DE1518950A1 - Process for the preparation of a sulfhydryl resin - Google Patents

Description

Process for the preparation of a sulfhydryl resin a.

The present invention relates to an ancestor of the manufacture of sulfhydryl resins and to theirs Use when hardening τοη epoxy resins. The present The invention relates in particular to a method for Production of τοη sulfhydryl arsenic by reacting hydrogen sulfide with the Bpoxyalkyläthern of the dimeric Alcohol of a polymerized fatty acid or the epoxyalkyl ester of the dimer acid of a polymerized fatty acid.

These sulfhydryl resins produced according to the invention are used as hardeners for epoxy resins, which give infusible products with a high degree of flexibility. These Converted products are therefore used in areas such as flexible adhesives, coatings and sealing agents such as putty and sealing materials.

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One object of the invention is a method of manufacture of sulfhydryl resins from the epoxyalkyl ether and / or esters by reacting them with hydrogen sulfide.

Another object of the invention is a method of curing epoxy resins with the sulfhydryl resins of US Pat present invention.

Briefly, the invention comprises the preparation of sulfhydryl resins by the reaction of hydrogen sulfide with certain epoxy alkyl esters and ethers. These Sulfhydryl resins can then be reacted with epoxy resins, thereby curing the epoxy resin to an infusible and insoluble product, but to a high degree is flexible.

The starting materials for the present invention are

1. Dimer acid - the dimer acid that is used during polymerization is obtained from fatty acids.

2. Dimer alcohol - the alcohol that makes up the above dimer acid.

The dimer acid and the dimer alcohol can through the formulas

Acid: HOOC-D-COOH
Alcohol »HOH ₂ CD-CH ₂ OH

be defined, in which D is the divalent carbon residue of the dimer, which was obtained by the polymerization τοη monovalent fatty acids with 8 to 22 hydrocarbon atoms. If the polymerized fatty acid is an acid with a chain of 18 carbon atoms such as oleic acid, linoleic acid or linolenic acid, a dimer acid with 36 carbon atoms is formed and therefore the remainder of a chain contains 34 carbon atoms.

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material atoms, where 2 carbon atoms represent the carboxyl group the acid or, in the case of hydrogenation, sum alcohol to form the CH groups. With other acids and with mixtures τοη acids with different chain lengths, the length of the carbon chain is different depending on the acids used as the starting material.

As indicated, the dimer acids are one of the starting materials for the products according to the invention; she are made by polymerizing fatty acids with 8 to 22 carbon atoms. The reaction product The polymerization of acids is a mixture of monomeric, dimeric and higher polymeric forms, these being higher polymeric forms are generally referred to as trimeric acids or trimers. The dimeric form or the dimer predominate in general and the semi-sch sometimes becomes referred to as "dimer acid". If the trimeric form predominates, the mixture is sometimes referred to as "frimeric acid". As a generic term is "polymeric fatty acids" the appropriate urine for the mixture, which includes both types. For the purposes of the present invention means the term "dimer acid" a polymeric fatty acid product in which the dimer form or the true dimer acid in an amount of more than 50% by weight and generally in contained in an amount of more than 70 wt. Products with a higher content of dimeric substance (more than £ 95 Dimers) are obtained by fractionating the polymeric fatty acids with a lower dimer content.

The term ¹¹ polymeric fatty acids "is the generic term for polymerized acids obtained from" fatty acids ". The term" fatty acids "includes saturated, ethylenically unsaturated and acetylenically unsaturated naturally occurring and synthetic monohydric aliphatic acids, the 8 to Contains 24 carbon atoms.

The saturated, ethylenically unsaturated and acetylenically unsaturated fatty acids are generally polymerized by somewhat different processes,

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due to the functional similarity of the ρpolymerieierte However, all products are referred to as "polymeric fatty acids".

It is difficult to polymerize saturated fatty acids; the polymerization can, however, at increased Temperatures can be reached with a peroxide catalyst such as dit-butyl peroxide. Because of in general low yields of polymeric products, these substances are currently of no economic importance. Suitable Saturated fatty acids are branched and straight chain Acids such as caprylic acid, pelargonic acid, capric acid, Lauric acid, myristic acid, palm! Tic acid, isopalmitic acid, Stearic acid, arachidic acid, behenic acid and lignoceric acid.

The ethylenically unsaturated acids are much easier to polymerize. It can be catalytic or non-catalytic polymerization processes are used. The non-catalytic polymerization generally requires a higher temperature. Suitable catalysts for the polymerization are acidic or alkaline clays, di-t-butyl peroxide, boron trifluoride and other Lewis acids, anthraquinone, soybean dioxide and the like. Suitable monomers are, for example, the branched and straight chain, poly- and mono-ethylenically unsaturated Acids such as 3-octenonic acid, 11-dodecenonic acid, linderic acid, Lauroleic acid, myrietoleic acid, tsuzuic acid, Paleitoleic acid, petroselinic acid, oleic acid, elaidic acid, Vaccenic acid, gadoleic acid, cetone acid, Hervonic acid, linoleic acid, linolenic acid, elaostearic acid, hiragonic acid, moroctic acid, timnodonic acid, Arachidonic acid, nisic acid, scoliodonic acid and chaulmoogric acid.

Ethyleniaoh unsaturated fatty acids can be polymerized by simply heating the acids. The polymerization of these highly reactive Substances are made without a catalyst. The acetylen! Sch

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Unsaturated satires rarely occur in nature and their synthetic production is expensive. As a result, they are currently economically void Meaning. All acetylenically unsaturated fatty acids, both with a straight chain and with a branched chain, both monounsaturated and multiply unsaturated, are useful monomers for the preparation of the polymeric fatty acids. Suitable examples such substances include 10-undecenonic acid, Tariric acid, stearoleic acid, behenolic acid and isamic acid.

Because of their ready availability and the relative ease of their polymerization, oleic acid and linolenic acid are the preferred starting materials for the preparation of the polymeric fatty acids. After the fatty acids have been polymerized, the product obtained can then be fractionated, for example, by conventional distillation processes or solvent extraction processes. They can be hydrogenated (before or after the distillation) under hydrogen pressure in the presence of a hydrogenation catalyst to reduce the unsaturated bonds .

Typisohe compositions of commercially available polymeric fatty acids based on unsaturated O ₁₈ - fatty acids are ι

monovalent G ^ acids (monomersβ ") 5-13 wt. - ^, divalent 0, ^ - acids (" Dieeree ") 60-80 Oew.-jl, polyvalent O ₅₄ (and higher) -8 acids (trimers")

10-35 ffew.-ji.

You ratios of monomer, Bimerem and trimer (or higher polymer! Ei he tem substance} in the unfrektionierten polymeric fatty acids are dependent on the musculature de · Auegangestoffee and the polymer! ONS factors beyond. Zweoke for the invention Torliegendan

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does the expression mimo-iaer · -? S * ett-err on the unpolished monom ^ TT ΒΆν.Τθη ? (?. ρτ Bor! · "· -» to j which unfold in the polymer fatty acids «n! specified? relates SiOH the term dirocre fatty acids anf the dimeric 3? oris vcm acids ^ of the other derivatives (which are formed by the Birjerisierung of two fatty acid molecules.), and the term trimeric fatty acids shall look to lie verblei bend en h3her ^a n polymeric forms * * The first rule consists of the intrinsic form of sinks? Ήγ derivatives but contain some higher polymeric forms.

wsi «€; t · by sin aaaljr ^ iai'r-r ^ t'Ar-oau-il.'V-Xi.iro ^ Defa'till fakr ^ n öefipiert · Is hsrde3t ei oh \ m that? er

vacuum (-A-te- ^ hal ^ ^ oü 5 M-) durotif ^ leads \ ind the monomer fraction is ^{calculated from the weight of the product boiling at 155 a} C, the dimsre! fraction from the awischer. 155 vai & 250 ⁰ O boiling products3 is calculated and the trimeric (or higher) fraction is calculated from the residue.

polymeric fatty acids can be converted by hydrogenation in alcohol "will · _t whereby GIycole with the same number of carbon atoms as the polymeric fatty acids are obtained, i ^ alls the Dimersäura is hydrogenated, the corresponding Diöl formed. In the case of the trimeric form, the triol is formed. The hydrogenation can be carried out in any conventional high-pressure hydrogenation plant using batch or continuous processes. A hydrogenation catalyst is required, and the complex copper tube catalysts are generally used in the aweokmeSigiter. nindi «s can, however, also change catalysts» is ^ »ixutcnriielt-KÄt & lyeÄtör ·» can be used.

BATH ORIGINAL

In general, a heating temperature of 200 to 250 ⁰ O and a hydrogen pressure of 100 to 500 atmospheres are used. For a further explanation of the production of these alcohols and also of the production of the polymeric fatty acids, reference is made to US Pat. No. 3.34-7.562.

The starting material, the dimeric fatty acid or the dimeric alcohol, is then converted into the epoxyalkyl ester or -ether implemented. In the case of alcohol, this can be achieved by converting it into a halohydrin ether by reaction with an epihalohydrin such as Bpichlorohydrin and subsequent elimination of hydrogen halide to form the glycidyl ether product. Epihalohydrin, those used in the manufacture of halohydrin intermediates are useful are epichlorohydrin, epibromohydrin and epiiodohydrin, preferably in alpha form. The latter substances are all characterized by a chain containing three carbon atoms; Analogs of the abovementioned bpihalohydrins can also be used. Examples of the latter are beta and gamma methylepichlorohydrins, 1,4-dichloro-2,3-epoxybutane etc. The specific halohydrin determines the alkyl group in the epoxyalkyl portion of the Molecule. The alkyl groups generally contain 3 to 6 carbon atoms and can be branched Have chain, the side chains being alkyl groups which generally contain 1 to 3 carbon atoms. In view of its availability and relatively low cost, Bpichlorohydrin is preferred as the one Epoxypropyl (glycidyl) polyether results.

When an epihalohydrin reacts with a dimer acid or a dimer alcohol to form a halohydrin ether or halohydrin ester composition condensation catalysts are used. Typical catalysts are Friedel-Crafts catalysts including anhydrous AlOl ,, ZnOl «» BP-,

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PeCl ,, SnCi ₇ , uM complexes such as the known BP, etherate, etc .; Acid type catalysts including HP, H ₂ SO ^, Η, ΡΟ ^ etc. j base type catalysts such as benzyltrimethylammonium hydroxide, dimethylbenzylamine, tri- (dimethylaminomethyl) phenol and others such as SbCIc etc. The concentration of the catalyst may vary depending on the individual catalyst to be different. For example, about 0.1 to about 0.2 6 BP * or its complexes, based on the total amount of reactants, give satisfactory results. In general, the conversion catalyst is used in a small concentration of up to about 5 %, usually less than 1 % based on the total reactants, especially when using catalysts of the BP1 type. With certain less active catalysts, ie SbClf- etc., larger amounts can advantageously be used.

The Halohydrinprodukte be conveniently prepared by reacting the epihalohydrin and the dimeric Pettsäoreprodukt in the presence of a suitable condensation ti iiskatalysators at a! Temperature between about 25 ° unl about 125 ⁰ C converts »temperatures iz * the order of 25 ⁰ C generally result in a slow Rate of reaction unless relatively large amounts of catalyst are used. Very satisfactory results, that is, a sufficient reaction rate and a bright coloring product can be obtained at temperatures close to 100 ⁰ C, if one wants to form the Halohydrinzwischenprodukt from dimer Pettsäure using an alkaline catalyst. The formation of the halohydrin intermediate product from the dimeric fatty alcohol is best carried out at a maximum temperature of 60 to 65 ^° C. using an acid catalyst. The condensation of the dimeric alcohol with the epihalohydrin can be carried out by adding the epihalohydrin dropwise to the mixture of the catalyst and the dimeric alcohol. The condensation takes place

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relatively slow in the beginning and becomes faster as the temperature rises as a result of the heat released. In general, the temperature rises noticeably, so that effective cooling must be used to avoid violent reaction. Bin preferred method consists in adding an alkaline catalyst to the alcohol and then adding the epihalohydrin, wherein the temperature is allowed gradually to rise to 10O ⁰ C. This gives a more uniform product and allows better control of the reaction. Since the reaction is exothermic, cooling can be used in order to shorten the time required for the addition of the epihalohydrin. By suitably regulating the cooling rate and the rate at which the epihalohydrin is added, the reaction can be carried out at the desired temperature in the shortest possible period of time. The condensation can take place in the presence or absence of suitable solvents or diluents.

Di · condensation of dimeric fatty acid and the epihalohydrin is preferably carried out by heating a mixture of the dimeric Pettsäure, the epihalohydrin and the catalyst at about 100 ⁰ C and holds the Eeaktionsgemisch several hours under stirring at this temperature.

Ideally, this can Halohydrinäther of the dimeric fatty alcohol reproduced from Epiühlorhydrin t by the following formula

t t

OS OH

in which D has the meaning defined above and X means a halogen atom such as chlorine *

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For conversion to the epoxyalxyl derivative, the haloliydrin product is then treated with an alkaline agent to cleave hydrogen halide from the product. This treatment can be carried out by adding the alkaline agent to the reaction mixture obtained in the above-described method, or the condensation product can be recovered from the reaction mixture by any suitable means such as distillation, extraction and the like, before it is combined with the alkaline agent, for this reaction any of the known agents for splitting off hydrogen halide can be used, such as sodium and potassium hydroxides, sodium and potassium carbonates and bicarbonates. Borax, hydroxides of magnesium, zinc? Lead, iron and aluminum and the corresponding oxides, etc .. Me aluminates »silicates and ZinScate of A: .kali salts such as about Hatrioi- and Kaliumalaminac to riatrium- and on potassium, Sini particularly good dehydrohalogenation agents when nearly or completely in a anhydrous medium is used.

The Aage üb & -verwendeten Halogenwasserstoffabspaltungsaittels is different and depends Gate * the number of groups ate "ν m where hydrogen halide to be eliminated" At least one mole of the agent should be used for each in a ipoxygruppe converted Kalohydringruppe. In most cases the hydrogen halide removal agent can be used with the halotydrin in the form of an aqueous solution or suspension or dissolved in an inert solvent such as ethers, esters, hydrocarbons, etc. If the above-mentioned aluminates, silicates or zincates are used as alkaline agents, the splitting off of hydrogen halide is preferably carried out in a non-aqueous medium, and the salts are dissolved as such or in organic solvents or diluents; Used! Carbon tetrachloride, 1,4-dioxane and Di fnlorätnyläther are used as solvents for

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this is particularly advantageous.

Epichlorohydrin can also be used as a solvent or diluents can be used for the elimination of hydrogen halide. This enables it to be used of caustic alkali, sodium hydroxide, as a hydrogen halide splitting agent without disadvantageous further reaction or with a minimum of further reactions during or after the formation of the glycidyl ether. The sodium hydroxide is used in an amount equivalent to the active chlorine of the chlorohydrin is or represents a slight excess. An Ohloratom on one is called an active Ohlor Carbon atom next to a carbon atom bearing a hydroxyl group.

The glycidyl esters are most easily made from the dimer fatty acids by the conversion of alkali metal salts of the dimeric fatty acids with a bpihalohydrin produced at elevated temperatures. As above given in the description of the halohydrin ethers of alcohol epichlorohydrin is preferred. The salts are made by simply adding the acid Potassium hydroxide or sodium hydroxide in an inert medium such as water, alcohol, benzene or the like. Mixes and implements. The liquid medium is then separated off and obtained the salt of the acid.

The salt is then reacted with epichlorohydrin 115 ⁰ O at temperatures of about 85 ° Ms. Higher temperatures can be used, but they may require the use of a pressure vessel. Temperatures on the order of 95 to 105 ° 0 are generally preferred. A catalyst such as the various quaternary ammonium salts described above in connection with the alcohol can be used.

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- Xd. -

At least one mole of the epihalohydrin is used for each -COOM group _f when M is an alkali metal and the use of an excess of 0.5 to 2 moles is preferred. It generally takes half an hour to about two hours to complete the reaction; then the alkali metal halide is filtered off and the excess epihalohydrin stripped off, the grlycidyl ester product remaining as a residue.

Ideally, the preferred glycidyl products, from which the sulfhydryl resins are made, represented by the following formulas:

1. Grlycidyl ester of the dimeric fatty acid

H ₀ C-OH-OH ₀ -OOO-D-COO-Ch ₀ OH-OH

² W ^{2 2} \ /

0 0

2. Grlycidyl ether of dimeric fatty alcohol

H ₀ C-OH-CH ₀ -OOH ₀ -D-OH ₀ O-Oh ₀ -OH-CH ² \ / ^{2 2 2 2} \ /

0 0

where D has the meaning given above.

The epoxyalkyl derivatives are then converted into sulfhydryl resins by reaction with hydrogen sulfide. The H ₂ S is used in an amount of 1 to 10 moles per equivalent of oxirane in the glyeidyl derivative. A two to four fold excess is preferred. The reaction is preferably carried out in the presence of an alkaline catalyst, such as, for example, alkali metal (sodium or potassium) hydrosulfides, alkoxides (methoxide or ethoxide), phenoxides or hydroxides; A »ino-

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compounds such as alkylene polyamines (ethylenediamine or Diethylenetriamine), di- or trialkylamines, (methyl or ethyl) pyridine, piperidine, dicyandiamide or melamine. The catalyst is used in an amount from 0.001 to 5 wt .-% and preferably from 0.1 to 1.0 wt .- # used.

The reaction can be carried out at atmospheric pressure or at superatmospheric pressures. At atmospheric pressure, ropes of the H ₂ S are blown through the GKLyoidylproduct for a short time and the mixture is then allowed to stand for a time before further part of the HgS is exposed. However, it is preferred to carry out the process under pressure. The HpS can be introduced into the pressure vessel all at once under pressure or periodically. Pressures in the range between 3.52 and 21.1 kg / cm are preferred. However, higher pressures up to 14-1 kg / cm can be used.

The temperatures used in the reaction may be between -15 ° and about 150 ⁰ O. Generally be applied from about 20 ° to about 125 ⁰ C, with a temperature between tree temperature and 100 ⁰ O is preferred. The reaction can be carried out in the presence or absence of solvents or diluents. Suitable solvents are, for example, toluene, benzene, oyolohexane, dioxane, alcohols such as ithanol, propanol or butanol, tetrahydrofuran, diethyl ether, dibutyl ether and mixtures of the aforementioned compounds.

The present invention can best be through the following · »examples are explained, which the preparation of the various GIyoidylderivat · as well as the Manufacture of Bulfhydrylhar »· from them» own.

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Example 1:

In 250 cc of cyclohexane, 300 g of a commercially available dimer acid Diglyoidylesters of TaIlölfettsäuren (X-71, supplied by Shell Oil Company) having a Oxiransauer off at content of 3171 1> dissolved. The solution was placed in a shaking autoclave and 1.0 g of sodium methoxide was added. 90 g of hydrogen sulfide gas was then introduced. The closed autoclave was then shaken at ambient temperature (26 to 30 ^° C.) for 27 hours, during which time the pressure fell from 6.33 kg / cm ² overpressure to 4.22 kg / cm overpressure. After opening the autoclave, the suspended catalyst was filtered off from the reaction mixture and the solvent was distilled off under reduced pressure (762 Torr at about 45 ⁰ O). The final product obtained was a clear liquid resin (322 g) with a Brookfield viscosity of 96 poises at 26 ⁰ C and a sulfur content of 6.9 # · Infrared analysis confirmed the presence of the expected hydroxyl and sulfhydryl groups.

Example 2;

498 g of the same diglycidyl ester used in Example 1 and 1.0 g of sodium methoxide were placed in a shaking autoclave. To this mixture, 106 g of hydrogen sulfide gas was fed. The vessel was then closed and ^{shaken at 27 °} C. for a period of 27 hours and during this time the pressure fell from 8.44 kg / cm ² to 6.33-7.03 kg / cm ² . After opening the autoclave, 350 ecm of chloroform were added to the reaction mixture in order to facilitate further treatment. The suspended solid was filtered off from the solution and the solvent was distilled under reduced pressure (635-711 Torr vacuum). The bathroom product,

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which was similar in appearance to the product of Example 1, weighed 540 g, had a Brookfield viscosity of 57-58 poises at 26 ⁰ O and a sulfur content of 7.12 ^. The infrared analysis was practically identical to that of the product of Example 1. In another preparation, practically identical to the above, 541 g of thiol resin with a Brookfield viscosity of 55-56 poises at 26.5 ⁰ O and a sulfur content of 7.1 i » produced. In a third preparation, which was essentially identical to the above, 520 g of thiol resin with a sulfur content of $ 7.05 and a sulfhydryl content (SH) of $ 6.81 were obtained.

Beis piel 3:

Bs, 300 g of the same diglycidyl ester used in Example 1 at 60 to 70 ⁰ O heated and HpS was blown for about 7 hours at atmospheric pressure by the hot resin. The resin was allowed to cool to room temperature and 10 drops of tri- (dimethylaminomethyl) phenol were added. Hydrogen sulfide gas was slowly bubbled through the resin for an additional 6.5 hours. During this time the resin temperature door rose to 43 ⁰ C. After cooling to room temperature, the resin was degassed under reduced pressure. The analysis of the product showed a sulfur content of 5 »6 #.

Example 4:

A mixture of 90.718 kg of the dimer acids obtained in the polymerization of tall oil fatty acids, 79.378 kg of 4-methylpentanol-2, 0.907 kg of p-toluenesulfonic acid and 22.679 kg of toluene were refluxed at 125 ° 0 for about four hours. The formed water was removed during the reaction. The ester was then washed and distilled off from the solvent removed and had the following analysis:

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Saponification number 155, 5

Acid number 0.65

The ester was then reduced to the alcohol, essentially as described in Ind. 4 Eng. Ohem., Vol. 39, 194-7, page 55 was used. The crude dimer alcohol was fractionated and a fraction with an average hydroxyl value τοη 183 was collected, which was used in the subsequent reaction,

With stirring, 1212 g (2.0 mol) of the above dimer alcohol fraction and 370 g (4.0 mol) of epichlorohydrin were mixed, and 1 ecm of BF-Xtherate was added. Within a period τοη about 3 hours, the reaction temperature rose (only as a result of the exothermic release of heat) to 35 ⁰ O. At this point in time 1 com ΒΡ ether was added and the reaction temperature rose to 65 ⁰ O within one hour. The reaction mixture was now cooled and the Ohlorhydrinätherprodukt obtained, which had a content of active Ohlor τοη 7.69 ^ (theory 8.98 Ji).

_{A solution of 2 g of VaOH in 10 com H 2} O was added to a mixture of 92.5 g (1.0 mol) of epichlorohydrin and 1.562 g (1.69 mol) of the Onlorhrdrinätherproduktes. Then, while stirring, a total of 135 g of powdery VaOH were added in about 8 equal ropes within about 1.5 hours. During this time the reaction temperature rose to a maximum value τοη 55 ⁰ O. After cooling to room temperature, the reaction mixture was filtered and the ipichiorhydrin was stripped off under reduced pressure at a temperature τοη 78 ⁰ O. The product was filtered and gave a clear liquid diglyoid ether with an oxirane oxide content τοη 3.45 J *.

To 500 g of the above GHyoidyläther · des Dimer alcohol was 1.0 g of sodium methoxide catalyst

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added. The reaction mixture was placed in a pressure vessel, and a total of 100 g of hydrogen sulfide gas was introduced into the vessel under pressure from a pressure cylinder. The autoclave was shaken at room temperature for 24 hours. After opening to remove excess HpS, the reaction mixture was dissolved in about 2 liters of cyolohexane, the solution was filtered and the cyolohexane was removed under reduced pressure. The product, a liquid orange resin having a viscosity of 63 poises at 24 ⁰ C had a sulfur content of 6.0 <f> and a content of 4.26 8H fL.

As indicated above, the sulfhydryl resins of the present invention are useful for curing Suitable for epoxy resins. The epoxy resins that can be used are Substances that contain more than one adjacent spoxy group, i.e. more than one

-Group included. These compounds can get saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and, if desired, can have substituents which do not take part in the reaction such as chlorine, hydroxyl group, ether residues and the like. Be substituted. In general, spoxy-terminated epoxy compounds are preferred. The epoxy resins can also be characterized by reference to their epoxy equivalent weight, the epoxy equivalent weight of the pure Ipoxy resin being divided as the average molecular weight of the resins by the average number of Spozyreste per molecule or in each jail they number of Grams of Bpoxy equivalent per one Bpoxy group or one Gram equivalent of Spoxyd. The one at the present

BATH

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'' YlU I

Epoxy resin materials used in the invention have Bpoxy equivalent weights τοη about 140 to about 2000.

Suitable epoxy resins are, for example, the reaction products of polyhydric phenols with polyfunctional ones Halohydrins. Typical polyhydric phenols useful in making such resins are Resoroinol and various bisphenols obtained from the condensation of phenol with aldehydes and ketones such as formaldehyde, acetaldehyde, acetone, methyl ethyl ketone and the like. A typical epoxy resin of this type is the reaction product of epichiorhydrin and 2,2-bis- (p-hydroxyphenyl) -propane (bisphenol A}, the resin has the following theoretical structural formula:

^m 3 ^0H ^ 3 O

H ₂ C - OH- (JH ₂ -O - (^) - 0 - / ^^ C) -CH ₂ -GH-CH ₂ O) ^^^)

OH, CH,

In which η means mull or an integer up to 10. In general, η will usually not be greater than 3 or 4 and may be 1 or less. You can also other types of epoxy resins. be used .

Another such epoxy resin is the reaction product of epichlorohydrin and bis (p-hydroxyphenyl) sulfone. Another group of epoxy compounds that can be used are the Slycidyleeter from polymeric fatty acids. These glycidyl esters are through Implementation of polymeric fatty acids with polyfunctional halohydrins such as s «B. Epichlorohydrins to the above way described. In addition, the glyoidyl esters are also commercially available Spoxydstof fe.

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The polymer fatty acids largely consist of dimers Acids are made up of their glycidyl esters through the the following theoretical idealized formula can be reproduced:

OO
.0 - OCH ₂ CH - CH ₂

C - OCHgCH - CH ₂

in the Ό the meaning given above ha / t, fflyöldylester other polyvalent acids, such as 2.B. Phthalic acid and sebacic acid can be used.

Other types of epoxy resins which can be used in the present invention and which are commercially available epoxies are the polyglycidyl ethers of tetraphenols which contain two hydroxyaryl groups at each end of an aliphatic chain. These polyglycidyl ethers are obtained by reacting the tetraphenols with polyfunctional halohydrins such as epiehlorohydrin. The tetraphenols used in the preparation of the polyglyoidyl ethers are a known class of compounds which are readily obtained by condensation of the corresponding dialdehyde with the desired phenol. Typical tetraphenols which can be used for the preparation of these epoxy resins are the alpha, alpha, omega, omega-tetrakLs- (hydroxyphenyl) alkanes such as jb.B.1,1,2,2-tetrakis (hydroxyphenyl) ethane , l, l, 4-, 4 - tetrakis (hydroxyphenyl) butane, l, l, 4 _t 4-tetrakis (hydroxyphenyl) -2-ethylbutane and the like. The epoxy resin reaction product of epichlorohydrin and tetraphenol can be obtained by the following theoretical structural formula can be reproduced:

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- OHOH ₂ O - / \

H ₀ O - 0HOH ₀ O - ² \ / ²

OOHgOH - OH ₂

in which E is an animal-valent aliphatic hydrocarbon chain with 2 to 10 and preferably 2 to 6 carbon atoms.

Nooh another group τοη epoxies are the epoxidized novolak resins. Ser-type resins are well-known substances and are readily available commercially. the Resins can be represented by the following theoretical idealized formula

0-0H ₂ -OH -OH ₂

0-0H ₂ OH - OH ₂

OH,

- ¹ U

0-OHo-OH - OH,

where R is a hydrogen atom or alkyl groups with up to to 18 carbon atoms and η a whole number τοη 1 to 10 means. In general η is a whole Number τοη more than 1 to su about 5 «

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Usually these resins are epoxidized obtained from the known novolak resins. You Hovolak resins are, as is known in the art, by condensing the phenol with formaldehyde in the presence of a Acid catalyst produced, but it can also Ηοτο-lak resins from other aldehydes such as a.B. Acetaldehyde, Chloral, butyraldehyde, furfuraldehyde and the like can be used. If an alkyl group is present, it can have a straight or branched chain. Examples of the alkylphenol from which the iovolak resins can be derived are oresol, butylphenol, tertiary butylphenol, tertiary amylphenol, hexylphenol, 2-ethylhezylphenol, sonylphenol, deoylphenol, dodeoylphenol and the like. Be is generally preferred however, it is not essential that the alkyl substituent be attached to the para-carbon atom of the starting phenol nucleus. However, novolak harae became produced whose alkyl group is in the ortho position.

The epoxidized hovolak resin is formed in a known manner by adding the hovolak resins to spichlorohydrin and then adding an alkali metal hydroxide to the mixture to cause the desired condensation reaction to effect.

Other epoxy resins which can additionally be used are epoxidized olefins such as epoxidized polybutadiene and epoxidized cyclohexenes and the like Biglycidyl ethers of the polyalkylene glycols. These latter Xther are readily available commercially and can be represented by the following theoretical idealized formula:

- OH-OH ₂ -O- (HO ^ _n -OH ₂ -

CH

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i .vU '

in which R is an alkylene group with 2 to 5 carbon atoms and η is an integer from about 1 to about 50. E is preferably ethylene or propylene or mixtures thereof and η preferably means from about 3 to about 10. It should be noted that η «represents an average value since the ethers often consist of a mixture of glycols such as tripropylene glycol, tetrapropylene glycol and the like. getting produced. Such epoxy resins can be prepared in the manner described in U.S. Patent 2,923,696 getting produced.

When using these sulfhydryl resins with the epoxy resins, a catalyst is generally used as usual when curing polysulphide epoxy resins is. A list of such catalysts is given in the publication "High Polymers", edited by Norman G. Gaylord, Interescience Publishers, 1962, p 197, Volume XIII, Rope III. Examples of some of the most commonly used catalysts and 2ri- (dimethylaminomethyl) phenol (DMP-30), dimethylaminomethylphenol (DMP-IO), Senzyldiäthyl- or dimethylaminj alkylenediamines or polyamines such as x.B. Ethylenediamine, diethylenetriamine, bimethylaminopropylaminej Amines such as diethylamine, triethylamine, friäthanolaminj acidic catalysts such as phthalic anhydride, pyromellitic dianhydride, boron trifluoride and polymers Catalysts such as the polyamino amides of polymeric fatty acids and alkylene polyamines. To get the explanation too Simplify and compare the different products in the following batches of curing epoxy resins To facilitate, DMP-30 was used as the catalyst in an amount of 10 wt% based on the epoxy resin used used unless otherwise specified and the cured epoxy resin was a bisphenol-A epichlorohydrin product Bit an epoxy equivalent weight of about 190. The corresponding amounts of sulfhydryl resins, Epoxy resin and catalyst have been carefully applied

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Mixed at room temperature and poured into a 88.9 diameter petri dish coated with a silicone solvent. The resin blend was then cured at 120-130 ⁰ G in a forced air oven. Physical properties were then determined, the results of which are given in the following examples.

Example 5t

A mixture of the following resins was prepared at room temperature: 25 g of a liquid dithiol resin (Example 1), 50 g of a bisphenol A-epichlorohydrin-epoxy resin with an epoxy equivalent weight of about 190 and 5 g of iri (dimethylaminomethyl) phenol. The liquid resin mixture gelled within 8 minutes of mixing. The temperature during gelation was 69 ⁰ C and the maximum temperature was by the exothermic heat release 100 ⁰ G. This mixture had hardened after 24 hours, a Barcol hardness of 35-45.

Example 6t

A mixture of 12.5 g of the liquid Dithiolarse of Example 3> 50 g of bisphenol A-Epichlorhydrinepoxyhars with an epoxy equivalent of about 190 and 5 g of tri- (dimethylaminomethyl) -phenol was ^{hardened at 100 0} C for 70 hours in a fan oven. The Barcol hardness of the cured mixture was 43-45 and the deformation temperature when bending (at 18.56 kg / cm load) was 69 °. The mixture was found to be an excellent adhesive.

Example 7:

At room temperature, a mixture of 20 g of the liquid thiol resin of Example 1, 20 g of the in

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- ZI- -

Example 5 used liquid epoxy resin and 2 g Tri- (dimethylaminomethyl) phenol produced. Am 0.127mm thick PiIm from this mixture was applied to a tin-plated sheet metal plate and after hardening overnight (about 12 hours) a very clear upper layer was created, which passed the floor test with 69 »12 cm kg according to Gardner.

The liquid dithiol resins of Examples 2 and 4 were used to cure epoxy resins as in the previous examples. In the epoxy resin it was the same resin that was used in Examples 5, 6 and 7, and the catalyst, tri- (dimethylaminomethyl) phenol, was added in an amount of 10 (Jew .- ^ ₁ to dag Epoxy resin used, used The results are shown in the table below

Sulfhydrylharζ of Example 2 4 Ratio of sulfhydrylharζ

for epoxy resin 2ti IO ItI 2ti

Gel time at 120 ⁰ O - 10 11 16 (minutes)

Shore Rarte + Θ0-85Α 82-91D 73-80D 75-90A

(ASTM D 17O9-59T)

Tensile strength (kg / cm ² ) at 29 »53 412.09 128.03 17.01 Room temperature

(ASTM D 1708-591)

JC elongation at room temperature 137 6 40 115 (ASTM D 1708-59T)

⁺ Shore Α or D hardness as indicated by letters.

The sulfhydryl resin is preferably in · 1η · Γ Amount used from 0.5 to 3 parts by weight per part of epoxy resin depending on the properties desired.

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Claims (7)

Claims; 1. The process only produces a sulfhydryl resin, which is characterized by the fact that, on hydrogen sulfide, there is an epoxy alkyl ester of the acid HOOO-D-OQOH and / or an epoxy alkyl ether of alcohol converts, where S is the equivalent · hydrocarbon residue means a diaeren fatty acid. 2. Terfahren according to claim 1, characterized in that "be without t ₍ that the calculation" between Bauetesiperatur and 10O ⁰ G is carried out. 3. The method according to claim 1 ₉ is characterized in that the bpoiyalkyl ester of the lyoidyl ether is terminated by the diaerlised tall oil fatty acids. 4. Terfahren according to claim 1, characterized gekenaseiohnet, dad as a Spoxyalkylather «ie the connection of the following foreelj 0 0 is used, where D is the equivalent hydrocarbon 909838/1488 ORIGINAL BATHROOM Substance residue from the dinning of polymerized potash oil fatty acids means. 5. Process including hardening of epoxy resins rather than an adjacent epoxy group, characterized in that the epoxy resin bit is a sulfhydryl resin produced by the process of one of claims 1-4. 6 · method according to claim 5 »characterized gekennseichn" t ₉ characterized in that the reaction is carried out in the presence of a catalyst · 7. The method according to claim 6, characterized in that tri- (dieethylasd.no- ■ ethyl) phenol is used as the catalyst. β. Method according to claims 5-7 * characterized in that an iupoxyhars with an epoxy equivalent weight of between 140 and 2000 is used. 9 * Method naoh claims 3-7 * characterized in that a polyglycidyl polyether is used as Bpoxyhars ▼ on bisphenol A and Bpichlorohydrin is used for Seneral Mille Inc, Lawyer 909838/1468