DE1289307B - Process for the production of thermosetting copolymers - Google Patents

Description

1 2

From French patent specification 1 273 327 it is butyl maleate, dihexyl maleate, di- (2-ethylhexyl) -ma-

known copolymers of styrene, ethyl acrylate, linate and / or the corresponding fumarates and / or

Acrylic acid and N-methylolacrylamide in organic the corresponding itaconates; Trimethylaconitate, tri-

Solvents in the presence of amines with mono-

to implement epoxies with heating. 5 (2-ethylhexyl) aconitate and / or those with alcohols

In the German Auslegeschrift 1038 754 from 1 to 18 carbon atoms, such as methanol, etha copolymers described, wherein in the presence of nol, propanol, butanol, iso-butanol, hexanol, 2-ethyl

an epoxy-carboxy catalyst and a cataly- hexanol, methylglycol, ethylglycol, butylglycol,

Sators for vinyl polymerization a short-chain esterified α, / ί-ethylenically unsaturated simple and

«, Jö-unsaturated monocarboxylic acid and a vinyl ίο mixed alkyl carboxylic acid ester.

monomer and a monoepoxide are implemented. Formaldehyde-releasing compounds are both

The end products are polyhydroxy copolymers, for example aqueous or alcoholic solutions of

sate. These products cross-link when stoving formaldehyde, paraformaldehyde, trioxane and / or

but not, so that hexamethylenetetramine has no solvent resistance.

present against aromatic solvents 15 polymerization initiators are organic peroxides,

is. such as benzoyl peroxide, p-tert-butyl peroxide, cumene

The invention relates to a process for hydroperoxide, "," "- azodiisobutyric acid dinitrile. White

thermosetting copolymers can be used as redox polymerization catalysts

Implementation of a copolymer that is used by poly- the following reducing agents: Lauryl-

merization of ao mercaptan, dodecyl mercaptan, thioglycolic acid.

\ η f ie / - · t. * 4. ο -λ 1 · 1. · ■ * The copolymers are made from mixtures in

a) 9 to 25 percent by weight, ^ athylenically unsat- _{GegeQWart vo} * _{intert or not} harmful

saturated carboxylic anhydrants and / or _solvents , z. B. xylene, toluene, butanol, butyl

M cu · ι «ο °° £ ^acidic '._,. . .. glycol, ethyl glycol, methyl isobutyl ketone individually or

b) 5 to 15 percent by weight, 0-ethylenically unsat- _a5 J ^ Q ^ J ₁ % ^ _under / _en conditions of the block

^ * u-,. ^ 8 ^te ?. ^Carbonsallie M? ¹ i ^e °. . . __ polymerisation in the presence of polymerisation

c) 5 to 35 percent by weight, ^ - ethylemically unsat- | _{escMeunigern has been} polymerized with heating. ^ ^ u- «η ^ ^e . \ ^a 5 ^{omatlS (} ; ^hen ^ compounds, _{they are then dissolved in} the

d) 5 to 50 percent by weight, ^ ethylenically unsat _{mixture with formaldelivd} releasing substances

saturated alkylcarboxylic acid esters _{3o and monoepoxyds} in the presence of basic

reacted in the presence of polymerization accelerators under catalysts. Heating has been prepared, in solution in inert. Mixtures of organic solvents with monoepoxides in _{a) 1Q big 15 percent by weight} t «, / J-ethylenically in the presence of tertiary amines and / or quater- _sätti ^ _en carboxylic acids and / or car -

naren ammonium compounds by heating the 35 acid anhydrides,

The method is characterized in that the environmental _{b) 5 to 15 weight percent} "^ -äthylenisch ungesetzung m simultaneous presence of formaldehyde _Saetti ^ _en carboxylic acid amides,

and / or formaldehyde-donating compounds _{c) 15 35 wt big chtsprozent} f "^ ethylenically ungedurchgefuhrt is ^ _u ~ saturated aromatic compounds,

Among α, / J-athylenisch unsaturated carboxylic acids 40 _{d) 30 to 50 wt chtsprozent} f "^ -äthylenisch understood ungewerden: mono- and / or dicarboxylic acids _Saetti ^ _en Alkylcarbonsaureestern

and / or Carboxylic acids, their anhydrides and

their monoesters, such as acrylic acid, acrylic anhydride, in the solvent mixture of xylene-butanol in Ge-methacrylic acid, Maleic acid, maleic anhydride, the presence of alkyl mercaptan and peroxides among Maleic acid monomethyl, ethyl, propyl, butyl 45 has been copolymerized by heating. you will be or 2-ethylhexyl ester, fumaric acid; Fumaric acid- then with warming impemic with alcoholic monomethyl-, -ethyl-, -propyl-, -butyl-, -hexyl-, formaldehyde solution and ethylene oxide and / or pro -2-ethylhexyl ester, itaconic acid; Itaconic acid monome- pylene oxide in the presence of tertiary amines or ethyl, ethyl, propyl, butyl, hexyl, -2-ethylhexyl quaternary ammonium bases, esters, aconitic acid and their mono- and / or diesters. 50 Suitable monoepoxides are, for example Acrylic acid, methacrylic acid, maleic ethylene oxide and / or propylene oxide are preferred. the acid monobutyl ester, itaconic acid. The amount of monoepoxide used depends on

As ", j8-ethylenically unsaturated carboxamides according to the amount of carboxyl groups to be esterified, are usable: acrylamide, methacrylamide, ethacrylic For 1 mole of carboxyl groups about 1.5 to amide, phenylacrylamide, maleic acid monobutyl ester - 55 2.0 mol monoepoxide used, amide, maleic acid diamide, fumaric acid monoethyl ester- The amount of formaldehyde used is directed

amide, fumaric acid diamide, itaconic acid monobutyl ester - depending on the amount of amide groups. For 1 mole amide, itaconic acid diamide. Amide group, 1 to 1.3 mol of formaldehyde are used

Under «, jS-ethylenically unsaturated aromatic turns.

Compounds are understood: styrene, vinyl toluene, 60. The acid numbers of the copolymers should be above α-methylstyrene and the styrenes substituted in the core of the reaction are about 50 to 120. The turnover as well as halogenated styrenes. tion of the copolymers with formaldehyde and

As "j5-ethylenically unsaturated monoepoxides Alkylcarbonsäure- is then dried at temperatures between esters are understood: methyl acrylate, ethyl acrylate, 70 to 90 ⁰ C. After the reaction of butyl acrylate, 2-ethylhexyl acrylate and / or the corresponding methacrylate and / or the corresponding acid number drops to 5 to 25 by means of propylene oxide and formaldehyde. In this way, especially the ethacrylates and / or the corresponding a-Phe-valuable products are obtained. The decrease in the acid acrylate, dimethyl maleate, diethyl maleate, di- numbers is due to the fact that oxyalkyl esters

in the copolymer by reacting the monoepoxide with the carboxyl groups of the copolymer arise, while the formaldehyde combines with the amide group to form methylol groups in the copolymer implements. There is probably an etherification of the methylol group with the monoepoxide with the formation of a methyloloxyalkyl ether in the copolymer, since more monoepoxide is consumed than is necessary for the esterification. The end products made from it result after Stoving at 150 to 180 ° C, chemical-resistant to aromatic solvents and ketones resistant, hard, tough elastic films with an excellent adhesive strength on metals and glass as well excellent resistance to yellowing. They are suitable in pigmented and unpigmented Condition as excellent stoving enamels with very good yellowing resistance, chemical resistance, Food resistance, excellent weather resistance, very good adhesion to glass, ceramics, Metals, wood and plastics.

The new reaction products are also very good as binders for masses to be pressed hot shaped structures suitable.

If the reaction is carried out under the same reaction conditions so that the copolymers containing carboxyl and amido groups are first treated with monoepoxides in the presence of tert. Amines are converted to polyhydroxyl-containing copolymers, the subsequent reaction with formaldehyde does not give the desired heat-curable copolymers. These products provide after baking at 150 to 18O ⁰ C brittle films that are not resistant to chemicals. In addition, the films yellowed at the specified temperatures.

If the reaction is carried out under the same reaction conditions so that the carboxyl and Copolymers containing amido groups first react with formaldehyde and then with propylene oxide in the presence of tert. Amines are reacted, so this reaction path leads before completion the implementation of gelatinization of the products. Surprisingly, therefore, it turned out that the copolymers containing carboxyl and amido groups are carried out under the same reaction conditions joint reaction with monoepoxides and formaldehyde in the presence of tert. Amines very valuable Products are obtained.

Making one in aromatic solvents

soluble, thermosetting copolymer. In a three-necked flask equipped with a stirrer, thermometer and reflux condenser

until the body content of the solution is 50%. The viscosity according to Gardner - Holdt at 2O ⁰ C

375.0
720.0
36.8
113.0
143.0
407.0
359.0
336.0

Parts by weight
Parts by weight
Parts by weight
Parts by weight
Parts by weight
Parts by weight
Parts by weight
Parts by weight

Butanol,

Xylene,

Lauryl mercaptan,

Methacrylic acid,

Acrylamide,

Styrene,

Ethyl acrylate,

Butyl acrylate

55

60

heated to boiling with circular distillation. To do this, leave the following mixture:

230.0 parts by weight of xylene,

18.4 parts by weight of di-tert-butyl peroxide,
run in 60 minutes and polymerize for about 4 to 5 hours at a temperature of 123 to 128 ⁰ C,

65

example

At 9O ⁰ C to the solution of the copolymer are added to 4.6 cc of triethylamine and of the feed of a mixture

196.0 parts by weight of a 40% strength butanolic formaldehyde solution and

110.0 parts by weight of propylene oxide

began. The feed has ended after 30 minutes. The reaction is then continued for a few hours at 90 ^° C. until an acid number of 15 to 20 is reached. The body content of the solution is 50% and the viscosity 250 to 300 DIN seconds. at 20 ⁰ C.

The product has excellent resistance to aromatic solvents and ketones after stoving at 150 to 180 ^° C. for a stoving time of 30 minutes. The adhesive strength on glass and metallic surfaces is excellent.

Comparative experiments

a) Based on example 9 of French patent 1 273 327, the following approach was used, which results in a copolymer which is in the range of quantities used in the process according to the invention Copolymer drops, produced:

In 14.2 g of isopropanol, the following mixture is refluxed and stirred vigorously in the course of IV2 hours added:

20 g styrene,

40 g ethyl acrylate,

15 g acrylic acid,

6 g N-methylolacrylamide corresponds to 4.22 g acrylamide,

2.5 g of benzoyl peroxide and
16.5 g isopropanol.

After a feed time of 1 hour and 25 minutes, the product gelatinized. 4 g of the mixture remained still back. Another possible reaction, as described in French patent specification 1,273,327, example 9, is therefore not possible.

b) The same batch was processed according to the method of the invention and showed this below described result.

In 14.2 g of isopropanol, the following mixture is refluxed and stirred vigorously:

20 g styrene,

40 g ethyl acrylate,

15 g acrylic acid,

4.22 g acrylamide,

2.5 g benzoyl peroxide,
16.5 g isopropanol,

added and copolymerized in IV2 hours been. After the end of the inflow, the mixture was polymerized for 4 hours under further reflux. After adding

2.9 g triethylamine (equivalent to 6% of acrylic acid),

46.4 g of a 5% isopropanolic formaldehyde solution and

4.85 g propylene oxide (equivalent to V30 der Acrylic acid)

the reaction is continued under reflux for 4 hours.

There were films with a wet film thickness of 90 μ. reared, ventilated for a long time to be bubble-free To obtain coatings, and baked at 150 ° C for 30 minutes.

Resistance to solvents and fuels

Exposure time 8 hours at Room temperature acetone Containing aromatics
Super fuels 2 Ibis 2 Xylene Ibis 2

(Judgement:

1. Films are not swollen.

2. Films are slightly swollen.

3. Films are more swollen with individual holes.

4. Films are pulled up.

5. Films are resolved.)

Claims (1)

Claim: Process for the production of thermosetting copolymers by reacting a copolymer, that by polymerization of a) 9 to 25 percent by weight α, / 5-ethylenic unge saturated carboxylic acid anhydrides and / or carboxylic acids, b) 5 to 15 percent by weight α, / 9-ethylenic unge saturated carboxamides, c) 5 to 35 percent by weight, jff-ethylenic unge saturated aromatic compounds, d) 5 to 50 percent by weight α, / S-ethylenic unge saturated alkyl carboxylic acid esters in the presence of polymerization accelerators with heating, in solution in inert organic solvents with monoepoxides in the presence of tertiary amines and / or quaternary ammonium compounds by heating, thereby marked e t that the reaction in the simultaneous presence of formaldehyde and / or formaldehyde donates Connections is carried out.