DE2528021A1 - Modified polyglycidyl ethers - contg. aliphatic, cycloaliphatic or aliphatic cycloaliphatic gps. or mixts. of these - Google Patents

Abstract

Prepn. of modified aliphatic and/or cycloaliphatic and/or aliphatic-cycloaliphatic polyglycidyl ethers of formula (I): (NZ2R2)-m1-R3-(NZ2R5)-m2-NZ2R4 comprises reaction of a mixt. comprising polyglycidyl ethers of formula (II): with polyamines of formula (III): (HNR2)-m1-R3-(NHR2)-m2-NHR4. where R1 = H and/or CH3 R2 and R4 = H or a 1-10C (pref. 1-2C) unsubstd. aliphatic, cycloaliphatic or aliphatic-cycloaliphatic residue on condition that if R2 and/or R4 = H in formula (III), R2 and/or R4 in formula (I) will in this case represent Z2. In addn. R3 and R5 = 2-10C unsubstd. aliphatic, cycloaliphatic or aliphatic-cycloaliphatic residues; R6 = 2-4C aliphatic, satd. unsubstd. organic residue and R7 = 2-20C unsubstd. aliphatic, cycloaliphatic or aliphatic-cycloaliphatic residue; X and Y = Cl or Br; k1, k2 and k3 = 0-12 ; k4 = 0-(6-n); k5 = 0-4; p = 0.01n-0.5n (pref. 0.2n-0.3n); m1 ; 1-3; m2 = 0-3, (m1+m2) pref. being 2 or 3 and n = 1-6, pref. a mixt. of different polyglycidyl ethers is involved and n = 1.8-3.4. The reaction is carried out with a deficit of NH- or NH2-gps. calculated on epoxy gps. (III) being gradually added to (II). Used as reactive diluents or plasticisers for epoxy resins and, owing to their freedome from yellowing, in coating resins and transparent castings. Better pot life and improved curing properties compared with other prods. of this type. In an example 158g. 3-aminomethyl-3,5,5-trimethylcyclohexylamine were added dropwise during 2 h. at 80 degrees C under N2 to 2000g neopentylglycol-polyglycidyl ether. After 4 h. more at 80 degrees C, the prod. was cooled at 20-30 degrees C.

Description

Process for the preparation of modified aliphatic and / or cycloaliphatic and / or aliphatic-cycloaliphatic polyglycidyl ethers.

Aliphatic and cycloaliphatic glycidyl ethers are increasingly gaining ground in importance; on the one hand, they are used as reactive thinners and for reactive elasticization of epoxy resins, on the other hand mainly because of the low tendency to yellowing in lacquer resins and for transparent casting resins.

Especially when using the di- and higher-functional aliphatic and / or cycloaliphatic and / or aliphatic-cycloaliphatic glycidyl ethers without mixing with epoxy resins based on bisphenol A result in curing with aliphatic, cycloaliphatic or cycloaliphatic-aliphatic Polyamines difficulties.

When using aliphatic polyamines occur relatively long pot life (potlives) very quickly to very high peak temperatures, which at larger castings can even lead to clogging. Thin films, on the other hand, harden bad or not at all without tempering. When using cycloaliphatic or aliphatic-cycloaliphatic polyamines often occur too long Pot life (potlives), the hardening is even with larger castings without tempering not satisfactory.

The object of the present invention is therefore a method for production of modified aliphatic and / or cycloaliphatic and / or aliphatic-cycloaliphatic Glycidyl ethers with improved hardening characteristics, measured on the 100 g pot life [Time to maximum temperature = t (min), maximum temperature = Tmax (° C)] and / or to provide the hardening in the lacquer film.

It is known that the hardening characteristics of glycidyl ethers through the use of polyols and / or tertiary amines and / or polysulphide compounds (DT-OS 1 696 645) can be improved.

Significant disadvantages of these methods are that these compounds either not incorporated during the hardening process and / or highly elasticized and / or have a strong odor nuisance.

Although a use of aliphatic amines for adduct formation with epoxy resins based on bisphenol A in excess reaction products of insufficient Provides storage stability, it has now surprisingly been found that aliphatic and / or cycloaliphatic and / or aliphatic - cycloaliphatic glycidyl ethers with aliphatic and / or cycloaliphatic and / or aliphatic-cycloaliphatic Polyamines have been converted under certain conditions, modified glycidyl ethers without free NH and NH2 groups * but with free epoxy groups, which delivers the have the desired hardening characteristics, are storage-stable and are water-white Keep color.

Polyamine-epoxy resin adducts that no longer contain epoxy groups, but contain free NH and NH2 groups, find modified hardeners for Epoxy resins use ("Epoxy resins", Jahn, 1969, p. 157 ff.) Also the use of adducts of polyamines with unsaturated nitriles, such as acrylonitrile for damping the exothermicity in the hardening of polyepoxides is described (US-PS 2Z753ß323) These However, adducts have a strong yellow to brown intrinsic color, which is often undesirable.

The present invention relates to a process for the preparation of modified aliphatic and / or cycloaliphatic and / or aliphatic-cycloaliphatic polyglycidyl ethers of the general formula 1 characterized in that polyglycidyl ethers of the general with polyamines of the general formula III, where the symbols used in formulas I, II and III denote, where R1 is H and / or CH3, R2, RH or an aliphatic or cycloaliphatic or aliphatic-cycloaliphatic unsubstituted organic radical with 1 to 10, preferably 1 to 2, C atoms, the condition applies when R2 and / or R4 in formula III is H, then R2 and / or R4 in formula I is correspondingly the radical z2, and R3 R5 is an alaphatic or cycloaliphatic or aliphatic-cycloaliphatic unsubstituted organic radical having 2 to 10 carbon atoms, R6 is an aliphatic , Saturated, unsubstituted organic radical with 2-4 carbon atoms, R7 denotes an aliphatic or cycloaliphatic or aliphatic-cycloaliphatic unsubstituted organic radical with 2 to 20 carbon atoms, X, Y denotes C1, Br, K1, K2, K3 denote a number from 0 to 12, K4 is a number from 0 to 6-n, K5 is a number from 0 to 4, p is 0.01n to 0.5n, preferably 0.2n to 0.3n , m1 represents a number from 1 to 3, m2 means a number from 0 to 3, where m1 + m2 is preferably 2 to 3 and n represents a number from 1 to 6, it is preferably a mixture of different polyglycidyl ethers and n has a value between 1.8 and 3, 4, in a stoichiometric deficit of NH or NH2 groups, based on epoxide groups, with mixing, the compound with the formula II being placed in the reaction vessel and the compound with the general formula III gradually being added with stirring.

A preferred mode of operation is characterized in that the Reaction under an inert gas atmosphere, e.g. nitrogen, at 20-1200C, preferably at 70 - 900C, within 2 - 6 hours, most preferably within 3 - 4 hours, with an equivalent ratio of polyglycidyl ether: polyamine = 4: 0.2 to 4: 2, am most preferably of 4: 1. The implementation is by tracking the EV value (Epoxy equivalent weight3 controlled and finished when the EV value is within from 30 to 60 minutes at reaction temperature by less than 10 to 50, preferably changes by less than 10-15.

The invention also relates to the new modified aliphatic and / or cycloaliphatic and / or aliphatic-cycloaliphatic polyglycidyl ethers with the formula (I).

The invention also relates to the use of the new polyglycidyl ethers with the formula (I) as cold-hardening epoxy resin with improved hardening characteristics for the production of coatings and moldings.

Examples of polyglycidyl ethers according to formula II that can be used as starting products according to the invention are: a mixture of (poly) ethylene glycol monoglycidyl ether and (poly) ethylene glycol diglycidyl ether of general formula IV and / or H and X Cl, Br and R1 CH3 and / or H, n is an integer from 0 to 12 and, K5 is an integer from 0 to 4 and / or a mixture of (poly) propylene glycol mono- and diglycidyl ether of the general formula V where R8 and n have the same meaning as in (IV) and / or a mixture of the mono- and diglycidyl ethers of the optionally oxethylated and / or oxpropylated neopentyl glycol of the general where R8, R1 and n have the same meaning as in formula (IV) and preferably n has the value zero and / or a mixture of the mono- and diglycidyl ethers of the optionally oxethylated and / or oxpropylated dibromoneopentyl glycol of the general formula (VII) where R8, R1 and n have the same meaning as in formula (IV) and preferably n has the value zero and / or a mixture of the mono- and polyglycidyl ethers, the optionally oxethylated and / or oxpropylated glycerol of the general formula VIII where R8 R1, and n have the same meaning as in formula (IV) and preferably n has the value zero and / or a mixture of the mono- and polyglycidyl ethers of the optionally oxethylated and / or oxpropylated pentaerythritol where R8, R1 and n have the same meaning as in formula (1V) and preferably n has the value zero and 1 to 2 radicals RH and / or a mixture of the mono- and polyglycidyl ethers of the optionally oxethylated and / or oxpropylated sorbitol, preferably wide of the D-sorbitol of the general formula X. where R8, R1 and n have the same meaning as in formula (IV) and preferably n has the value zero and 2 to 4 radicals R8 have the meaning of H, and / or a mixture of the mono- and polyglycidyl ethers of the optionally oxethylated and / or oxopropylated mannitol, preferably D-mannitol of the general formula XI where R8, R1 and n have the same meaning as in formula (IV) and preferably n has the value zero and 2 to 4 radicals R have the meaning of H and / or a mixture of the mono- and polyglycidyl ethers of the optionally oxethylated and / or oxpropylated dipentaerythritol of the general formula XII where R9 is the meaning of and R8, R1 and n have the same meaning as in formula (IV) and preferably n has the value zero and 2 to 4 radicals R8 have the meaning of H and / or a mixture of the mono- and diglycidyl ethers of the optionally oxethylated and / or oxpropylated 2,2-bis (p-hydroxycyclohexyl) propane of the general formula XIII where R9, R8, R1 and n have the same meaning as in formula XII and preferably n has the value zero, and / or a mixture of the mono- and diglycidyl ethers of the optionally oxethylated and / or oxpropylated bis (1,4-hydroxymethyl) -cyclohexane of the general formula XIV where R9, R8, R1 and n have the same meaning as in formula XII and preferably n has the value zero and7or a mixture of the mono- and polyglycidyl ethers of the optionally oxethylated and / or oxpropylated trimethylolpropane of the general formula XV where R9, R8, R1 and n have the same meaning as in formula XII and preferably n has the value zero and / or a mixture of the mono- and diglycidyl ethers of the optionally oxethylated and / or oxpropylated 3 (4), 8 (9) -Bis- (hydroxymethyl) -tricyclo [5.2.1. o2 6 | decans of the general formula XVI where R9, R8, R1 and n have the same meaning as in formula XII and preferably n has the value zero.

Most preferred are the polyglycidyl ethers of the formula VI with the Value n equal to zero, the formula VII with the value n equal to zero, the formula VIII with the value n equal to zero, the formula IX with the value n equal to zero, where 1 to 2 R radicals have the meaning of H, of the formula XIII with the value n equal to zero, the Formula XIV with the value n equal to zero and the formula XV with the value n equal to zero Use.

The formulas of the polyglycidyl ethers that can be used are idealized insofar as than for technical purposes, of course, those on a technical scale with the Polyglycidyl ethers accessible to impurities known to those skilled in the art are used can be. For example, the mono-polyglycidyl ether mixture contains pentaerythritol the general formula IX still minor admixtures of dipentaerythritol, nor minor polypentaerythritol mono (poly) glycidyl ether mixtures. These include in the technical products usually contain impurities without Restriction of the implementation according to the invention of the above Polyglycidyl ether.

Examples of polyamines of the formula III which can be used according to the invention are: alkylene polyamines. of the general formula XVII (XVII) H2N- (CH2-CH2-NH-) - CH2-CH2-NH2 where n is an integer from 0 to 3 and / or 2.24-trimethylhexamethylenediamine of the formula XVIII and / or 3-aminomethyl-3.5.5-trimethylcyclohexylamine of the formula XIX and / or 1. 4-bisaminomethylcyclohexane of the formula XX and / or bis (4-amino-3-methyl-cyclohexyl) methane of the formula XXI The polyamines described by means of chemical formulas, which can be reacted according to the invention, can also be used in technical quality, as are customary in the trade, without hesitation. For example, the alkylene polyamines according to formula XVII are generally 99% pure and are essentially contaminated by their higher or lower homologues. Trimethylhexamethylenediamine is an isomeric mixture of 2.2.4- and 2.4.-4-trimethylhexamethylenediamine.

In order to adequately describe the polyamines which can be used, some additional characteristic values of polyamines which can be used according to the invention are given below as an example: Polyamine density boiling point melting point d24 ° 09 / ml1 L0cJ 760 mm Hg F0c Xthylenediamine 0.9089 117 Diethylenetriamine 0.9542 206.9 -39 Triethylenetetramine 0.9818 277.4 -35 Tetraethylene pentamine 0.9980 340 -3o (Decomposition) 2.2.4 (2.4.4) trimethyl hexamethylenediamine 0.867 232 -80 3-aminomethyl-3.5.5- trimethylcyclohexyl- amine 0.924 247 10 Bis (4-amino-3-methvl- 20 mm Hg: cyclohexyl) methane 0.945 200-212 - The polyglycidyl ethers which can be prepared according to the present invention and can be described by the general formula I, preferably up to 90 ° C., and most preferably liquid at room temperature, have an improved hardening characteristic compared to the known polyglycidyl ethers of the general formula II and are characterized by the fact that larger castings have considerably reduced , exothermic heat tint can be produced from the polyglycidyl ethers of the general formula I according to the invention and aliphatic polyamines as known cold hardeners; In some cases, as is often also desired, the hardening speed in the casting is increased.

This improvement in curing characteristics can best be achieved follow, by using a polyglycidyl ether-polyamine test mixture of 100 g Temperature maximum (= TmaxF0C3) and at the same time the time required to reach the temperature maximum (- tmaX Lminj) is determined.

The hardening characteristics with regard to the hardening process in the The paint film is improved, i.e. one achieves with the same layer thicknesses compared to conventional aliphatic, cycloaliphatic or aliphatic-cycloaliphatic Polyglycidyl ethers of the general formula II take a shorter time to dry as dust or for thorough drying, which is desirable. The dust-drying time and through-drying time are either determined simply by finger pressure, which is the case with comparative tests is quite sufficient, or suitable test equipment is used, e.g. so-called.

"Drying time recorder" as they can be obtained on the device market.

The polyglycidyl ethers according to the invention are combined as preparations with aliphatic and / or cycloaliphatic and / or aliphatic cycloaliphatic Polyamines as cold hardeners can be used primarily in the cast resin sector, e.g. because of the low viscosity for embedding certain materials, for model making or also for the production of relatively non-yellowing moldings or for production of molded bodies with a relatively high hydrogen content, which is the case when used in nuclear engineering is of interest. In the coating sector, the polyglycidyl ethers can e.g. in the production of low-viscosity} low-yellowing paints or glazes Find.

In the following examples, epoxy equivalent weight is denoted by "EV" abbreviated.

Example 1: 2000 g of neopentyl glycol polyglycidyl ether xl with an epoxy equivalent weight of 130 are heated to 80 ° C. with stirring and nitrogen and within 2 h 158 g of 3-aminomethyl-3.5.5-trimethylcyclohexylamine were added dropwise. Then one leaves under Stir at 800C for 4 h and cool down to 20-300C. You get a clear Liquid with an epoxy equivalent weight of 170, xl) According to the literature well-known 2-step processes (see e.g. "Epoxy compounds and Epoxy Resins "A.M. Paquin (1958) at pages 166-168 and cited there Literature).

a viscosity, measured at 25 ° C., of 300 m Pas and a Gardner color number of <1.

The reaction product shown in Example 1 is a polyglycidyl ether of the general formula (I) in which R1 denotes H5 R and RH denotes R3 the remainder and R7 the rest means. K1, K2 and K3 mean zero, K4 represents a number of about 0.3, K5 a number of about 0.2, p represents 0.25 nn, where n is about 1.8. m2 is zero and m1 is 1. X means Cl.

Example 2: 2755 g of dibromoneopentyl glycol polyglycidyl ether x2 (EV = 265) are heated to 80 ° C. with stirring and nitrogen. Within 2 h 116 g of 3-aminomethyl-3.5.5-trimethylcyclohexylamine were added dropwise. Then let it be react further (approx. 2-4 h) until the EV value is no stronger when checked every hour than increased by 10. The filtered reaction product obtained has a viscosity from 12000 - 13 500 m Pas and an EV of 330 - 335.

The reaction product shown in Example 2 is a polyglycidyl ether of the general formula (I) in which R1 is H R2 x2) As xl, see also US-PS 3,686,358, GB-PS 1,310,961 and tYr-OS 2 030 611.

K1 means 2 and Y means Br. K2 and K3 mean zero, K4 represents a number of about 0.3, K5 a number of about 0.2, p represents 0.26 n, where n is about 1.8. m2 is zero and ml is 1.

X means Cl.

Example 3: 3200 g of pentaerythritol polyglycidyl ether, x3 with an epoxy equivalent weight of 140 are heated to 80 ° C. with stirring and under a nitrogen atmosphere. Within 50 g of 2.2.4 (2.4.4) trimethylhexamethylenediamine are added dropwise over a period of 2 hours. Then lets one after-reacting (about 2 - 4 h) until the EV value is checked every hour did not increase by more than 10. The filtered reaction product obtained had a Gardner viscosity from Z1 to Z2 and an epoxy equivalent weight from 176.

The reaction product shown in Example 3 is a polyglycidyl ether of the general formula (I), in which R1 is H, R2 and R4 are H, and R3 is the remainder and / or the rest R7 the rest means. K19, K2 and K3 represent zero, K4 represents a number of about 0.75, K5 a number of about 0.4, p represents 0.06 n, where n is about 3.25; m2 is zero and ml is 1.

X means Cl.

The following are comparative hardening tests to prove the technical progress achieved. The processing temperature is in all tests 23 ° C, the amount of hardener is always equivalent to the EV of the resin has been chosen.

x3) Manufactured according to example 1 of DOS 1 956 490.

A. Potlife tests No. hardener comparative tmax Tmax invention tmax Tmax product [min] [° C] according to [min] [° C] product 1 3-aminomethyl neopentyl 240 80 product 75 102 3.5.5-tri-glycol poly-; according to methylcyclo-glycidyl example hexylamine ether x1 1 2 triethylene- "60 320" 27 185 tetramine 3 trade pro- dibromeneo- 15> 300 product 18 120 pentylglycol- according to "Beckopox polyglycidyl cabbage example Special hardener x2 lung " ter EH 605 " x4 4 3-aminomethyl pentaerythritol 38 120 product 28 126 3.5.5-tri-polyglycidyl according to methylcyclo-ether example hexylamine X³ 3 B. Tests for filir hardening (film thickness 200 ijm, 230C) No. Hardener Comparative Dust- Adhesive- Through- Invention- Dust- Adhesive- Through- product dry- # free drying- dry- free drying- ken [f] nung according to ken [h] nung [h] [h] product [h] [h] 3-amino-neopentyl>24>24> 24 product 4,4 - <24 methyl glycol according to 3.5.5- polygly- # example trimethyl cidyl ether 1 cyclo- 1 hexyl amine 2 2.2.4 (2nd pentaery- 3.5 5.7> 24 product 1.7 4.5 22 4.4) Tritrite poly- according to methyl glycidyl example hexa- ether 3 methylene diamine x4) Modified, aliphatic polyamine, solvent-free from the Hoechst AG delivery program. Hydrogen equivalent weight = 59, viscosity at 250C = 850 m Pas, density = 1.02.

Described in the leaflet "Epoxy Resin Hardener" edition 7/1974 of the company Hoechst AG as a commercial product "Beckopox special hardener EH 605".

Examples 4 and 5: each with a mixture of 170 g of polyglycidyl ether according to Example 1 and 43 g of 3'-aminomethyl-3.5.5-trimethylcyclohexylamine were a.) a printed circuit to protect against mechanical damage and b.) a biological one Preparation, which was previously dried, then pre-impregnated with the above mixture and hardened was poured. There were transparent, air bubble-free castings with a mirror-like finish Surface preserved. All castings were without tempering after 1.5 hours demoldable.

Example 6: A chipboard printed with a "wood pattern" "Freudenberg fleece was provided with a mixture of 176 g of polyglycidyl ether coated according to Example 3 and 43 g of 3-aminomethyl-3.5.5-trimethylcyclohexylamine. It became completely tack-free after 5-6 h without heat treatment and also without any aftertreatment A mirror-like surface is obtained, the scratch resistance of which is very high on further storage is good (pencil hardness 9H)

Claims (3)

Claims 1. experienced for the preparation of modified aliphatic and / or cycloaliphatic and / or aliphatic-cycloaliphatic polyglycidyl ethers of the general formula I. characterized in that polyglycidyl ethers of the general with polyamines of the general formula III, where the symbols used in formulas I, II and III denote, where R1 is H and / or CH3, R2, R4 is H or an aliphatic or cycloaliphatic or aliphatic-cycloaliphatic unsubstituted organic radical having 1 to 10, preferably 1 to 2, carbon atoms, the condition when R2 and / or 4 in Formula III is an H. so R² and / or R4 in formula I is the radical Z2 furthermore R3, R5 an aliphatic or cycloaliphatic or aliphatic-cycloaliphatic unsubstituted organic radical with 2 to 10 carbon atoms, R6 represents an aliphatic saturated, unsubstituted organic radical with 2- d represents carbon atoms, and R7 denotes an aliphatic or cycloaliphatic or aliphatic-cycloaliphatic unsubstituted organic radical having 2 to 20 carbon atoms, X, Y denotes C1, Br, K1, K2 and KX denote a number from 0 to 12, K4 represents a number from 0 to 6-n, K5 represents a number from 0 to 4, p represents 0.01 n to 0.5 n, preferably 0.2 n to 0.3 n, m1 represents a number from 1 to 3 represents, m2 means a number from 0 to 3, where ml + m2 is preferably 2 to 3 and n represents a number from 1 to 6, it is preferably a mixture of different polyglycidyl ethers and n has a value between 1.8 and 3.4, in the stoichiometric deficit of NH or NH2 group pen based on EpoxidgruspenJunter mixing, the compound with the formula II being placed in the reaction vessel and the compound with the general formula III being gradually added with stirring. 2. New modified aliphatic and / or cycloaliphatic and / or aliphatic-cycloaliphatic polyglycidyl ethers of the formula (I). 3. Use of the new polyglycidyl ethers with the formula (I) as cold-curable Epoxy resin with improved curing characteristics for the production of coatings and moldings.