DD229140A1 - PROCESS FOR MODIFYING AND NETWORKING THEMOPLASTIC EPOXYED AMINE ADDITION POLYMERS - Google Patents

Abstract

The invention relates to a process for the modification and postcrosslinking of thermoplastic epoxide-amine addition polymers of the structure I ... -NCR ... -NC-CH-... OH by reacting the hydroxyl groups with cyclic dicarboxylic acid anhydrides, such as succinic, maleic acid or phthalic anhydride. The post-crosslinking of the modified polymers can be carried out by thermal, photo or radiation-chemical reactions.

Description

Modification and postcrosslinking process of thermoplastic epoxide-amine addition polymers

Field of application of the invention

The invention relates to a process for the modification of higher molecular weight, soluble epoxy-amine addition polymers by conversion of the hydroxyl groups with a bifunctional compound in such a way that form as a modification product Dicarbonsäurehalbester which confer the modification products new technically interesting properties by their content of carboxyl groups

 This includes

1. the polyelectrolyte character which increases with the degree of modification, which is due to the ionization of the carboxyl groups,

2. the complexation behavior and adhesiveness increased via the carboxylate groups and

3 the possibility of intermolecular and intramolecular formation of ionic or / and ester bonds enabling physical or chemical crosslinking of the thermoplastic polymers.

I i

* OC-R'-COOH Il 0

Modified higher molecular weight epoxy-amine addition polymers are soluble or / and thermoplastic and allow versatile use for adhesives, paints, coatings, films, laminates, and composite matrix materials. Due to the versatile possibilities of ionic, complex chemical and H-bonding interactions with metallic, metal ion-containing and organic-chemical solid-state surfaces such as metals, glasses, ceramics, stone, salts, wood, plastics, fiber materials, paper, leather and others. They can also serve as a primary adhesive layer for plastic coatings, as a fixing aid for dyes.

Other applications are in the use as polymeric chemical reagents, macromolecular complexing agents, additives to printing inks, adhesives, as a paper and textile auxiliaries.

Especially due to the possibility of thermal post-crosslinking, the use as an adhesive, larainier and matrix material for composites is substantially determined. In the case of the introduction of olefinically unsaturated dicarboxylic acid residues, the possibility of photochemical after-reaction also opens up.

Characteristic of the known technical solutions

Soluble, higher molecular weight and thermoplastic epoxy-amine addition polymers containing as poly (amino alcohols) the characteristic β-hydroxyaminoalkyl unit I,

1 i N-C-CH- ·· I

I i OH

are in great structural diversity by polyaddition reactions of diepoxides and aromatic, araliphatic

see, cycloaliphatic and certain aliphatic primary monoamines, disecondary diamines, primary-tertiary diamines or carboxylic acid, accessible, wherein solution or melt polymerization processes are known (see H. H Hörhold, 3. Klee, K. Bellstedt: Z. Chem. 22 (1982) 166-1.76) (DD 141 677, DD 154 935, DD 155324). Such polymers have already been esterified at the hydroxyl groups by reaction with activated carboxylic acid derivatives, such as acetic anhydride, acrylic anhydride, acid chlorides (DD 143 265, DD 208 365). By reaction with isocyanates, urethane grouping can be introduced into the macromolecule via the OH groups (DD 209 467), and it is also known that the soluble, high molecular weight poly (aminoalcohols) can be modified to poly (ammonium salts) and poly (quaternary ammonium salts) (DD 146 056, DD 211 573) Polyquats of this type are valuable polyelectrolytes which have also been used as membrane material for ultrafiltration and reverse osmosis (A. Renner, Thermoplastic resins, polyquats and membranes based on epoxies: Proceedings p. 75 IUPAC MACRO 82, Amherst, MA, USA 12.-16.7.1982)

 R

t i

...- N-C-CH

I i

OC-R "

i! ο

R "= aromatic, aliphatic radical. (Monocarboxylic acid ester) = NH-R (urethane)

R β is aromatic, aliphatic, cycloaliphatic, araliphatic radical

© '-N- CH ₉ - CH -

i i

R "'OH

R '' β H _# aliphatic araliphatic radical (quaternary ammonium salts)

High molecular weight half-esters of dicarboxylic acids based on the thermoplastic epoxy-amine addition polymers which have free carboxyl groups according to the invention and thus introduce a new functional group into the macromolecule for further reactions are not yet known.

i! t .. - N - c - CH - *

I 1

OC-R * -COH 1! -Il 0 0

Object of the invention

The object of the invention is to devise a process for the modification of higher molecular weight poly (aminoalcohols) resulting from polyaddition processes of diepoxides and amines, wherein the modification in the introduction of the dicarboxylic acid half-ester moiety on a part or all of the hydroxyl groups of the poly (aminoalcohol ) and the modification product retains its solubility so that it can be formed from solution or thermoplastic into coatings, coatings, bodies, films, films, fibers, etc., and can be used as a laminating material or matrix material for composites. Optionally, subsequent crosslinking of the high molecular weight, soluble or thermoplastic modification products should be achievable via the reaction of the free carboxyl groups or carboxylates. This is to pursue the goal, in, their degree of crosslinking influence, postcurable adhesives, coatings,

Laminate and matrix materials with reduced internal stress and altered properties with respect to epoxy resins directly cured with amines or acid anhydrides

Explanation of the essence of the invention

The object of the invention is achieved by using higher molecular weight epoxide-amine addition polymers, such as those in greater variety by polyaddition of diepoxides with aromatic, araliphatic, cycloaliphatic and certain aliphatic primary monoamines, disecondary diamines, primary tertiary diamines or carboxylic hydrazides as soluble or thermoplastic Poly (amino alcohols) with the characteristic structure groups I are formed according to Eq. (1) with or without additional catalysts with internal dicarboxylic acid anhydrides,

R / ^{00 00} X ^R Eq. (DNC-CH- · + R ¹ O - ··· -NC-CH--

OH ^ CO ^f OC-R-COOH.

CycL carboxylic acid g ¹ anhydride ^

preferably with maleic anhydride, dichloromaleic anhydride. Succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, reaction products of _t- maleic anhydride with a second unsaturated compound, tetrahydrophthalic anhydride, nadic anhydride and like cyclic carboxylic anhydrides are converted to the half-ester II of the higher molecular weight poly (aminoalcohol) to form a higher molecular weight uncrosslinked soluble modification product having free carboxyl groups.

Residue R of the soluble higher molecular weight epoxy-amine addition polymer is unsubstituted

or substituted aromatic, araliphatic, cycloaliphatic or aliphatic radical, ζ. 3. the phenyl, 4-chlorophenyl, benzyl, methyl, ethyl, cyclohexyl, 1-adamantyl, 3-hydroxypropyl, 2-hydroxyethyl radical or an amide radical, such as -NHCOGp-H--, - NHCOCH. The radical R * represents a bifunctional aromatic, aliphatic or cycloaliphatic radical which may be substituted again in a variety of ways:

-CH = CH-, -CCl = CCl-, -CH ₂ -CH ₂ -, (R eg C ₁₂ H ₂₃ )

The process of modifying the higher molecular weight epoxy-amine addition polymers by reaction with cyclic dicarboxylic anhydrides can be carried out, for example, advantageously in a solution. For this purpose, a solution of the higher molecular weight epoxy-amine addition polymer is prepared, for example in tetrahydrofuran, DMF, DMSO, or e.in inert solvent mixture such as toluene / cyclohexanone, chlorobenzene / chloroform or optionally also in toluene and 0.1 to 1.0 mol of dicarboxylic anhydride per mole of hydroxyl groups of the poly (aminoalcohol) and reacted by reaction at room temperature or elevated temperature »In the modification reactions of polyamino alcohols based on aliphatic, araliphatic and cycloaliphatic amine groups, it is not necessary to add catalysts for the conversion. The tertiary amino group of the aminoalcohol segment adjacent to the hydroxyl group to be modified in these cases has an accelerating effect on the modification reaction. If this effect is not enough,

For example, in order to speed up the modification, a known esterification catalyst may be added, such as a tertiary amine.

With suitable poly (aminoalcohol) -Anhydridpaaren can be achieved in the limiting case, a virtually complete conversion of the hydroxyl groups. However, the method can also be applied so that only a portion of the OH groups of the addition polymers are modified by the use of 0.1 to 0.9 moles of carboxylic anhydride per mole of OH groups. To achieve a complete conversion of the OH groups and an excess of carboxylic anhydride can be applied.

Suitably, the modification reaction is carried out in tetrahydrofuran. The polymers modified with free carboxyl groups generally remain in solution. They can be processed from the viscous solutions to films, coatings, coatings, threads, films and bodies and are used in a known manner as adhesives. The solutions are also suitable for impregnating or wetting laminating fabrics and fillers of various kinds. By evaporation of the solvent, the still thermoplastic solid can then be cured by heating to 100 - 250 ⁰ C in a differentiated manner. Especially in the case when only a part of the hydroxyl groups (0.1-0.5 moles) is modified with the dicarboxylic acid half ester, crosslinking elements are presumably formed to form new ester groups.

For technical use, it is extremely advantageous that this curing reaction proceeds with minimal volume change and can be controlled by the concentration of the modifying elements. In this way, flexible films, layers, adhesive bonds and matrix properties can be achieved. The graded mechanical, thermal, and chemical properties inherent in the variety of epoxy-amine addition polymers

However, the dicarboxylic acid monoester moiety introduced by the modification is also accessible to further curing / crosslinking reactions, such as, for example, an addition reaction to entrained double bonds (in US Pat MA ₁ dichloro-MA, etc.) In the absence of post-crosslinking, however, the modification of epoxide-amine addition polymers according to the invention can also be used to change the solubility and the complex-forming capacity of the soluble addition polymers. So z. B. a thin layer of succinic anhydride modified high molecular weight addition polymers of benzylamine and diglycidyl bisphenol-A (Molverh.: 1), which is not soluble before modification in aqueous solvents, after the modification according to the invention in a concentrated aqueous ammonia solution soluble.

example 1

0.954 g (2.15 mmol) of an addition polymer of bisphenol A diglycidyl ether and 3-cylamine (M 15800) are dissolved together with 0.431 g (4.31 mmol) of succinic anhydride in 10 ml of THF and stirred at room temperature for S hours. Thereafter, the THF is distilled off in vacuo, the polymer in 10 ml CHC1_ / CH QH (4: 1) and precipitated in 300 ml of hexane. After drying at 50 C and 0.01 Torr remain l, 15 <j modified polymer in GHCl ₃ ZGH ₃ OH (4: 1) is soluble, THF, dioxane and in 30 / pc alcohol aqueous ammonia ·

^ 36 "" UlN ⁰ Wn '( ⁶⁴⁷ ' ⁷ ) _n ^Ber * ^{G 65} '75 ^{H 6} ' ^{38 N 2} ' ^1S

Gef. C 56.90 H 7.33 N 2.01

The addition polymer thus obtained was dissolved in 2 ml of THF and cast into a film which was dried first at room temperature and then at 60 ^° C. and 0.01 torr for 30 hours. The film was then thermally crosslinked under argon protective gas at 132 ⁰ C for one hour.

Example 2

0.420 g (0.97 mmol) of an addition polymer of bisphenol A diglycidyl ether and aniline (M 11500) are dissolved together with 0.190 mmol (1.94 mmol) of maleic anhydride in 10 ml of THF and stirred for 10 hours at room temperature. Thereafter, the THF is removed under reduced pressure, the polymer is taken up in 10 ml of CHCl ₃ / CHOH (4: 1) and precipitated in 300 ml of hexane. After drying at 60 ^° C. and 0.01 torr, the modified polymer is obtained.

From a '! Part of the THF solution was poured into a film which was dried at room temperature and then at 60 C and 0.01 Torr for 30 hours.

After 3 hours of irradiation of this film with a UV immersion lamp (UVS 125), a polymer insoluble in organic solvents was obtained.

Example 3

0.419 g (0.53 mmol) of an addition polymer of bisphenol A diglycidyl ether, N, N'-dibenzyl-4 _{<4'-diaminodiphenylmethane} (M _n 12,500) and 0.043 g (0.29 mmol) of phthalic anhydride were stirred together in 10 ml Dissolved THF and stirred for 20 hours at room temperature. Subsequently, the modified polymer was poured into a film and dried at 60 ⁰ G and 0.01 Torr for 30 hours. Under argon protective gas was carried out in the course of 2.5 hours at 132 C, a thermal crosslinking of the modified polymer.

Example 4

10.000 g (17.22 mmol) of an addition polymer of bisphenol-A diglycidyl ether and N, N dibenzyl-ethylenediamine ^f (R _n 13660) become (34.42 mmol) dissolved together with 3.375 g of maleic anhydride in 30 ml of THF for 6 hours Stirred at room temperature and then precipitated by dropwise addition of this solution in about 1 1 petroleum ether (bp 60-85 ⁰ C). Thereafter, the modified polymer is filtered off with suction and dried at room temperature for 8 hours at 0.2 Torr. Yield: 13.2 g (98.7 % of theory )

(C ₄₅ H ₄₈ N ₂ O ₁ Q) _n , (776.9) _n Ber. C 69.41 H 6.48 N 3.59

Gef. G 69.13 H 6.31 N 3.23

The modified polymer is soluble in CHGl ₃ ZCH ₃ OH (4: 1), THF, DMSO, DMF, dioxane and pyridine.

Example 5

10,000 g (17.22 mmol) of an addition polymer of bisphenol A diglycidyl ether and Ν, Ν'-dibenzylethylenediamine (M 13660) are dissolved together with 3.454 g (34.52 mmol) succinic anhydride in 80 ml THF, stirred for 6 hours at room temperature and then by dropwise addition of this solution in about 1 1 petroleum ether (bp. 60-85 ⁰ C) from

like. Thereafter, the modified polymer is sucked off and dried at room temperature at 0.2 torr for 8 hours

Yield: 13.0 g (95.3 % of theory )

The polymer is soluble in THF, DMSO, DMF, dioxane, CHClo / CH-OH (4: 1) and pyridine, and can be cast into films from these solutions.

Claims (2)

invention claim A process for the modification and post-crosslinking of thermoplastic epoxy-amine addition polymers, characterized in that epoxide-amine addition polymers formed by reacting diepoxides with primary monoamines, di-secondary diamines, primary-tertiary diamines or carboxylic hydrazides according to known methods, with internal dicarboxylic acid anhydrides, such as preferably maleic anhydride, succinic anhydride, phthalic anhydride, dichloromaleic anhydride. Reaction products of maleic anhydride with a second unsaturated compound, tetrahydrophthalic anhydride, Nadinsäureanhydrid and similar cyclic carboxylic anhydrides are reacted to soluble or thermoplastic half esters of the structure IT, which have free carboxyl groups or carboxyl groups, I 1 OC-R "-COOH II where R is an aliphatic, cycloaliphatic, aromatic or araliphatic radical and R * -CH = CH-, -CCl = CCl-, -CH ₂ - CH ₂ -, -CH ₂ - CHR- (R eg C ₁₂ H ₂₃ ) means. 2 * Process according to item 1, characterized in that the soluble or thermoplastic modification products are obtained by thermal, photochemical or radiation chemical reactions are postcrosslinked. Process according to item 1, characterized in that the modification of the epoxide-amine addition polymers is carried out in the presence of solvents or diluents, preferably in tetrahydrofuran solution. Process according to items 1 and 3 _f, characterized in that in the presence of esterification catalysts, such as tertiary amines, is reacted. Process according to item 1, 3, 4, characterized in that only part of the hydroxyl groups present in the epoxide-amine addition polymer are esterified.