DE1951524A1 - Process for the production of molded bodies and coatings - Google Patents

Description

File 21i »3

REICHHOLD-ALBERT-CHEMIE AKTIENGESELLSCHAFT, 2 Hamburg 70, Iversstrasse 57

Process for the production of moldings and coatings

It is known to use aliphatic, cycloaliphatic, araliphatic or heterocyclic polyamines, such as diethylenetriamine or triethylenetetramine, for curing epoxy resins at room temperature. The hardening products obtained in this way are, however, relatively brittle, and their water and acid resistance is only moderate, especially when an excess of amine is used. Pur many applications is occurring during curing heat development is disadvantageous because, for example can be achieved in the production of larger castings due to poor heat dissipation particularly in the interior of the casting maximum temperatures of about 200 ⁰ C, whereby stress cracking, discoloration and an additional shrink the properties of the Affect hardening products.

It is known that phenols can be added to the polyamines in order to accelerate the curing reaction, which, especially at low temperatures, for example around zero, practically does not proceed at all, and at high humidity leads to cured coatings and moldings with sticky and cloudy surfaces. The addition of phenols accelerates the reaction and lowers the curing temperature, but the chemical properties of the cured products are adversely affected.

009824/1885

It is also known to cure epoxy resins with adducts of epoxy compounds and certain polyamines in order to improve the surface hardening of the amines, which leads to what is known as "blue tarnishing" in atmospheric humidity, ie the formation of a cloudy, sticky surface. However, these amine adducts fail even at lower temperatures, for example below 15 ^° C., at which the curing proceeds too slowly. In addition, the chemical properties of the cured products are not always satisfactory.

Furthermore, the use of condensation products from polyvalent aliphatic amines, one or polyhydric phenols with at least one aldehyde-reactive core site and aldehydes for curing "Compounds with more than one epoxy group per molecule are known.

The use of these hardeners for hardening epoxy resins based on the known amines, such as ethylenediamine, Diethylenetriamine, triethylenetetramine and Tetraäthylenpentamin, brings a hardening acceleration and curing at low temperatures, but molded parts are obtained after curing of considerable brittleness, which makes the possible uses for these resin-hardener combinations forbid in many areas where a certain elasticity is required.

) The tendency to brittleness has the use

prevented by epoxy resins for purposes for which they would otherwise be excellently usable. For example, the electronics industry makes extensive use of resins for embedding purposes, but most curable epoxy resins cannot be used for embedding steel and other metal articles because they cannot withstand the stresses that arise when the casting is moved from reaction temperature to room temperature or cools underneath.

009824/1885

It is well known that a variety of materials can be incorporated into the epoxy resins to to plasticize the hardened products, i.e. the hardened products less brittle and opposite to make mechanical stresses less sensitive, e.g. by giving them flexibility and elasticity to lend. However, the plasticizers known up to now have certain disadvantages, including the number the uses for which they are suitable. Most emollients bring with it an undesirable increase in the viscosity of the uncured mixtures. This is what she does , unsuitable for pouring complicated articles or for impregnating fibrous materials. In some cases, a satisfactorily low viscosity can be achieved by increasing the temperature of a uncured mixture can be achieved, but this reduces the useful life or the time during which the mixture can be used for the intended purpose. Some plasticizers increase in undesirable extent, the time required to cure the epoxy resin mixture. Other plasticizers bring about a considerable deterioration in the quality of the cured products, e.g., loss occurs moisture resistance or a decrease in tensile strength.

The known use of polyoxypropyleneamines as hardeners for epoxy resins avoids the Lack of brittleness. '

These known polyoxypropyleneamines can

e.g. represented by the following formulas: CH, CH,

NH ₂ - CHCH ₂ (-OCH ₂ CH-J _x JJH ₂ χ = 1 to 50, (I)

009824/1885

8AD OWGiNAL

ί3 CH ₂ (-OCH ₂ CH-

CH

(OHg) _n O-CH ₂ (-OCH ₂ OH- I

x, y and ζ = 1 to 50

η * Ό to 5 (II)

, X = NHg or - OHj

I ί3 CH ₂ (-OCH ₂ CH-) _Z X

CH-,

ι · ⁵

OHR (-0CH ₂ CH) _x -NH ₂

CH

(CH (-0CH ₂ CH) _y -X) _u

CH.

CH,

J,

- X

CH ₃

R = - H or - CH,

χ, y and z = 1 to

u = 0 to 4 (III) X = -NH ₂ or -OH

and

CH ₅ x, y, z and u = 1 to 50 CH ₂ (-OCH ₂ .CH) -NH ₂ X = - NHg or - OH (IV)

CH ₂ (-0CH ₂ .CH) ₂ - X CH-

₂ (-QOH ₂ -CH) ₁₁ -X

When used for curing polyepoxides, however, these polyether amines have the disadvantage of very long curing times at room temperature. At temperatures around ⁰ ° C. there is almost no hardening at all. At high humidity, the "blue tarnish" also occurs, ie the au-

009824/1885

formation of a cloudy, sticky surface. The following table shows the pot life of some polyoxypropylenamines again. (The pot life is understood as the time in which a mixture of 100 g of a polyglycidyl ether made from bisphenol A and epichlorohydrin with an epoxide equivalent of about 190 and an equivalent amount of the respective hardness component is gelled at room temperature.)

TABLE 1

Polyoxypropylene amine type I. Molecular Pot life I. weight in hours I. 190 4 to 5 Formula I. I. 250 7 to 8 Il 400 24 Il 1000 r 24 Il 2000 5-24 ti

The aim of the present invention is to provide a process for the production of moldings and coatings to find in which the aforementioned disadvantages do not occur.

The invention relates to a process for the production of moldings and coatings by reacting epoxy compounds with more than one 1,2-epoxy group per molecule, optionally mixed with monoepoxides, with polyether amines, characterized in that the polyether amines are condensation products of polyoxypropylene amines , Phenols and aldehydes.

The condensation products of polyoxypropyleneamines »phenols and aldehydes can be obtained by the general Formula. · OH

009824 / 188S

' BAD QRlGtNM-

where R ₁ = H-, CH ₃ -, C ₂ H ₅ -, C ₃ H ₇ -, C ₄ H ₉ -

or

CH

= - NH- (C-CH ₂ O) ₃₅ . - A, χ = 1 to 50 = H-, CH ₃ -, (CH ₃ J ₃ C -, HO-,

-O-

or HO

B = - CH ₂ -, -C (CH ₃ ) ₂ - or - SOg-,

η = whole numbers from 1 to 3 "and m = whole numbers from 1 to 3, and where A represents the following radicals:

CH

CH CH

- CHCH ₂ -, CH ₃ (CH ₂ ) _n C-CH ₂ (-OCH ₂ CH-) _y NH ₂

H ₀ (-0CH ₀ CH-) " X,

I f3
(CHi-OCH ₀ CH) -X)

t .C

CH
₂ CH) ₂

CH ₃
CH ₂ (-OCH ₂ CH) ₂ - X and

/ t /> CH "(-OCH ₉ .CH) _ - NH ₉

^ CH ₃

(-QCH ₂ .CH) _y - X

^CH 3 (-0CH ₂ .CH) ₂ - X,

where R = 5 - H or - CH ₃ ,

u, x, y and ä = »1 to 50,

χ * - NH ₂ or - OH are represented.

The aforementioned new condensation products can through / reaction of phenols of the general formula

009024/1885

.8ADUJfUOlNAt,;

in the. R ₃ «H-, CH ₃ , (GH-J ₃ C-, HO- or HO ff \. B -

m = an integer from 1 to 3 and B = - CHp-j - C (CH,) _p - or r SO ₉ - represent, with polyoxypropylamines of the general formula

CH,
I 3
A - (-OCH ₂ CH-) _χ Μ ₂ with χ = 1 to 50,

, where A - represents the following radicals:

CH ₅ CH ₂ OH,

NH ₂ - CHCH ₂ -, ^ CH ₃ (CH ₂ ) _n C-CH ₂ (-OCH ^ GH-) NH ₂

I ^ H-t

CH ₂ (-OCH ₂ CH-) ₂ X;

.CH CHR ■ „ _w / ^d CH ₃

I ^H 3 /

(CH (-OCH ₂ CH) -X) ₁₁ // ^CH 2 (

I? ^H 3 ^C \ <T? ^H 3

CH ₀ (-0CH ₀ CH) -X and V ^ CH ₉ (-OCH ₉ .CH) -X

2 2 z \ ^0H 3

(R β H- or CH ₃ -) XJH ₃ (-OCH ₂ CH) ₃ -X

and with aldehydes of the general formula RHCO, where R = H-, CH ₃ -, C ₉ H ₅ -, C ₃ H ₇ -, O ₄ H ₉ -

or \ / means

V— .. ':; ί /

will be received *

009824/1885

You can file the polyoxypropyleneamines for "·.. ration of the properties of these condensing products to a greater or lesser extent by other condensed aliphatic, araliphatic, heterocyclic and / or cycloaliphatic amines be replaced ".

The molar ratios of the individual components. Amine, aldehyde and phenol, can depending on the desired viscosity and characteristics of the ~ o * .- & condensation products within wide limits "at dor ^ n /.Yr position have been varied.

The molar ratio of the components "in the π ·.: Preparation the condensation products of monohydric or polyhydric phenol to the polyhydric amines "oot" 0.01: 1 to 5: 1, preferably 0.1: 1 to 2: ^. The molar ratio of phenol to aldehyde is 1: 0.1 at 1: 2, preferably 1: 0.5 at 1: 1.2, the unreacted fractions remain as modifying additives in the condensation product.

In the manufacture of condensation products are suitable for mixing with those already mentioned. Polyoxypropylenamines to be reacted, for example: aliphatic, saturated or unsaturated, ciiu-iktionelle Amines, such as lower aliphatic ^ l.-cylene polyamines, such as ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, hexamethylenediamine or polyalkylene polyamines, e.g. homologous polyethylene polyamines such as diethylenetrianine, Triethylenetetramine or analogous polypropylene polyamines, such as dipropylenetriamine. In addition, other aliphatic and cycloaliphatic ones are also readily available or araliphatic amines with at least two amine-hydrogen functions for mixing can be used for the purpose of conversion, such as ß, 3-diamino-di-n-propylamine, cycloaliphatic amines, such as xylylenediamine, 3,5, S-trimethyl-J-aminomethylcyclohexylamine, Menthane diamine, 2,2,4- (2,4,4-tri-

0 0982A / 1885

methylhexamethylenediarain, cyclohexane-bis-methylamine, Cyclohexanediamine.

The mixing prior to the reaction with the "other amines mentioned" is mainly carried out when the polyoxypropylene amines intended for the preparation of the condensation products are inert due to their higher molecular weight "during the mixing. The "pot life" of the polyoxypropyleneamines can be used as a measure to assess the necessary mixing before the condensation. Mixing is generally recommended when the pot life of the polyoxypropyleneamine is -ρ- 24 hours, which is at a molecular weight of -> 400 on the Pail, the pot life mentioned here being applicable in accordance with the conditions in the table.

Monohydric or polyhydric phenols with at least one aldehyde-reactive core site for production the condensation products are e.g. phenol, o-, m-, p-cresol, xylenols, resorcinol, pyrocatechol, Hydroquinone, phloroglucinol, pyrogallol, α- and ß-naphthol, p-tert-butylphenol, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone and other.

Both aliphatic and aromatic aldehydes, such as formaldehyde, Acetaldehyde, butyraldehyde, benzaldehyde, find use.

The novel polyoxypropylene condensation products is carried out in a simple, conventional 'manner by condensation of amines, at least nonoreaktiven phenols and aldehydes, and heating these mixtures at temperatures of for example 100 to 150 ⁰ C. After completion of the condensation reaction, the water of reaction formed is distilled off, wherein the condensation products remain as oily to resinous masses. Before-

009824/1885

SAD ORIGINAL

The operation is additionally carried out in such a way that the amine or amines and the phenol component are mixed in a reaction vessel and heated ^{to 90 to 100 °} C., preferably 30 to 50 ^{° C.} In these temperature ranges, the aldehyde, for example formaldehyde, is added in an aqueous 30 to 45 percent by weight solution or as a polymeric paraform, optionally with cooling, if the exothermic reaction is too strong. After subsidence of the reaction is then, preferably under a vacuum of 15 Torr bis 60, water from the reaction mixture under temperature increase up to 15O ⁰ C, preferably from 100 ⁰ C, removed. But one can also submit phenol and formaldehyde at 20 to 100 ⁰ C, preferably 30 to 5O ⁰ C, if appropriate with cooling, add amines, on the other hand one can also operate by initially introducing the amine alone, and first, with cooling at 20 up to 100 ^° C., preferably 30 to 50 ^° C., formaldehyde and then phenol are added. This is followed by work-up, as already indicated above.

After filtration and cooling, light to dark yellow condensation products are obtained, which correspond accordingly their "hydrogen active equivalent" with Epoxy resins can be implemented. The "active hydrogen equivalent" results from the yield of condensation product divided by the equivalents of nitrogen present in the reaction mixture bound hydrogen, minus the amount consumed by the conversion with the aldehyde. However, depending on the intended use of the resin-hardener mixture, it is also possible to use excess or too little Work hardener quantities.

009824/1885

From the large number of epoxy compounds that contain more than one 1,2-epoxy group in the molecule and which, according to the invention, are converted into moldings and coatings with the condensation products can be mentioned:

The epoxides of polyunsaturated hydrocarbons (vinylcyclohexene, dicyclopentadiene, cyclohexandiene, Cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadienes, divinylbenzenes and the like), oligomers of epichlorohydrin and the like, polyvalent epoxy ethers Alcohols (ethylene, propylene and butylene glycols, polyglycols, thiodiglycols, glycerine, pentaerythritol, Sorbitol, polyvinyl alcohol, polyallyl alcohol and similar), epoxy ethers of polyhydric phenols (resorcinol, Hydroquinone, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, Bis (4-hydroxy-r 3,5-dibromophenyl) methane, bis (4-hydroxy-3,5-difluorophenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (4-hydroxy-3-methylphenyl) -propane, 2,2-bis- (4-hydroxy-3-chlorophenyl) propane, 2,2-bis- (4-hydroxy-3,5-dichlorophenyl) propane, Bis (4-hydroxyphenyl) phenylmethane, Bis- (4-hydroxyphenyl) -diphenylmethane, bis- (4-hydroxyphenyl) -4'-methylphenylmethane, 1,1-bis- (4-hydroxyphenyl) -2,2,2-trichloroethane, Bis (4-hydroxyphenyl) - (4-chlorophenyl) methane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, bis-C4-hydroxyphenyl) -cyclohexylmethane, 4,4'-dihydroxydiphenyl, 2,2'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl sulfone. as well as their hydroxyethyl ether, phenol-formaldehyde condensation products, such as phenol alcohols, phenol aldehyde resins and the like), S- and N-containing Epoxides (Ν, Ν-diglycidylaniline, N, N'-dimethyldiglycidyl-4,4-diaminodipheny! Methane) as well as epoxides, which are made from multiple un-

0 0 9 8 2 4/18 85

saturated carboxylic acids or monounsaturated carboxylic acid esters of unsaturated alcohols have been, glycidyl esters, polyglycidyl esters obtained by polymerization or interpolymerization of Glycidyl esters of unsaturated acids can be obtained or from other acidic compounds (cyanuric acid, Diglycidyl sulfide, cyclic trimethylene trisulfone or their derivatives and others) are available.

Just as well as the above pure epoxides, their mixtures as well as mixtures with monoepoxides, optionally in the presence of solvents or plasticizers, according to the present.

fc procedures are implemented. For example the following monoepoxides can be used in a mixture with the aforementioned epoxy compounds: epoxidized monounsaturated hydrocarbons (butylene, cyclohexene, styrene oxide and others), halogen-containing epoxides, such as epichlorohydrin, epoxy ethers of monohydric alcohols (methyl, ethyl, Butyl, 2-ethylhexyl, dodecyl alcohol and others), epoxy ethers of monohydric phenols (phenol, cresol and other phenols substituted in o- or p-position), glycidyl esters of unsaturated carboxylic acids, epoxidized esters of unsaturated alcohols or unsaturated carboxylic acids and the acetals of the

P Glycidalduhyds.

The epoxy compounds mentioned, which according to the invention can be converted into moldings and coatings fillers, dyes, pigments, solvents or flexibilizers and curing accelerators can be added before curing.

The moldings and coatings according to the invention can optionally be produced by means of additives accelerating substances from the group of monohydric or polyhydric phenols, in particular Aminophenols, the mono- or polyvalent

00982Λ / 1885

Alcohols or by compounds such as mercapto compounds, thioethers, dithioethers or compounds with nitrogen-carbon-sulfur groups or sulfoxide groups.

In the method according to the invention, the hardening the polyepoxy resins or epoxy compounds that contain more than one epoxy group in the molecule, with the condensation products used according to the invention, depending on the reactivity of the epoxy resins or of the condensed polyamines, carried out at room temperature or at significantly higher temperatures will.

Typically, a temperature range is from 0 to 15O ⁰ C into consideration. These new condensation products are expediently used as curing agents in amounts equivalent to the epoxy resin, but in many cases an excess of up to 50% or a deficit of up to 25 % of the condensation products is readily possible. The curing reaction can optionally be accelerated or influenced by adding alcohols, carboxylic acids, epichlorohydrin, hydrogen halide and other accelerators and also by adding polyamidoamines. It should be emphasized that. a curing takes place with the new curing agents even at low temperatures down to zero around and under circumstances at -5 ⁰ C. It is also possible to cure at high humidity, and in some cases even under water. A suitable choice and amount of the component of the condensation product, namely amine, aldehyde and phenol, allow the reactivity, elasticity and chemical resistance to be matched to the particular application.

If the new hardeners are used for the production of coatings, this can be done here achieve good flow and good pigmentability.

00 9824/1885

6AD ORfGINAL

The process of the invention can be used to obtain cured epoxy resins which have excellent properties Water, acid and chemical resistance, good surface gloss and sometimes very good elasticity own. They are well suited for the production of large-volume cast bodies, e.g. for the Toolmaking. But they can also be used as lamination resins, adhesives, putties, as synthetic resin cement and as Coating, lining and repairing materials can be used for concrete flooring and concrete pipes. In contrast to many common amine hardeners, the described new condensation products for see and also in combination with epoxy resins with bitumen, asphalt and similar tar products compatible. Such combinations with tar products can be used to advantage in surface and corrosion protection, used in road construction and construction. For example, the following may be mentioned: and adhesives, sealing and insulating materials.

The moldings or coatings to be produced from the epoxy resins to be cured according to the invention can e.g. 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 with Grain sizes from 0.5 to 5 mm »must be provided.

The following information and examples explain the production of the new condensation products and their use as hardeners for the production of shaped bodies and coatings. Condensation product 1;

380 g of polyoxypropylenediamine (MW = 190, 2 mol) were ^{heated to 40 °} C. and 69 g of a 44 percent strength by weight formaldehyde solution (1 mol) were added with cooling over the course of 45 minutes. After a further 30 minutes, 94 g of phenol (1 mol) liquefied by heating was added. After 30 minutes

009824/1885

, vu-Vv " ¹ - i> SAO OBiGtNAL

ton stirring, was distilled off under Wassorstrahlvakuum of about 20 Torr and with slow heating to 100 ⁰ C, water. At 100 ⁰ C v / urde the reaction product for 30 minutes under the Wasstrstrahlvakuum left. This gives a niedrigviwkoses reaction product having a viscosity of 71 ep (25 ⁰ C), a density of 0.983 (25 ⁰ C), one of: hydrogen equivalent weight (hereinafter abbreviated as PLHV) of 69.5 and a Gardner Farbzahl'vor. 4 to 5. The pot life was 137 minutes at 22 ^ 0. The condensation product 1 consists mainly of the compound

OH CH, CH,

\ ' ^{3 3}

CH ₂ NH-CH CH ₂ (-0-CH ₂ CH) ₂ NH ₂

Condensation product 2;

273 g of polyoxypropylenediamine (MW = 248, ± _t ± v _c i; and 66.5 g of phenol (0.71 mol) were ^{heated to 40 °} C. Within 30 minutes, 34 g of a 44 percent strength by weight aqueous formaldehyde solution were added 30 minutes stirring was UNR ^ r a water pump vacuum of about 20 torr, and under slow mAufheizen to 10O ⁰ C, distilled water. In the case of 10O ⁰ C the reaction product was left for 30 minutes under "the water-jet vacuum. this gives a low-viscosity reaction product with a viscosity of 78 cp (25 ° C), a density of 0.991 (25 ° C), an HAV of 88.5 and a Gardner color of 5. The pot life was 128 minutes at 22 ⁰ C.

009824/1885

S&D ORiQiNAL

The condensation product 2 consists mainly of

CH ₂ NH "CH'CH ₂ (-OCH ₂ CH) ₅ - ₂

Condensation product 3;

The procedure is as described for the preparation of the condensation product 2, However, there are 398 polyoxypropylenediamine (M.G-. 398.1MoI), 34 g of 44 weight percent aqueous formaldehyde solution (0.5 mol) and 100 g of phenol (0.06 mol) ■ used. ■

"The hardener has an HAV of 144, one

Viscosity, measured in the Höppler viscometer at. 25 ⁰ C, of 151 cp and a pot life (100 g of a Polyglycid2 / läthers based on bisphenol A and epichlorohydrin with an epoxy equivalent weight of 190 and 76 g of the curing agent mixed) of 144 minutes, measured at 22 C. The condensation product 3 consists of main thing

off '. ■ '.

OH CH, CH-
\ ί ³ I ³

₍₁ -CH ₉ CH'CH-CH ₉ (-OCH ₉ CH)

kv U

Condensation product 4:

The procedure is as described for the preparation of the condensation product 1. However, there are 146 g of triethylenetetramine (l mol), 146 g polyoxypropylenediamine (M.G. 1000, 0.146 mol), 94 g of phenol (1 mol) and 68.5 g of a 44 percent strength by weight aqueous formaldehyde solution (1 mole) used.

The curing agent has a HAV of 89.51, a viscosity of 455 cP, measured in the Höppler viscometer at 25 ^° C., a density of 1.03 (25 ^° C.),

0 09824/18 85

ßAD

ο inc Arninzahl of 441 and a pot life (100 g Dines polyglycidyl ether of bisphenol A and epichlorohydrin having an epoxide equivalent basis of 190 and 47 g of the curing agent mixed) of 17 minutes, measured at 22 ⁰ C.

The condensation product 4 ″ consists of a mixture the end

OH CH, CH,

^ JLCH ₉ NH "CH.OH ₉ C-OOHp-CH) -

OH · ^and

CH ₀ CH ₀ ) ₀ > NH KU ^ ^

Condensation product 5?

The procedure is as described for the preparation of the condensation product 1. However, 380 grams of polyoxypropylenediamine (McG. 190, 2 moles), 188 grams of phenol (2 moles) and 138 grams a 44 percent strength by weight aqueous formaldehyde solution (2 moles) is used.

The curing agent has an HAV of 99, a viscosity of 1554 cP, measured in a Hoppler viscometer at 25 ⁰ C, a density of 1.035 ('25 ⁰ O), an amine number of 372 and a pot life (IOC g of a polyglycidyl ether of bisphenol a and epi- chlorohydrin • base having an epoxy equivalent of 190, and 52 g of the curing agent mixed) of 70 minutes, measured at 22 ⁰ C.

The condensation product 5 consists mainly of the end

OH CH,

CH ₂ NH • CH • CH ₂ (-OCH ₂ CH) ₂ -NH

009824/1885

_l8 '. 1351524

Condensation product 6; . '

It will be accordingly, as in the manufacture of the condensation product! described, worked. However, 273 g of polyoxypropylenediamine (M.G. 248, 1.1 moles), 103.5 g phenol (1.1 moles) 'and 75 g a 44 percent strength by weight aqueous formaldehyde solution (1.1 moles) are used.

The curing agent has HAY of 118, a viscosity of 964 cP, measured in a Hoppler viscometer at 25 ⁰ C, a density of 1.02 (25 ⁰ C), an amine number of 305 and a pot life (lOO g of a polyglycidyl ether of bisphenol A - and epichlorohydrin base mixed with an epoxy equivalent of 190 and 62 g of the curing agent) for 140 minutes, measured at. 22 ⁰ C.

The condensation product 6 consists mainly of

OH CH, CH,

! 3 ι 3.

. CH ₂ NHCH • CH ₂ (-OCH ₂ • CH), • ₂

Condensation product 1:

The procedure is as described for the preparation of the condensation product 1. However, 398 g of polyoxypropylenediamine (MW 398 » 1 mole), 94 g phenol (1 mole) and 69 g of a 44 weight percent aqueous formaldehyde solution (1 mol) used.

The curing agent has a HAS of 165 _s a viscosity of 555 cP _s measured in a Hoppler viscometer at 25 ⁰ C, a density of 1,0.1 '(25 ⁰ O), an amine number of 219 and a pot life (100! G of a polyglycidyl ether based on bisphenol A and epichlorohydrin with an epoxy equivalent of 190 and 87 g of the curing agent mixed) for 7 hours, measured at 22 0 »

009824/1885

SAO ORJG) NAL.

The condensation product 7 ″ consists mainly

from OH

CH.

CH * j 3

CH ₂ KHCHOH ₂ (OCH ₂ Ch) _{5 3ö} .,

Condensation product 8;

It will be accordingly, as in the manufacture of the condensation product 1 described, worked. However, 249 g of polyoxypropylene diamine (M.G.996, 0.25 mol), 94 g of phenol (.1 mol) and 17 g of a 44 percent strength by weight aqueous formaldehyde solution are used.

The curing agent has an HAV of 458, a viscosity of 781 cP, measured in a Hoppler viscometer at 25 ⁰ C, a density of 1.00 (25 ° C), an amine number of 118 and a pot life (100 g of a polyglycidyl ether of bisphenol a and epichlorohydrin with a base Bpoxidäquivale-nt of 190 and 242 g of the curing agent mixed) of 8 hours, measured at 20 ⁰ C.
The condensation product 8 consists mainly

OH CH, CH, Γ JLCH ₉ 'KH-CH-CH ₉ (-OCH' CH)

₉₁ -NH ₂

Condensation product 9;

The procedure is as described for the preparation of the condensation product 1. However, 136 g of polyoxypropylene diamine (M.G. 190, 0.72 mol), 136 g of xylylenediamine (e.g. a mixture of isomers of 70 percent by weight, the 1.3 and 30 percent by weight of the 1,4 compound) (1 mol), 161 g Phenol (1.72 moles) and 82 g of a 44 weight percent aqueous formaldehyde solution "-used.

The hardener has an HAV of 77.5, one Viscosity of 1280 cP, measured in the Höppler visco

00 9824/1885

■ 20

simeter at 25 ⁰ C, and a pot life (100 g of a polyglycidyl ether based on bisphenol A and epichlorohydrin with an epoxy equivalent of 190, and 4-1 g of the curing agent mixed) of 21 minutes, measured "at 20 ⁰ C.

The condensation product 9 consists of a mixture from

OH CH- '' CH

H ₂ 'NH-CH «CH ₂ (-OCH ₂ -CH) ₂ -M ₂ and OH

'EXAMPLE·. 1:

190 g of a polyglycidyl ether based on bisphenol A and epichlorohydrin with an epoxy equivalent of 190 are mixed with 69.5 g of the condensation product 1 and poured into 4 mm thick sheets without bubbles. Demand 24 hours curing at room temperature, the plates are heated for 2 hours at 100 ⁰ C. In addition, coatings are made on glass · * · and metal plates in the appropriate mixing ratio. The tests of the mechanical properties and chemical resistance gave excellent results. The resin-hardener mixture applied in thin layers was tack-free after 7 hours and 30 minutes and cured to a high-gloss, elastic coating after 20 hours.

This mixture is particularly suitable when the moldings and coatings are at temperatures below 5 ° C to be cured.

EXAMPLE 2:

The production of a shaped body or coating took place as described in Example 1, but were

00 982 4/1885

^ER ^ l ^% toNAl.

88.5 g of the condensation product 2 used as a hardener.

The mixture of polyglycidyl ether and condensation product When applied in thin layers, 2 was tack-free after 7 1/2 hours and scratch-resistant after 24 hours cured to a high-gloss, elastic coating.

EXAMPLE 3:

A molding or coating is produced as described in Example 1, however 144 g of the condensation product 5 were used as hardener.

Equivalent results were obtained. A coating applied to a glass plate layer was tack-free after 7 l / 2 hours and after 24 hours scratch resistant cured to a high gloss ₃ elastic coating. "

EXAMPLE 4t '

The production of a molded body or coating takes place as described in Example 1, but 89.5 g of the condensation product 4 were used as hardener used.

Equivalent results were obtained. A layer applied to a glass plate was 117 minutes after application is complete, non-tacky, and after 217 minutes scratch-resistant to a high-gloss, elastic coating cured ..

EXAMPLE 51

The production of a molded body or coating took place as described in Example 1, however were 99 g of the condensation product. 5 as a hardener used. "

Equivalent results were obtained. A layer applied to a glass plate was tack-free 251 minutes after the end of application, and cured after 12 hours scratch-resistant to a high-gloss, elastic coating.

009824/18 85

1851524

22nd . . ■■■ -.-. ■■■■

; '■. EXAMPLE 6:

The production of a molded body Tdzw · "coating takes place as described in Example 1, but 118 g of the condensation product 6 were used as hardener used. ·>. - _

Equivalent results were obtained. A layer applied to a glass plate was tack-free 410 minutes after application was complete, • dry and after 18 hours to a high gloss finish, ' cured elastic coating.

EXAMPLE ?;.

A molded body or coating was produced as described in Example 1, however. W 165 g of the condensation product were used as a hardener.

Equivalent results were achieved »A layer applied to a glass plate was cured tack-free after 24 hours to a high-gloss, elastic coating.

EXAMPLE 8;

A molded body or coating was produced as described in Example 1, however 458 g of the condensation product 8 were used as a hardener used. . .

- Equivalent results were obtained. A layer applied to a glass plate was tack-free after 24 hours to give a high-gloss, cured elastic coating.

EXAMPLE 9 i

A molded body or coating was produced as described in Example 1, however 77.5 g of the condensation product 9 were used as a hardener used,

Equivalent results were obtained. A layer applied to a glass plate was 120 minutes after the application is finished, tack-free and after 2 1/2 hours scratch-resistant on a high-gloss

\ 00S824 / 1885

the, elastic coating cured-. These Mixing is particularly suitable when the moldings and coatings are to be cured at temperatures below 5 C.

EXAMPLE 10; .

170 g of a polyglycidyl ether based on bisphenol F and epichlorohydrin with an epoxy equivalent of 170 are _{mixed with 69}} 5 g of the condensation product 1 and poured into 4 mm thick sheets without bubbles. After 24 ~ hours curing at room temperature, the plates are heated for 2 hours at 100 ⁰ C. In addition, coatings are applied to glass and metal plates in the appropriate mixing ratio. The tests of the mechanical properties and chemical resistance gave excellent results. The resin-hardener mixture applied in thin layers was tack-free after 7 1/2 hours and hardened to a high-gloss, elastic coating after 20 hours, making it scratch-resistant.

This mixture is particularly suitable when the moldings and coatings are at temperatures below 5 ° C to be cured.

EXAMPLE 11:

130 g of a mixture of 70 percent by weight of a polyglycidyl ether made from bisphenol A and epichlorohydrin. with an epoxy equivalent of 190 and 30 weight percent vinylcyclohexene diepoxide. are mixed with 69.5 g of the condensation product 1 and poured bubble-free to form 4 mm thick plates. After 24 hours curing at room temperature, the plates are .getempert further 2 hours at 100 ⁰ C. In addition, coatings are made on glass and metal plates in an appropriate mixing ratio. The tests of mechanical and chemical resistance gave excellent results. Those in thin layers

009824/1885

~ ■ ■. ■■ ...:. . 2V

applied resin-hardener mixture was after 9 hours non-sticky and hardened to a high-gloss, elastic coating after 22 hours, scratch-resistant.

EXAMPLE 12:

175 g of a hexahydrophthalic acid diglycidyl ester with an epoxide equivalent of 175 are mixed with 69.5 g of the condensation product 1 and poured into 4 mm thick sheets without bubbles. After 24 stundiger curing at room temperature, the plates are heated for 2 hours at 100 ⁰ C. In addition, coatings are applied to glass and metal plates in the appropriate mixing ratio. The tests of the mechanical properties and chemical resistance gave excellent results. The resin-hardener mixture applied in thin layers was tack-free after 7 hours and cured scratch-resistant after 19 hours to give a high-gloss, elastic coating.

EXAMPLE 13:

190 g of a polyglycidyl ether made from bisphenol A and epichlorohydrin with an epoxide equivalent of 190 are mixed with 35 g of condensation product 1 and 72 g of condensation product 3 and poured into 4 mm thick sheets without bubbles. Compartment 24 hours curing at room temperature, the plates are heated for 2 hours at 100 ⁰ C. In addition, coatings are applied to glass and metal plates in the appropriate mixing ratio. The tests of the mechanical properties and chemical resistance gave excellent results. The resin-hardener mixture applied in thin layers was tack-free after 9 1/2 hours and cured scratch-resistant to a high-gloss, elastic coating after 22 hours,

EXAMPLE 14:

The mixture according to Example 9 was prepared. There were an additional 50 g of quartz powder, 25 g of talc and

009824/1885

25 g chromium oxide green mixed in. The crowd was on

Cement brick applied in a thick layer, which before hardening in about 8 hours a completely flat Surface formed. After 24 hours of curing, a high-gloss, hard-wearing coating was achieved. The present invention also relates to a product which can be obtained by the process.

0098 24/1885

.,>. ^, BADORIQiNAL

Claims (1)

Claims Process for the production of moldings and coatings by reacting epoxy compounds with more as a 1,2-epoxy group per molecule, optionally mixed with monoepoxides, with polyether amines, characterized in that the polyether amines are condensation products of polyoxypropylene amines, Phenols and aldehydes are used. Process according to Claim 1, characterized in that the condensation products of polyoxypropyleneamines Phenols and aldehydes compounds with the general formula.,. OH .R ₂ ) where R ₁ = H-, CH ₃ -, C ₂ H ₅ -, C ₃ H ₇ -, C ₄ H ₉ or CH ■ - 1 R ₂ s - - NH - (0 - CH ₂ O) _x - A, χ = 1 to 50 R ₃ = H-, CH ₃ -, (CH ₃ ) ₃ G- ,. HO-, or HO - B- B = -CH ₂ -, -C (CH ₃ ) - or -SO ₂ -n = integers from 1 to 3 and m = integers from 1 to 3, and wherein A represents the following radicals; 009824/1885 © AD 0RIOWAL CH- CH ^ j- CH I ³ - CHCH ₂ -, CH ₃ (CHg) _n O-CH ₂ (-OCH ₂ CH -) '^ SH ₂ . CH ₂ (-.0CH ₂ CH-) _Z X, (CH (-OCH ₅ CH) -X) ₁₁ Z-OH ₉ (-OCH ₉ -CH) -BH ₉ CH ₂ (-0CH ₂ CH) ₂ -X and \ ^CH ₂ (-0CHg.CH) -X ΠΙΤ (CSC-TX ntlS V VjIl ₉ ^ --ULiJtI ₁ -. \ JsX) - Ji. where E = - H or - CH-, u, x, y and ζ = 1 to 50, X = - NHp or - OH, can be represented and used. Process according to claim 2, characterized in that condensation products are used in which the polyoxypropyleneamines have been replaced to a greater or lesser extent by other condensed aliphatic, araliphatic, heterocyclic and / or cycloaliphatic amines in order to vary the properties. Process according to one or more of Claims 1 to 3, characterized in that the condensate Ionic products and modifiers are used in mixtures in which the molar ratio of the Components in the production of the condensation products from mono- or polyhydric phenol to the polyvalent amines 0.01: 1 to 5: 1 »preferably 0.1: 1 to 2: 1 and. the molar ratio of phenol to Aldehyde 1: 0.1 to 1: 2, preferably 1: 0.5 to 1: 1.2, and wherein the unreacted proportions are contained as modifying additives in the condensation product. 009824/1885 5 »A product, obtainable according to the" in the An. according to 1 to 4 mentioned procedures * 009824/1885