DE1059178B - Process for the preparation of polyethers containing N-methylol groups, N-methylene ether groups and N-methylenoxy groups - Google Patents

Description

The production of higher molecular weight linear or branched ones Polyether containing N-methylenoxy groups from N-polymethylol compounds and polyfunctional ones The patent application relates to polyalcohols containing ether or thioether groups F 21161 IVb / 39c (German Auslegeschrift 1049094).

Polyethers containing more highly branched N-methylenoxy groups can also be selected from any other Polyalcohols and N-polymethylol compounds produced in the presence of very small amounts of acid will. However, in order to reduce the number of reactive NH groups during etherification and thus To largely eliminate crosslinking via methylene groups, for example, have to be done during manufacture of urea-based polycondensation products, tri- and tetramethylol compounds of urea used or dimethylol compounds of urea in the presence of formaldehyde for Reak tion to be brought; Crosslinking reactions via methylene ether groups occur in this polycondensation reaction not a. In all cases, such branched polycondensation products are, for example those from N-polymethylolureas and water-soluble polyalcohols, their melting viscosities range from 3 to 22,000 cP 75 ° C water soluble.

Often it is a modification of higher molecular weight polycondensation products from N-polymethylol compounds and polyalcohols by reacting their free methylol groups with reactive components he wishes. In the presence of acids, however, this modification usually leads to the formation of cross-linked, gelatinous products. On the other hand, one obtains with an excess of low molecular weight Reaction partners, for example mono- or bifunctional alcohols, modified, but by Alcoholysis largely degraded products.

It has now been found that linear or weakly branched N-methylenoxy groups containing polyethers with N-methylol groups, for example those from N-polymethylolureas and di-, tri- or higher-functional alcohols, with N-polymethylol compounds with a p _K value of at least 6 can be modified without degradation and without crosslinking even under vigorous condensation conditions. In this case, the modification takes place largely through methylene ether linkage of the reaction components. Accordingly, polyethers with N-methylol groups, N-methylene ether groups and N-methylenoxy groups are obtained.

The products which can be prepared in this way are soluble in water or alcohol, even when modified with relatively poorly soluble, low molecular weight N-polymethylol compounds. Through the inven-tion process
for the production of N-methylol groups,

N-methylene ether groups

and containing N-methylenoxy groups

Polyethers

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk

Dr. Kuno Wagner, Leverkusen,
has been named as the inventor

proper modification reactions are very reactive. Polyethers rich in N-methylol groups obtained, which have largely more favorable properties than for various purposes the reaction components on their own.

The modification reaction according to the invention is advantageously carried out in solvents since the highly viscous polyethers containing N-methyloxy groups and N-methylol groups are necessary for modification used N-polymethylol compounds, for example hexamethylol melamine, tetramethylol acetylene urea or tetramethylol-dimethylacetyleneurea, do not dissolve sufficiently; as a solvent are preferably water, polyalcohols, e.g. B. technical hexanetriol, or mixtures of water with Polyalcohols used. The basic catalysts are inorganic or inert organic bases suitable. The use of alkali hydroxides is favorable.

The reaction is carried out, for example, in such a way that the polyether containing N-methylenoxy groups and N-methylol groups is dissolved in concentrated form in a little water and, after addition of small amounts of alkali and an amount of hexanetriol equivalent to the amount of water, the N-polymethylol compound is added at temperatures around 90.degree. When modifying with hexamethylolmelamine, it is advisable to add a saturated, boiling hot aqueous solution to the polyether to be modified. The p _a value of the reaction mixture, which slowly falls during the condensation as a result of the formation of formic acid, can be reduced by adding small amounts of base

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be kept constant. Is allowed to fall off the _pH value of the reaction mixture within a few hours to 6.5 to 6.2, is obtained likewise water-or. alcohol-soluble, but partially etherified products.

As methylenoxy groups and N-methylol groups Polyethers containing, for example, those rich in methylol are suitable for the process according to the invention Polyethers based on di-, tri- and tetramethylol compounds of urea and thiourea and polyfunctional alcohols such as glycerin, glycerin mixed with hexanetriol or butanetriol, hexanetriol, Butanetriol, butanetriol mixed with pentaerythritol, polyethylene glycols mixed with trifunctional Alcohols and any oxyethylated aliphatic alcohols. N-methylenoxy groups are also suitable and polyethers containing N-methylol groups, starting from hexamethylene diurea, Dicarboxylic acid diamides, hydrazodicarbonamide or unsubstituted diurethanes, e.g. B. tetramethylene diurethane. Also on polyethers made from polyalcohols and tetramethylol acetylene urea or dimethylacetylene urea the base-catalyzed modification reaction can be carried out.

Suitable N-polymethylol compounds are, for example Hexamethylol melamine, tetramethylol acetylene urea, Tetramethylol - dimethylacetylene urea ,. Tetramethylol hydrazodicarbonamide, polymethylol compounds of adipic acid dihydrazide and adipic acid diamide; there are also polymethylol compounds called by unsubstituted diurethanes.

The N-methylenoxy groups, N-methylol groups obtained by the process according to the invention and polyethers containing N-methylene ether groups are characterized by excellent properties, even when stored for a long time Consistency. They are valuable tools for increasing the wet tensile strength of Paper and for paper bonding.

In the following examples, which further illustrate the process, parts by weight are related to parts by volume in the ratio of grams to milliliters.

example 1

A freshly prepared slurry of 306 parts by weight is added to a solution, heated to 90 to 95 ° C., of 430 parts by weight of a trimethylolurea-hexanetriol-l ^ -butanedioxyethylglycol polyether with a melt viscosity of 10,200 cP (at 75 ° C.) in 172 parts by weight of water Hexamethylolmelamine in 292 parts by weight of water or the boiling hot, still basic solution of the freshly prepared hexamethylolmelamine was added and 30 parts by volume of In-NaOH were added to the reaction mixture. 400 parts by weight of technical grade hexanetriol are added with thorough stirring, and the clear solution is heated at an internal temperature of 90 to 100 ° C. for 2 to 3 hours. Here, the _pH value slowly decreases as a result of forming in a small amount of formic acid to 7 to 6.5. The clear solution obtained can be diluted with water in all proportions. Even with a condensation time of 8 hours at 100 ° C., neither crosslinked products nor sparingly soluble condensation products of hexamethylolmelamine are formed.

Example2

The procedure is as in Example 1, but using 582 parts by weight of a polyether made from trimethylolurea and oxethylated trimethylolpropane, which has a melt viscosity of 4000 cP (at 75 ° C.). 400 parts by weight of hexanetriol and 25 parts by volume of 1N are added to the melt at 90 ° C. Na OH and, more basic reaction solution of 306 parts by weight of hexamethylol melamine in 300 parts by volume of water prepared fresh was added. the condensation is as has dropped until the _pH value of the reaction mixture to p _H = 6.4 in example 1. It is a clear Obtained solution of the modified polyether of excellent shelf life.

Example 3

Analogously to the procedure of Example 1, N-methylenoxy groups and N-methylol groups are used Polyether

a) a concentrated solution of 500 parts by weight of a highly branched polyether made from trimethylolurea and hexanetriol (melt viscosity 17,500 cP at 75 ° C) in 224 parts by weight of water,

b) a hot solution of 524 parts by weight of a trimethylolurea - hexanetriol - pentaerythritol polyether mixture in 224 parts by weight of water,

c) a hot solution of a tetramethylolureaglycerol - triethylene glycol - hexanetriol - polyether (Melt viscosity 20,000 cP at -75 ° jC) in 200 parts by volume of water,

d) a hot solution of 510 parts by weight of a trimethylolurea-butanetriol polyether (6800 cP at 75 ° C) in 190 parts by volume of water.

After adding 25 to 35 parts by volume of In-NaOH the reaction mixture is kept at 95 ° C. for 4 to 6 hours. Stable solutions of the modified polyethers which are miscible with water in all proportions.

Example 4

200 parts by weight of a trimethylolurea rich in methylol groups - hexanetriol -1,4 - butanedioxäthylgly kol-polyethers (melt viscosity 10200 cP at 75 ° C) are according to the procedure of Example 1

a) with 200 parts by weight of hexanetriol and a solution of 177 parts by weight of hexamethylol-adipic acid dihydrazide in 150 parts by volume of water or

b) with 200 parts by weight of hexanetriol and a solution of 148 parts by weight of tetramethylol-tetramethylene diurethane or

c) with 200 parts by weight of hexanetriol and 102 parts by weight of polymethylol dicyandiamide in 150 parts by volume Water or

d) with 200 parts by weight of hexanetriol and a solution of 191 parts by weight of polymethylol-hexamethylene diurea in 150 parts by volume of water or

e) with 200 g of hexanetriol and a solution of 112 parts by weight Tetramethylol adipic acid diamide in 190 parts by volume of water or

f) with 200 g of hexanetriol and a solution of 135 parts by weight Tetramethylol-acetylenureas in 80 parts by volume of water or

g) with 200 parts by weight of hexanetriol and a solution of 146 parts by weight of tetramethylol dime thylacetylenurea added in 80 parts by volume of water.

In all cases, condensation is carried out at 95 ° C. and with the addition of 20 to 30 parts by volume of In NaOH. To A condensation period of 4 to 3 hours is stable with water in all proportions mixable solutions.

Claims (4)

Patent claims: 1. A process for the preparation of N-methylol, N-methylene ether groups and N-Methylenoxygruppen containing polyethers, characterized in that one or more N-methylol groups and N-Methylenoxygruppen polyether containing at a p _H -value of at least 6 with N-polymethylol implements. 2. The method according to claim 1, characterized in that the N-methylol groups and polyethers containing N-methylenoxy groups with low molecular weight N-polymethylolvers binds. 3. The method according to claim 1 and 2, dadurcr. characterized in that as N-polymethylol compounds Hexamethylol melamine and / or tetramethylol acetylene urea and / or tetramethylol dimethylacetylene urea used. 4. The method according to claim 1 to 3, characterized in that the reaction in one Executes water-hexanetriol mixture. © 909 530/402 6.59