritol. Sorbitol and its reaction product with ethylene oxide and / or propylene oxide are used. _{4 <i}

From the group of alcohols which are suitable for reaction with cpoxide-containing compounds, there may be mentioned: monohydric and polyhydric aliphatic. cycloaliphatic, fatty aromatic or aromatic alcohols, preferably those with primary or secondary hydroxyl groups. Examples of such monohydric alcohols are the simple saturated or unsaturated fatty alcohols with straight or branched carbon _{chains with 8 to 18 carbon atoms, for cycloaliphatic alcohols, cyclopenta-5S} nol, cyclohexanol and their substitution products, for aromatic alcohols benzyl alcohol. Phenylethyl alcohol as an example of a fatty alcohol and partially etherified with monohydric or polyhydric phenols polyalcohols, such as. B. the phenyl ether of glycol, of glycerol [2,2-bis-4 - (/ i-oxy-ethoxy) -phenyl] - propane, 2,2 - bis - [4 - fi, ·· - dioxy - propoxy) -pbenyl] propane. Examples of polyhydric alcohols are: ethylene glycol, neopentyl glycol, propylene glycol, bulylene glycol, hexanediol, higher glycols, which can be obtained, for example, by hydrogenation of dicarboxylic acid, xylylene glycol, hexahydroxylylene glycol, l ^ cyclohexanediol, glycerol. Diglyccrine. Triglycerine and higher polyglycerols. Methylglycerin. Trimelhylol ethane. Trimethylol propane. Pentaerythritol. Dipintacrylhril. l'entite. Hexite as well as mono-. Di- and polysaccharides, which can optionally be partially etherified or esterified. This also includes polyglycols. which are formed, for example, by polymerization or copolymerization of olefin oxides and both low molecular weight products such as diethylenulycol. Triethylene glycol as well as higher molecular weight products can include.

Also polyvinyl alcohol, partially acylic polyvinyl alcohol, Polyallyl alcohol and the copolymers of allyl alcohol with other unsaturated Compounds or partially or completely saponified polymers of vinylidene carbonate can be used with Epoxides are implemented.

The group of polyhydric alcohols should also include compounds that additionally Contain ester groups, such as esters of oxyacids with mono- or polyhydric alcohols, z. 15. Tartaric acid esters. Castor oil or polyester, made from polycarboxylic acids and an excess of polyols have arisen. Also alcohols containing sulfur or nitrogen, such as. B. thiodiamine glycol. N.N-diethylalhanolamine. Triethanolamine. mono- and polymethylol compounds. those containing, for example, by reacting amino groups Compounds with formaldehyde are formed, such as methylolureac. Methylolmelamine, can be \ orlcilhafl implement according to the method according to the invention.

The partial glycidyl ethers can also be polyvalent Alcohols mentioned above for Implementation with the epoxy compounds are used, for. B. the Monoglvcidyläther von GIykolcn. like ethylene glycol. Neopentyl glycol. Propylene glycol and butylene glycol. the mono- and polyglycidyl ethers more than dihydric alcohols, as they have already been mentioned, as far as one free hydroxyl group is available. and the corresponding glycidyl ethers by polymerization or Copolymerization of the dihydric and polyhydric alcohols and olefin oxides such as ethylene oxide or propylene oxide, if a free hydroxyl group is still present.

Advantageously, the reaction products obtained in a known manner can be used without isolating the reaction products Reaction products from the polyhydric alcohols mentioned and epichlorohydrin. which in general Glycidyl ether containing hydroxyl groups and polyglycidyl ethers free of hydroxyl groups in addition to contain each other, are reacted according to the process according to the invention, whereby polyglycidyl äthcr of the polyhydric alcohols mentioned arise that are free from monofunctional epoxy compounds fertilizers which, when hardened, lead to a deterioration in mechanical strengths ren.

Polyhydric alcohols such as Α thy lenglycol are preferred. Neopentyl glycol. Propylene glycol. Butylene glycol, hexanediol. Hexahydroxylylcnglycol. Glyccrir trimethylol ethane. Trimethylol propane. Pentaerythri and / or their copolymers with olefin oxides such as ethylene oxide and / or propylene oxide, esters voi Hydroxycarboxylic acids, such as glycolic acid, -hydroxy propionic acid and ricinoleic acid with the above Alcohols and partial glycidyl ethers are preferred

named alcohols in which at least one hydroxyl group is present, used.

From the group of the mercapto compounds which are suitable for reaction with epoxides are the called simple mercaptans, thiophenols and polymercaptans. Also several mercapto groups containing polysulfides, which by reaction of an aqueous solution of alkali polysulfides with aliphatic Dihalides and reductive cleavage of the polysulfide groups in the aqueous dispersion with Calcium hydrogen sulfite, sodium sulfite or other reactants according to the Swiss patent 1 27 540, British Patent 3 02 270 and German Patent 6 70 140 can be obtained can and have an average molecular weight Can have 50 to 10,000 are suitable for the implementation according to the invention. To be favoured Lauryl mercaptan, dodecyl mercaptan, octyl mercaptan, nonyl mercaptan, 1,2-ethanethiol and / or 1,2-propane! Hiol used.

The products prepared according to the invention can be hardened with the known hardeners for epoxy resins such as aliphatic, cycloaliphatic and aromatic polyamines, anhydrides such as phthalic anhydride or hexahydrophthalic anhydride and catalytically active hardeners such as BF ₃ complexes. They can be used alone as resin components or for plasticizing epoxy resins based on bisphenol A and epichlorohydrin. Relatively little heat develops during the hardening process. The special properties of the cured products include their high impact strength, their extraordinarily good resistance to temperature changes, their good aging resistance and their very good plasticity even in low temperature ranges.

The products produced according to the invention can be used as casting resins in the electrical industry especially when temperature-sensitive switching elements and components have to be embedded. They can also be used as a base resin for the production of fillers, sealants and potting compounds serve. They can also be used in conjunction with polyamidoamines serve as hardeners for the manufacture of adhesives. Before curing, the invention manufactured reaction products with fillers such as silicon dioxide, hydrated aluminum oxide, Titanium dioxide, glass fibers, wood flour, mica, graphite, calcium silicate and / or sand as well as the usual pigments, for example, be provided with grain sizes of 0.1 to 5 mm. Farther can dyes. Solvents or sensitizers such as phthalic acid esters of monoalcohols, z. B. n-butanol, amyl alcohol. 2-ethylhexanol. Nonanol, Benzyl alcohol alone or in a mixture,; -Butyrolactone, ^ -Valerolaclone. j-caprolactone, furfuryl alcohol, lower and higher molecular weight polyolc. z. B. glycerine, trimethylol propane. Ethylcnglycol as well oxäthyliertc or oxpropylicrte polyols are added. f> o

The hardening of the reaction products prepared according to the invention can optionally be effected by means of additives accelerating substances from the group of monohydric or polyhydric phenols, in particular Aminophenols, monohydric or polyhydric alcohols or compounds such as epichlorohydrin. Mercapto compounds. Thioether. Dithioethers or compounds with nitrogen-carbon-sulfur groups or sulfoxide groups. be shortened.

The following examples explain the process according to the invention.

example 1

215 g of castor oil, 270 g of an epoxy resin based on bisphenol A and epichlorohydrin with a viscosity of 11,000 cP (25 C) and an epoxy equivalent of 187 and 13 g of an HF, -Monoüthylamine complex were under an atmosphere of dried nitrogen with stirring on a Reaction temperature of 130 C heated. At this temperature, the epoxy equivalent was determined at intervals of 30 minutes. An epoxy equivalent of 475 was reached after 5 hours. The reaction was terminated by cooling to 120.degree. An excess of the 3F ₍ complex was rendered harmless by adding 3.5 g of finely powdered calcium hydroxide and stirring for 30 minutes. It was then cooled to 100 ° C. and filtered.

The homogeneous reaction product had a viscosity of 22,40OcP. measured at 25 C with the Höpplcr-Viskosimeler, and a pot life (H) Og of the reaction product with 6 g of triethylentetramine homogeneous mixed) of 75 minutes at 20 C. Under pot life is the period of time between the mixing understood the components and the gelation of the mixture. The reaction product according to the invention is a homogeneous, internally plasticized epoxy resin with a pale yellow color.

Example 2

215 g of castor oil, 285 g of an epoxy resin based on bisphenol A and epichlorohydrin with a viscosity of 1130OcP (25 C) and an epoxy equivalent of 188 and 1.3 g of a BF, benzylamine complex were under an atmosphere of dried nitrogen with stirring to a Reaction temperature of 130 C heated. At this temperature, the epoxy equivalent was determined at intervals of 30 minutes. An epoxy equivalent of 510 was reached after 60 minutes. The reaction was terminated by cooling to 120.degree. An excess of the BF ₃ complex would be rendered harmless by adding 3.5 g of finely powdered calcium oxide and stirring for 30 minutes. Thereafter, to 100 "C gekühli and filtered. The homogeneous reaction product hold a viscosity of 4100OcP at 25 ^[C gemesser mil the Hoppler Viskosimeler, and a Topfzeii (100g Reaktionsproduklcs with 6 g of triethylene tetramine homogeneously mixed) 75 minutes be 20 'C

The reaction product produced according to the invention dukt is a homogeneous, internally plasticized epoxy resin with a pale yellow color.

Example 3

380 g of an epoxy resin based on bisphenol A and epidilorhydrin with a viscosity of 11,30OcF (25 C) and an epoxy equivalent of 188,200 1 of a polyoxypropylene glycol with an average molecular weight of 400 and 1.5 g of a BF, benzylamine complex were among the Same conditions as described in Examples 1 and 2 heated to a reaction temperature of 130 C.

An epoxy equivalent of 450 was reached after 3 hours. The reaction was interrupted by cooling to 120.degree. Any excess portion of the BF ₃ complex was rendered harmless by adding 3.5 g of fuller's earth and stirring for 30 minutes. It was then cooled to 100 ° C. and filtered. The homogeneous reaction product had a Gardner-Holdt viscosity of about Z ₆ , measured at 25 ° C., and a pot life (100 g of the reaction product mixed homogeneously with 6 g of triethylenetetramine) of about 3 ¹ A hours at 20 C.

The reaction product according to the invention provides a homogeneous internally plasticized epoxy resin pale yellow in color.

B e ι s ρ ι e 1 4

500 g of an epoxy resin based on bisphenol A and epichlorohydrin with a viscosity of 11,30OcP (25'C) and an epoxy equivalent of 188, 300 g of a polyoxypropylene glycol glycidyl ether with an epoxy equivalent of 326 and a viscosity of 66 cP (25 ° C), 200 g of a polyoxypropylene glycol with an average molecular weight and 400 and 1.8 g of a BF ₃ -benzylamine complex were heated to a reaction temperature of 130 to 135 ° C. under the same conditions as described in Examples 1 and 2 reached an epoxy equivalent of 400. The reaction was interrupted by cooling to 120 ° C. Any excess portion of the BF, complex was rendered harmless by adding 5.5 g of fuller's earth and stirring for 30 minutes and filtered. The homogeneous reaction product had a viscosity of 4200 cP, measured at 25 ° C. with the Höppler viscometer, and a pot life (100 g of the reaction product with 6 g of triae ethylene tetramine mixed homogeneously) of 5 ¹ Z ₂ hours at 20 C.

The reaction product produced according to the invention represents a homogeneous, low-viscosity, internal plasticized epoxy resin with a pale yellow color.

Example 5

215 g castor oil, 275 g of an epoxy resin based on bisphenol F (a mixture of the isomers of 2,2'-, 2,4'- and 4,4'-dihydroxydiphenyimethane) and epichlorohydrin with a viscosity of 270OcP (25 "C) and an epoxy equivalent of 174 and 1.4 g of a BF ^ -Benzylamine complex were under the same conditions as described in Examples 1 and 2 to a reaction temperature of 130 ° C warmed up. An epoxy equivalent of 450 was reached after about 4 hours. By cooling to 120 C the reaction was interrupted. A roughly excess portion of the BFj-Kompcxcs was through the addition of 3 g of finely powdered calcium oxide and stirring for 30 minutes made harmless. It was then cooled to 100 ° C. and filtered. The homogeneous reaction product had a viscosity act of 17 00OcP. measured at 25 C with a Höppler viscometer. and a pot life (100 g des Reaction product mixed homogeneously with 6 g of triethylenetetramine) for 105 minutes at 20 C.

The reaction product produced according to the invention is a homogeneous, relatively low-viscosity product internally plasticized epoxy resin with a pale yellow color.

Example 6

76 »an epoxy resin based on bisphenol Λ and ^ epichlorohydrin with a viscosity of 10 50OcP (25 C) and an epoxy equivalent of 185 65 Si of a polyoxypropylene glycol glycidyl ether with an epoxy equivalent weight of 326 and a viscosity of 66 cP (25 C), 93 g Ri Inus oil and 0.5 g of a BF, benzylamine complex were heated to a reaction temperature of 130 to 135C under the same conditions as described in Examples 1 and 2. An epoxy equivalent of 550 was reached after around 4 hours. The reaction was interrupted by cooling to 120 ° C. An approximately excess portion of the BF ₃ complex was rendered harmless by adding 2 g of fuller's earth and stirring for 30 minutes. It was then cooled to 10 ° C. and filtered. The homogeneous reaction product had a viscosity of 4000 el ' measured at 25 ° C. with a Höppler viscous agent and a pot life (100 g of the reaction product with 6 g of triethylenetetramine mixed homogeneously) of about 8 hours.

The reaction product produced according to the invention represents a "homogeneous, low-viscosity, internal plasticized epoxy resin with a pale yellow color.

Example 7

225 g of an epoxy resin based on bisphenol Λ and epichlorohydrin with a viscosity of 10 50OcP (25 ⁰ C) and an epoxy equivalent of 185, 125 ρ of a polyoxypropylene glycol diglyeidylether with an epoxy equivalent of 326 and a viscosity of 66 cP (25 C), 125 g of a polyoxypropylene glycol with an average weight of 750 and 0.7 g of a BF ₃ -benzylamine complex were heated to a reaction temperature of 130.degree. C. under the same conditions as described in Examples 1 and 2. An epoxy equivalent of 400 was reached after around 3 hours. The reaction was stopped by cooling to 120 C ^c. An approximately excess portion of the BF, complex was rendered harmless by adding 3 g of fuller's earth and stirring for 30 minutes. It was then cooled to 100 ° C. and nitrided. The homogeneous reaction product had a viscosity of 220 ° C, measured at 25 ° C. with a Höppler viscometer. and a pot life (100 g of the reaction product mixed homogeneously with 6 g of triethylenetylamine) of about 6 ¹ ₂ hours.

The reaction product produced according to the invention is a homogeneous, low-viscosity, internal plasticized epoxy resin with a pale yellow color.

Example 8

a) 312 g ncopentylglyco! and 1680 g of Fpichlorohydrin were stirred in an apparatus with a condenser and a distillation receiver, which the Separation of water and recycling of the l-.pichlorhydrin allowed, heated to the boil. As soon as epichlorohydrin was distilled into the template started doing that. 531 g of aqueous 45% by weight sodium hydroxide solution into the reaction mixture using a dropping funnel to drop. A sump temperature of 115 C and a vapor temperature of 105 C maintained and thus the water resistant

The azeciropic water-epichlorohydrin mixture is distilled from the reaction mixture into the template. »Σ after separation of the phases, AI ED ^: chlorohydrin was continuously returned to the reaction mixture and the water was removed. After 4 hours, the addition of the aqueous sodium hydroxide solution was complete, and the batch was cooled to about 30.degree. Excess epichlorohydrate was distilled off under reduced pressure at 15 to 20 mm Hg. At the end of the distillation, the reaction mixture was heated to 80 ° C. The distillation residue was dissolved in 900 g of methyl isobutyl ketone, the sodium chloride formed was dissolved by KXM) ml of water - "5" ram ', whereby the water in the receiver became Mufcefan'en and methyl isobutyl ketone was returned to the batch. After the water had been separated off, 100 ml of methyl isobutyl ketone were distilled off The pressure was concentrated at 13 to 70 mm Hg and kept under this reduced pressure for a further 60 minutes at 120 ° C. The epoxy equivalent of the reaction product was 178 5, the viscosity was 47 ° C., measured at 25 ° C. with a Höppler viscometer the Ncopentylglykolmonoglvcidylälher, to about 30 weight percent from Nconentylglykoldiglyci dyHither and about 20 percent by weight of a polymcien diglyc.dylaiher of neopentyl glycol. .

b) 388 ε of the mixture a) and 0.9 g of a Bl ·., - BenzylamTn complex were heated to a reaction temperature of 130 ° C. under the same conditions as described in Examples 1 and 2. After 5 ¹ A hours, an epoxide equivalent of was reached. The reaction was interrupted by cooling to 120.degree. An approximately excess portion of the BF ₃ complex was ^{v "r" lead} made long by the addition of 2 a bleaching earth and 30 minutes harmless. Then it was cooled to 100 L and nitrated. The homogeneous reaction product had a viscosity of 2200 cP, measured at 2d C with a Hüpplcr viscobimcier. and a total ch'.ony content of 1.15 percent by weight. The reaction product produced in accordance with the invention is a mixture of diglycidyl ethers of neopentyl glycol with different degrees of condensation and low viscosity, which, either alone or with other epoxy compounds, can easily be converted with the usual epoxy resin hardeners to form tough-elastic molded articles or coating towers.

The reaction products according to Examples 1. 4, 6 and 7 were used as plasticizing additives to bisphenol A-epichlorohydrin base resins mechanical and electrical tests.

A. 20 g of reaction product Example 1,

56 g of a bisphenol A epichlorohydrin base resin with an epoxy equivalent of about 190.

24 g ρ - tert. - Butylphenylglycidyl ether was mixed homogeneously.
The hardening was with

28 g of a mixture consisting of 44 percent by weight from an addition product of 1 mol of triethylenetetramine and 1 mol of propylene oxide (a) and 56 percent by weight of an addition product of one mole of triethylenetramine. 1 mole of propylene oxide and 1 mole of acrylonitrile (b)

(a): H ₂ N (CH ₂ · CH ₂ NH)., · CH ₂ · CH (OH) CH.,

= C- ■ CH ₂ CH ₂ · NH (CH ₂ · CH ₂ · NH) ₃ ■ ■ CH ₂ CH (OH) CH ₃

which was stirred homogeneously into the mixture for 24 hours at room temperature and made for 2 hours at K) OC in 10 and 4 mm thick plate molds-24 g p-terl-Butylphenylglycidyläther with 27 g of said hardener mixture implemented and hardened.

men.

Table 1

HH-Il.

After removal from the mold, the corresponding test bars were used in the table compiled tests.

B. According to the information under A.

20 g of reaction product Example 4. 56 g of the base resin mentioned, 24 g of p-tert-butylphenylglycidyl ether with 26 g of said hardener mixture implemented and hardened.

C. According to the information under A.

20 g of reaction product Example 6.

56 g of the aforementioned basic hair / es.

24 g of p-lcrt.-Bulylphenylglyeidylälher with

26 g of said hardener mixture implemented

and hardened.

D. According to the information under Λ, 20 g of reaction product Example 7. 56 «of the aforementioned basic har / es.

Mixtures with Example 1, Example 4, Example 6, Example 7

Tensile strength 700 610 740 650

in Kp cm ² ^

Impact-resistant 13 21 34

55 speed in

Kn cm cm ²

726 1140 Π 50 Π 90

wedge in

* ° ^ Il from 32000 42000 37500 40500 Flexural strength- ^

wedge Kp cm ²

Kueldruck- 1180 »53« _(s hardness M) ".

"* ^pcmi 95 9.

Shore

Hardness Λ

continuation

Worth it,
° C

Surface resistance,
Ω, 1000 V
Volume resistance,
Ll · cm
Dielectric con-
constant at
(O ⁶ Hz

Dielectric
Loss factor
at 10 ^b Hz
Tracking resistance

Mixtures mil

Example 1 Example 4 Example 6 Example?

47 42 56

10 "10" 10 "ό

10 ¹⁴ 1O ^U 10 ¹⁵

ι

3.20 3.20 3.30

20th

0.040 0.026 0.042

KA 3c / KA 3c, KA 3c

0.4 mm 0.6 mm 0.5 mm

Further examples

Preparation of that used in the following examples Polyoxypropylene Glycidyl Ethers:

820 g of an anhydrous polyoxypropylene glycol with an average molecular weight of 400 will be in

600 ml of mineral spirits and dissolved under a nitrogen atmosphere heated to 70 C. It will

6 ml tin tetrachloride (anhydrous), dissolved in

40 ml light petrol (anhydrous), added dropwise within 10 minutes. While stirring vigorously and under a nitrogen atmosphere

370 g of epichlorohydrin were added dropwise over the course of 3 hours, the reaction temperature increasing to 70 ° C. After stirring at 70 ° C. for a further hour, the same temperature

500 g of 22.5 percent strength by weight aqueous sodium hydroxide solution were added dropwise over the course of one hour. Man stirs for two more hours at 70 ° C. and washes with it

500 g of water. At 70 ^c C will be again

500 g of 45 percent strength by weight aqueous sodium hydroxide solution were added over the course of an hour and still Stirred for two more hours at 70.degree. You then wash with

750 g of water and then with

100 g of water, acidified with 20% by weight phosphoric acid to pH 5.5 to 5.0 at i .-. Ul distilled solvent and water under a vacuum of about 50 mm Hg up to a temperature of 90 C and filtered after cooling to <30 C.

A polyoxypropylene glycol glycidyl ether with an epoxide equivalent of 330 and one is obtained Viscosity of 5OcP, measured at 25 C.

Example 9

140 e of an epoxy resin based on bisphenol A and epichlorohydrin with a viscosity of 100OcP PS ¹ C) and an epoxy equivalent of

187 130 g of the above-described polyoxypropylene alkymycidyl ether, 186 g of castor oil and 0.7 g of a BF, benzylamine complex were under one atmosphere of dried nitrogen to about 130 C heated with stirring. The epoxy equivalent was determined every hour. After 5 hours it was Hn epoxy equivalent of 593 reached. It was cooled to <100 ° C and, after adding 1 g of calcium hydroxide powder, calcium hydroxide filtered.

"The homogeneous reaction product had emc viscosity of 174OcP, measured at 25 L, and is an internally plasticized epoxy resin with a pale yellow color.

Example 10

380 g of an epoxy resin based on bisphenol A and epichlorohydrin with a viscosity of 1130OcP (25'C) and an epoxy equivalent of

188 190 g of the above-described Polyoxypropyknalyk'olglycidyläthers, 95 g each of Polyoxypropyienolykolen with the average molecular weights 400 and ToOO and 1 g of a BF ₃ -benzylamine complex were heated under an atmosphere of dried nitrogen to about 130 ° C with stirring. The epoxy equivalent was determined every hour. An epoxide equivalent of 390 was reached after 2 hours. It was cooled to <100 ^° C. and, after the addition of 1 g of fuller's earth, filtered. The homogeneous reaction product had a viscosity of 250OeP. It is measured at 25 C, and is an internally plasticized epoxy resin with a pale yellow color.

The reaction products according to Examples 9 and 10 were used as plasticizing additives to bisphenol A-epichlorohydrin base resins subjected to mechanical and electrical tests.

E. According to the information under A.

14 g of reaction product Example 9,
60 g of the base resin mentioned,

26 g of p-tert-butylphenol glycidyl ether with

27.5 g of said hardener mixture reacted and hardened.

F. According to the information under A.

20 g reaction product example 9,

56 g of the base resin mentioned,

24 g of p-tert-butylphenol glycidyl ether with

27 g of said hardener mixture implemented

and hardened.

The results are shown in Table 2.

Table 2

ftüfmethod test standard. Dimension mixtures mil
DIN

Example ¹ ) Example 10

Flexural strength 53452 K prm ² 1020 11 50 speed Blow 53453 Kp- 13th 16 toughness cm 'cm "

continuation

Prüfniethoiic test number Dimension blends with DIN

Example 9 Example 24

Prülmelhode test standard. Dimension mixtures mil DIN

Example ¹ ) Example

Tensile strength 53455 Kp cm 670 620

Fracture 53455% 5.1 4.5

strain

Ball 53456 Kp cm ² 1360 1310

pressure or (505)

Shorehurtc

Ε module 53457 Kp cm ² 40000 40000 _I5 zitäts-

from bending "constant

test at 10 ^h Hz

44 48

Irish

KA 3c KA 3c 20 loss

0.6 mm 0.9 mm factor

Martens- 53458 C

Creeping

electricity-

strength

53480

Upper 53482 U

cursing

resistance

Diameter - 53482 cm

gangly

resistance Dielcktri- 53483

Dielck- 53483

at IO ⁶ Hz

10 "10"

10 ¹ '

ίο ¹ ·

3.20 3.20

0.050 0.050

The reaction products according to Examples 1 and 2 can be represented by the following formula:

CH ₂ -CH-CH ₂ -O- ^ O %. 1 tf ^c ^

CH ₃

-O-CH ₂ -CH-CH ₂

1 '

OH O CH ₂ OOC-R ₂ -CH-R ₁

R ₁ -CH-R ₁ -COOCH

CH,

CH, -CH-CH, -O- '<;
O

OH

> -O-CH, -CH CH, CH ₂ OOC-R ₂ -CH-R ₁

CH,

CH ₃

CH ₂ -CH-CH ₂ -O OH

> —Q-CH ₂ -CH

0 CH ₂

CH ₃

R ₁ = - (CH ₂ ) S-CH ₃ .

R ₂ = - (CH ₂ ) T-CH = CH-CH, -

The reaction product according to example! 5 can be represented by the following equation:

CH ₂ -CH - CH ₂ -O- / O CH ₁

-Q-CH ₂ -CH OH

-CH ₂ O

R ₁ -CH-R ₂ -COOCH

CH,

CH ₂ -CH-CH ₂ -O
O

OH V- Q-CH ₂ -CH - CH ₂ COO-R ₂ -CH-R, CH ₂ OOC-R ₂ -CH-R ₁

Q-CH ₂ -CH - CH ₂

CH,

- CH - CH, - O - f

CH, - CH - CH, - O OH

-0-CH ₂ -CH

R, = - (CH ₂ ) ₅ -CH ₃ .

R ₂ = - (CH ₂ K-CH = CH-CH ₂ -

-CH ₂

609 618/185

26th

Further examples of the reaction of epoxides with —OH— and / or SH— groups Compounds to modified epoxy compounds soluble in organic solvents:

Example equivalents (VaIl der Lipoxidverbindunu

11 4 Bisphenol A diglycidyl ether (Epoxy equivalent equivalency = 190)

12 4 Bisphenol A diglyeide \ lather (Epoxy equivalents / gcwichl = 190)

13 4 Bisphenol A diglycidyl ether (Epoxy equivalent weight = 190)

14 4 Bisphenol A diglyeidyl ether (Epoxy equivalence weighted ^ 190)

15 6 Neopcnlyl glycol diglycidyl ether (epoxy equivalent weight = 135)

16 4 polyoxypropylene glycol diglycidyl ether (Epoxy equivalent weight = 33Ö)

17 4 Novolak polyglycidyl ether (epoxy equivalent weight = ISO)

18 4 vinyl cyclohexene dicpoxide

EquiviilcnlclVall der Oll b / w. SII -Vcrbiiulunj!

2 Pohoxypropylcnghkol (MW '= 400)
2 Polyoxypropyleiiulyköl (MW '= 700)

2 polyoxypropylene glycol

(MG '= ΊοοοΓ

2 1,2-propanethiol

3 glycerin

2 Hexaliydrox \\ ylylcnghkol

2 poly oxy propylene ul ycol IMG '= HK) O)'

2 polyoxypropylene glycol (MG "= Ί (K) O) '

The epoxy compounds obtained have the general formula

O CH ₂ -CH-CH ₂ -OAX- "B

niM.ilc des Hl · ', - amine complexes ·

35 BF ₁ -IkM-35 BF _, - Benz \ lamin 40 BF _, - Monoälh \ lamin 35 BF, -Ben / vlamin 40 BF, -Mono; ithslamin 35 BF, -Ben / \ l.imin 40 BF \ -Mono; ith \ laniin 30 BF, -Mono; ith \ lamin

with A =

OH

HO—- ·

-CH ₂ - OH C-CH, - Ο- and OH CH-CF CH, ^ CH ₂ -CH I, - CH,
pn ί
o4- - LM - OH CH ₂ - 3-5 V ' ΓΠ v, M - , -CH ₂ -CH ₂ -CH-CH, - - -CH ₂ CH,
—-CH ^ -CH-O- CH, -

6o V-CH, -

tind X = —O— or —S—. wherein the condition holds that

= ^ -CH ₃ -CH-O ^ CH ₂ -CH-

CH ₃ CH ₃

for π = 2 and B = -CH ₂ -CH-CH, -

⁶⁵ for π = 3.

In a preferred embodiment, ^{1 mol of a dicpoxide} compound is used. z / b. a low-

ti

Viscous diglycidyl ether of bisphenol A and / or bisphenol F or a diglycidyl ether of a polyoxypropylene glycol with an average molecular weight of 400 to 1000, individually or in a mixture with 0.6 to 1 VaI of a polyol compound, e.g. B. a polyoxypropylene glycol with an average molecular weight of 400 to 1000 in the presence of 5 to 10 mmol BF _r benzylamine or 20 to 35 mol BF, ethylamine reacted.

In the most preferred embodiment, I is mol ♦ ines diglycidyl ether of bisphenol A with a viscosity of 6000 to 15,000 cP (25 C) with 0.8 to 1.0 Valcn (based on the hydroxyl group) castor oil implemented in the presence of lOmMol BF, -Bcnzylamin.

Example 11

215 g of castor oil, 270 g of a Hpoxidharz.es based of 75% bisphenol F (isomer mixture of 2.2'-, 2.4'- and 4.4'-dihydroxydiphenylmethane). 25% bisphenol A and epichlorohydrin with a viscosity of 3200 cP (25 "C) and an epoxy equivalent of 173 and 1.4 g of a BFj-benzylamine complex under the same conditions as described in Example 1 and 2, to a reaction temperature of Brought 130 C and held at this temperature until an epoxy equivalent of 430 was reached. What was the case after about 4 hours. The reaction product was quickly cooled to room temperature and filtered after adding a filter aid. The homogeneous product had a viscosity of 11 80OcP (25 C).

The reaction product produced according to the invention is a homogeneous, relatively low-viscosity, internally plasticized epoxy resin with a pale yellowish color Coloring.

The reaction product obtained contains a mixture of plasticized epoxy resins, their formulas correspond to those for Examples 1 and 5.

Comparative searches to demonstrate technical progress

1. a) An epoxy resin was prepared using the reaction components of the present invention and the reaction conditions of Example 4 of the United States patent specification 28 9 (1955 ISOg epoxy resin based on bisphenol A and epichlorohydrin with a viscosity of 8900 cP ( 25 C) and an epoxy equivalent weight of 180 were ( _{mixed with 370 g of castor oil and 3.6 g of BF 3} -benzylamine complex. (This quantitative ratio is the ratio given in Example 4 of the USA patent.) The mixture was stirred well, to 170 C and heated for 10 hours at this temperature gehal- »s. after a 2 ¹ a hours, the mixture was completely gelatinized, and an elastic rubber-like substance had formed, which no longer change after further heating time.

b) To test the stability, an internally plasticized epoxy resin was used according to the present invention made from 810 g of an epoxy resin based on 75 percent by weight bisphenol F and 25 percent by weight bisphenol A and epichlorohydrin. this has a viscosity of 230OcP (25 C) and an epoxy equivalent weight of 170 has. 645 g of castor oil and 3 g of BF ^ -Benzylamine Complcx. Per epoxy group 0.365 VaI hydroxyl groups were used. The reaction product has a viscosity of 10,70OcP (23 C) and an epoxy equivalent weight of 432. This according to the present invention manufactured product that still contains free epoxy groups contains, was now according to the information in Example 1 of the USA. Patent 28 90 195 to 170 C. heated and for 10 hours at this temperature

ίο held. After cooling, the measurement showed the Viscosity an increase of 10% to 11,700 cP; and the epoxy equivalent weight had increased to 438. The product was not cured despite the use of this extreme temperature and viscosity and epoxy equivalents had risen only slightly, while the resins of the United States patent completely hardened under these conditions.

2. According to British Palentcription 1100 187 (DT-PS 1282970) was a mixture of 215g

jo castor oil, 270 g epoxy resin based on bisphenol A with a viscosity of 12 10OcP (25 C) and an epoxy equivalent weight of 190 and 1.3 g of BFj-piperidine complex slowly heated to 210 ° C. with stirring in the following steps: 1 hour at 130 ° C, 2 hours at 150 ° C, 2 hours at 170 ° C and 4 hours at 210 ° C. The reaction mixture was then cooled to room temperature. The The reaction mixture was almost black due to polymerization of the epoxide groups. and one after Phase separation which occurs during cooling shows that the reaction components are reacted in the presence of the BFj-pipcridin complex did not take place has. The epoxy equivalent weight of the mixture had only increased from 340 to 400.

The reaction products according to Examples 1. 3. 4. 5. 6. 7. Sb. 9. 10. 12. 15 and IS of the present Invention were subjected to further mechanical and electrical tests. The respective epoxy equivalent Corresponding amounts were mixed with 154 g of hexahydrophthalic anhydride (HHPSA) and 1.5 g of benzyldimelhylamine (BDMAI. In the case of Example IS with 1 g of tin OH-octoal as accelerator mixed with heating to 50 to 70 ° C. The bubble-free mixtures were in 10 and 4 mm strong flatness and 2 hours Cured SO C. 2 hours at 100 ° C. and 2 hours at 120 ° C. The one containing the cycloaliphatic epoxide Mixture according to example IS was a further curing of 4 hours at 150 C and Subjected at 160 ° C. for 2 hours.

After hardening were on hand from Prüfsiäbcii carried out the examinations compiled in the following table.

For comparison, those closest to the invention were

Examples 9 and 10 lying in the OE-PS "2 47 006 were reworked. It could only be partially homogeneous Make castings as final mixing took place during the hardening process. The test values therefore make the mean values of measured values larger Fluctuation.

A comparison of the test results shows that after the use according to the invention hardened products with high impact strength besides other things provide sufficient mechanical strength

let fis. Also to be emphasized are the very good electrical ones Properties of the cured resins according to the present invention: in comparison to those of the OE-PS 2 47 006.

Table 3

/ Ib

30th

Mixtures with HHI'SA < UI) MA

Example I Example 3 Example 4 Example Examples Example 7 Example Xb Example 9

Tensile strength wedge in Kp / cm ² 255

Impact strength in Kp ■ cm / cm ² > 40

(Limit) flexural strength wedge in Kp / cm ² 440

Ball indentation hardness 60 ". Kp / cm ² 330

Surface resistance. U. 100 VK) ' ⁴

Continuous understanding. 12 cm K) ¹⁵

Dielectric constant at 10 "Hz

Dielectric loss factor at 10 "Hz

Creeping rome strength wedge

425 265 270 280 290 2 (K) 275 > 4 () > 40 > 40 > 40 > 40 35 > 4 ( 890 750 460 720 750 350 720 550 620 370 630 650 280 610 K) ' ⁴ K) ' ⁴ K) ' ⁴ K) ' ⁴ K) ' ⁴ K) '' K) ' ⁴ K) ' ⁵ KV- K) ¹⁵ K) ' ⁵ IO ^IS K) ' ⁴ K) ' ⁵ 2.90 2.85 2.81 2.85 2.89 3.21 2.90

2.80 0.053 0.044 0.041 0.051 0.049 0.053 0.029 0.047

KA 3c KA 3c KA 3c KA 3c KA 3c KA 3c KA 3c / KA 3c 0.5 mm 0.5 mm 0.5 mm 0.5 mm 0.6 mm 0.4 mm 0.5 mm 0.5 mm

(Continuation)

Sndll-ocloal Austrian patent specification 2 47 (XXi

Example H) Example 12 Example Ii Example IK Example 10 Example 4

Tensile strength in Kp. Cm ²
Impact strength in Kp · cm ² (Limit) flexural strength in Kp cm ² Ball indentation hardness 60 ". Kp / cm ² surface resistance, ii. 100 V volume resistance. <> ■ cm dielectric constantc at 10" H / dielectric loss factor at 1 (T Hz tracking resistance

280 430 210 260 620 680 > 40 38 > 40 37 17th 20th 730 730 320 450 850 930 640 580 290 370 860 970 IO ¹⁴ K) ' ⁴ 10 ¹³ K) ' ⁴ K) " 10 " K) ' ⁵ ίο " K) ' ⁴ 10 ' ^s 10 ' ^Λ K) ¹ ' 3.13 3.10 3.3! 2.8! 5.24 4.98 0.051 0.048 0.051 0.027 0.079 0.083 KA 3 c KA 3 c KA 3 c KA 3 c KA 3b KA 3 b 0.6 mm 0.5 mm 0.5 mm 0.5 mm 0.5 mm 0.4 mn

Claims (5)

Patent claims: 1. Process for the preparation of modified, organic solvent-soluble internally pl decorated epoxy resins of the general formula with A = O CH, —CH —CH ₁ —OA — X - CH ₃ i CH ₃ "B OH -O — CH ₁ -CH-CH, - OH O —CH ₁ —CH — CH, - A = CH ₃ OH -CH ₁ -C-CH ₁ -O-CH ₁ -CH-CH, - "I. CH, CH, CH ₂ -CH-O CH ₃ OH 7-10 OH CH ₁ -CH- CH, - (-CH ₁ -CH-O-CH ₁ -CH-CH ₁ - OH CH- CH, - and X = —O— or —S—, where the The condition is that CH ₃
CH ₁ -CH-O CH ₃ -CH, -CH- 45 CH _{2 N} -CH, - for / i = 2 and B = -CH ₁ -CH-CH, - 'ί
for / 7 = 3, 55 CH ₇ -OOC-R, CH-O-CH, -CH-CH, <»B = CHOOC-R, CH-O-CH ₁ -CHCH, - "A," _ts CH ₁ -OOC-R ₁ -CH-O CH ₁ CH-CH, "I" I R, CH, - for η = 3 and R ₁ = - (CH ₂ I ₅ -CH ₃ R ₂ = - (CH ₁ I ₇ -CH = CH-CH ₂ - by converting polyepoxides)! of my formula CH ₂ -CH-CH ₂ -OD ₇ O-CH ₂ -CH - (where D = or -CH ₁ - CH ₃ -CH ₁ -C-CH, - I,- CH ₃
CH ₂ -CH-O CH ₁ -CH or the connection is O
CH-CH, with compounds of the general formula [HX] _n B wherein X, B and / i have the above meaning, reacts in the presence of BF, -complexes, characterized in that those BF, -amine complexes are used which are soluble in the reaction mixture and in which the amine forming the complex has a pK _b value in aqueous solution from 15 to 4.5 and has a per gÄquivalent reacted with a hydroxyl group of an epoxy group gÄquivalent 1 to lOOmMol BF ₃ complex used _s _2, and that per equivalent of an epoxy group is 0.1 to 0.9 equivalents of the hydroxyl groups containing compound are used. 2. The method according to claim 1, characterized in that containing hydroxyl groups as Compounds esters of ricinoleic acid are used. 3. The method according to any one of claims 1 and 2, characterized in that as SH groups Compounds containing lauryl mercaptan, dodecyl mercaptan, octyl mereaptan, nonyl mercaptan. i.2-ethanthiol and or 1,2-propanthioI used will. 4. A modified and internally plasticized epoxy resin with the following formula O
CH, -CH-CH, -O-A-X mil Λ = - · ■ CH ₃ CH ₃ X-r H -Z OH Vo-CH ₂ -CH-CH ₂ - OH Q-CH ₇ -CH-CH, - CH ₃ OH -CH ₂ -C-CH ₂ -O-CH ₂ -CH-CH, -CH ₃ CH ₃ CH ₃ OH CH ₂ -CH-OI CH ₂ -CH-O-CH ₂ -CH-CH ₂ - OH CH ₂ -CH-CH ₂ -O- CH, - χ-χ ί - 5 HO OH
- CH-CH, - 50 and X = —O— or —S—, where the The condition is that CH ₃ B = -f-CIK-CH-O CH, CII, -CH- 55 60 - CH, - ( for / i = 2 and for / ι CH ₁ -CH-CH, - R ₁ CH ₂ -OOC-R, CH-O-CH ₂ -CH-CH ₂
H = CH-OOC-R, CH O CH, CH CH, i '■■ : I R, CH, C) OC · -R, ■ ■ CH - O Ci I, CW -CH, R. for Ii = 3 and R ₁ = (CH ₂ ), CH ₃ R, = (CH,) -— CH- CU Cl 1, 5. A modified and internally plasticized epoxy resin with the following formula CH ₁ -CH-CH ₁ -O--: O CH ₃ CH ₁ ,. -C) -CH ₂ CH -CH ₂