DE1247651B - Process for the production of molded articles on the basis of epoxy polyadducts - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

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German class: 39 c -13

1247 651 U9089IVd / 39c 3rd July 1962 17th August 1967

It is known to produce polyadducts by 1 mol of a diepoxide with at least 2 mol of a diamine. The polyadducts obtained can be used for the further conversion of epoxy compounds be used. Moldings produced from such mixtures by reaction are but usually hygroscopic, have a cloudy appearance, contain bubbles, have a slight mechanical strength and take a relatively long time to manufacture.

The invention relates to a process for the production of moldings based on Polyadducts by reacting epoxy compounds with more than one epoxy group in the molecule with amine adducts, which is characterized in that the amine adducts used are compounds of the general formula

Process for the production of moldings based on epoxy polyadducts

Applicant:

Union Carbide Corporation, New York, N.Y. (V. St. A.) Agents:

Dipl.-Ing. H. Görtz, patent attorney, Frankfurt / M., Schneckenhofstr. 27

Named as inventor:

Ralph Franklin Sellers, Middlebush, N. J .; Charles Fremont Pitt, Basking Ridge, N.J. (V. St. A.)

Claimed priority:

V. St. v. America July 3, 1961 (121358) - -

N - (CHa) ₃ - O - (C _n H _2n O), - (CH ₂ ) ₃ - NH ₂

OH R ¹

CH ₂ - CH - CH ₂ O

O
OCH 2 -CH-CH ₈

Ο - (CH ₂ ) S-NH ₂

used. In this formula, η denotes a whole 50 alkyl radicals with 1 to 4 carbon atoms. Preferred number from 2 to 5, χ an integer from 1 to 85, sometimes η = 2 or 3 and χ an integer a = O or 1, R and R ¹ hydrogen atoms or a number from 2 to 50.

709 637/672

Examples of epoxy compounds with more than one epoxy group in the molecule are Consider the diglycidyl ethers of mononuclear divalent phenols, for example, resorcinol, pyrocatechol or hydroquinone, of polynuclear dihydric phenols, such as the bis (p-hydroxyphenyl) alkanes, among them, for example, bis (p-hydroxyphenyl) methane, 1,1-bis (p-hydroxyphenyl) propane, 2,2-bis- (p-hydroxyphenyl) -propane or 2,2-bis- (p-hydroxyphenyl) -butane, and of dihydric phenols, which contain alkyl, aryl and / or halogen ring substituents. To the latter connections include, for example, the methylresorcinols, the tribromoresorcinols and the substituted bisphenols.

The diglycidyl ethers of dihydric alcohols, for example the reaction products, are also suitable of epichlorohydrin and aliphatic compounds containing 2 hydroxyl groups, for example ethylene glycol, propanediols or butanediols.

Further suitable diglycidyl compounds are the diglycidyl esters of dicarboxylic acids, for example the diglycidyl esters of adipic acid or phthalic acid. Diglycidyl compounds are also suitable, which are obtained by reacting epichlorohydrin with aromatic amines, for example Aniline, 2,6-dimethylaniline, p-toluidine, m-chloroaniline or p-aminodiphenyl. Specific compounds include N, N-diglycidylaniline, among others and N, N-diglycidyl-2,6-dimethylaniline.

The so-called peracetic acid epoxies can also be used in the process according to the invention, obtained by epoxidation of double bonds using peracetic acid, for example 1,2,5,6-diepoxydimethylcyclooctane, 3,4 - epoxy - 6 - methylcyclohexylmethyl - 3,4 - epoxy - 6 - methylcyclohexanecarboxylate, 2 - ethyl-1,3 - hexanediol - bis - (3,4 - epoxycyclohexanecarboxylate), Bis (2,3 - epoxycyclopentenyl) ether, vinylcyclohexenedioxide, dicyclopentadiene dioxide, diethylene glycol - bis - (3,4 - epoxy - 6 - methylcyclohexane carboxylate), S ^ -epoxycyclohexylmethyl-M-epoxy-6 - methylcyclohexanecarboxylate), 3,4 - epoxycyclohexylmethyl-S ^ -epoxycyclohexanecarboxylate, 3,4-epoxy-1 -methylcyclohexylmethyl-S ^ -epoxy-1 -methylcyclohexanecarboxylate, 1,6-hexanediol bis (3,4-epoxycyclohexanecarboxylate), bis - (3,4 - epoxycyclohexylmethyl) - oxalate, 3,4 - epoxy - 6 - methylcyclohexylmethyl - 9,10 - epoxystearate, 1,1 - bis (2,3 - epoxy-2-methylpropoxy) -ethane, 4,5-epoxypentyl-4,5-epoxypentanoate, bis - (3,4 - epoxy - 6 - methylcyclohexylmethyl) - sebacate, diglycidyl acetal, divinylbenzene dioxide, dipentene dioxide, 1,2,5,6-diepoxycyclooctane, Bis - (3,4 - epoxy - 6 - methylcyclohexylmethyl) adipate, glycidyl 2,3-epoxy-cyclopentyl ether, 3,9-bis (1,2-epoxy-1-methylethyl) -spiro-bi- (m -dioxane), Bis-3,4-epoxycyclohexyl) sulfone, glycidyl - 2,3 - epoxybutyl ether, bis (2,3-epoxy-2-methylpropyl) ether, 1,1-bis (2,3-epoxy-2- methylpropoxy) ethane, Di (6-methyl-3,4-epoxycyclohexylmethyl) ether, (6-methyl-3,4-ep-. Oxycyclohexylmethyl) - (3,4-epoxycyclohexylmethyl) ether and other similar diepoxides that are free of amino, amide, carboxyl and anhydride groups are.

Further epoxy compounds with more than one epoxy group in the molecule, according to the invention Can be reacted with the amine adducts, apart from the diepoxides already mentioned above the polyglycidyl ethers of the polyhydric phenols, for example the polyphenyls, such as the novolak condensation products of a phenol and a saturated or unsaturated aldehyde containing on average between 3 and 20 phenylene groups or more contained per molecule. Examples of suitable, one of a phenol and an unsaturated aldehyde, for example acrolein, derived polyphenylenes are the triphenols, pentaphenylenes and heptaphenylenes, the polyglycidyl ethers of polyhydric alcohols, e.g. B. the reaction products of epichlorohydrin and polyhydric alcohols such as glycerine, hexanetriols and the like, the polyglycidyl compounds of aminophenols, such as p-aminophenol, 5-amino-l-naphthol, 4-aminoresorcinol, 2-methyl-4-aminophenol, 2-chloro-4-aminophenol and the like. Specific compounds include, among others Ν, Ν, Ν ', Ν' - Tetraglycidyl - 4,4 '- diaminodiphenylmethane, the triglycidyl derivative of p-aminophenol, the amino hydrogen and OH hydrogen atoms being replaced by glycidyl groups.

The proportions of the implementation participants are usually calculated so that each Epoxy group. Amino hydrogen atom is omitted. This value can go up by about 25% or deviated downwards, although proportions by no more than 10% deviate from the stoichiometric ratio are preferable.

The reaction between the amine adducts and the epoxy compounds occurs when the adduct and the epoxy are simply mixed together. The reaction proceeds slowly at temperatures of approximately 10 ^{° C.} The reaction lasts 2 days below about 20 ° C '. As a rule, the mixture is heated to temperatures between about 30 and 200 ° C, preferably at 20 to 150 ⁰ C, warmed.

If the epoxy compound is a liquid of relatively low viscosity, it will be Amine adduct mixed in immediately. Epoxies that mix easily with the amine adducts too are viscous can be heated to reduce their viscosity. To the desired thin liquid To achieve, liquid solvents can also be added. Solid epoxies are usually used melted or mixed with liquid solvents.

Suitable solvents, the highly viscous or normally solid epoxy compounds the desired Mediate thin liquid are ketones such as acetone, methyl isobutyl ketone, isophorone and the like, Esters such as ethyl acetate, butyl acetate, ethylene glycol monoacetate or acetate of ethylene glycol monomethyl ether, Ether alcohols, such as methyl, ethyl and butyl ethers of ethylene glycol or diethylene glycol, chlorinated hydrocarbons such as trichloropropane or trichloromethane. As an admixture to the other

'60 given solvents are also aromatic hydrocarbons, such as benzene, toluene or Xylene, alcohols such as ethyl alcohol, isopropyl alcohol or n-butyl alcohol. The amount of used Solvent depends in detail on the epoxy present. If you wish, you can instead Solvents of the type described above or in addition to these known in a known manner reactive liquid diluents that contain a

only epoxy group

C - C -

can be used to obtain the desired thinness of the epoxy compounds.

In a known manner, additional substances such as fillers, pigments, fibers, dyes, plasticizers, Flame retardants and the like, as desired, the epoxy compounds or the amine adducts can be added.

Molded body, e.g. B. Paints from the. mixtures described prepared according to the invention are characterized by excellent impact resistance and good flexibility. The too Mixtures used in their production do not foam during implementation and react quickly Time, even in moist air, to be free of voids and bubbles, very clear, infusible and not adhesive moldings.

Example of manufacture

an amine adduct used according to the invention, for the purposes of this invention

no protection is sought

600 g (1.56MoI) of diglycidyl ether of 2,2-bis- (p-hydroxyphenyl) propane with an epoxy equivalent weight of 192 and an epoxy equivalent of 2 were heated to 70 ° C and, with stirring, 2400 g ( 10.9 mol) of di- (3-aminopropyl) ether of diethylene glycol preheated to 40 ° C. was added. ■ During this 45-minute period increased a slightly exothermic reaction, the temperature of the mixture to a maximum of 75 ⁰ C. It was then allowed to the thus-formed product at room temperature (approximately 23 ° C) stand until it was cooled to room temperature.

The liquid product had a viscosity of 193 cSt at 25 ° C, a calculated equivalent weight of 74.1 grams per gram equivalent of amino hydrogen and contained a calculated amount of 42.8 percent by weight of amine adduct.

The di- (3-aminopropyl) ether of diethylene glycol given in this and in the following examples has the formula

H ₂ N - (CHa) ₃ - O - (CH ₂ - CH ₂ - O) ₂ - (CH ₂ ) ₃ - NH

example 1

100 g of diglycidyl ether of 2,2-bis (p-hydroxyphenyl) propane were at about 23 ° C with 39 g of the liquid reaction product of 600 g of diglycidyl ether of 2,2-bis (p-hydroxyphenyl) propane with 2400 g of di (3-aminopropyl) ether of diethylene glycol in an oven at 175 ° C for 5 minutes implemented in an infusible product.

No foaming of the mass occurred during the reaction.

The molded body produced in this way had no voids and bubbles. ^p

Example2

The procedure of Example 1 was repeated with the difference that 39 g of the liquid reaction product from 72 g of butyl glycidyl ether and 528 g of the diglycidyl ether of 2,2-bis (p-hydroxyphenyl) propane with 2400 g of di (3-aminopropyl) ether of diethylene glycol were used. The same good results have been obtained.

Example 3

'100 g of the liquid product obtained according to Example 1 were at about 23 ⁰ C with 43 g of the liquid reaction product of 96 g of butyl glycidyl ether and 704 g of 2,2-bis (p-hydroxyphenyl) -propane with 2400 g of di- ( 3-aminopropyl) ether mixed with diethylene glycol. Otherwise, the procedure according to Example 1 was followed. The same good results were obtained.

Example 4

100 g of the liquid reaction product obtained according to Example 1 were mixed with 39 g of the liquid reaction product mentioned in Example 1 at about 23 ° C. The mixture was with a Brush applied to steel panels, which then at a humidity of 80% for 8 hours to about 80 ° C were heated. The resulting coating was non-sticky and had excellent gloss.

Example 5

90 g of the liquid reaction product obtained according to Example 1, 10 g of triphenyl phosphite as Anti-inflammatory agent, 20 g of methyl ethyl ketone, 10 g of xylene, 10 g of butanol and 39 g of the in Example 1 mentioned liquid reaction product were mixed at about 23 ° C and applied with a brush Linoleum panels painted on. After 12 hours of storage at 25 ° C and a humidity of 80% of the coating was tack-free and dry to a glossy finish.

Example6

100 g of the liquid reaction product obtained according to Example 1, 50 g of titanium dioxide and 39 g of the liquid reaction product mentioned in Example 1 were mixed at room temperature. The mixture was cracked, eroded with a brush Painted wood. After 5 hours, the spread was tack-free and dried to a glossy finish.

Claims (1)

Claim: Process for the production of moldings based on polyadducts by reaction of epoxy compounds with more than one epoxy group in the molecule "with amine adducts, characterized in that the amine adducts used are compounds of the general formula N - (CHg) ₃ - O - (C _n H _2n O) _x - (CH _{2) 3} - NH ₂ OH R ¹ CH ₂ -CH-CH ₂ O H ₂ C-HO-CH CH ₂ N - (CH ₂ ) ₃ - (OC ₁ H _2n ) * - O - (CH ₂ ) ₃ - NH ₂ where η is an integer from 2 to 5, χ is an integer from 1 to 85, a = O or 1, R and R ¹ denote hydrogen atoms or alkyl radicals having 1 to 4 carbon atoms. References considered: U.S. Patent No. 2,651,589. 70Sh 637/672 8.67 © Bundesdruckerei Berlin