Patent GB-360909-A (GB)
Title: Improvements in the manufacture and production of artificial masses
IPC: C08G12/42
Filed: 1930-07-07
Abstract: Artificial masses obtained by the condensation (preferably in the presence of acid or alkaline condensation agents, but substantially in the absence of water) of a urea and formaldehyde or of a methylol urea or an anhydride thereof in the presence of organic substances containing a free hydroxyl group and at least one further reactive group, namely halogen, primary or secondary amino, carboxyl or an additional hydroxyl group or a double linkage, are further treated to form groups containing oxygen such as ethers or esters from the reactive group with organic compounds, namely alcoholates, phenols, phenolates, carboxylic acid halides, anhydrides, or esters, salts of carboxylic acids or alkylene oxides.  The products may also be subsequently brought into reaction with further reactive compounds so far as the products contain reactive groups.  Suitable reagents comprising at least one hydroxyl group and another reactive group are polyhydric alcohols such as mono-, di- or polyethylene glycol or glycerol or their derivatives having at least one free hydroxyl group and another reactive group such as monoalkyl or monoarylethers of glycerol, halogen substitution products such as chlorhydrin, glycerol a -monochlorhydrin or a -b -dichlorhydrin and esters of polyhydric alcohols with polybasic organic acids such as esters of phthalic, oxalic, succinic, adipic or tartaric acids and esters of benzoic or other monobasic aromatic or aliphatic saturated or unsaturated acids with polyhydric alcohols. It is preferable to use halogen substitution products of polyhydric alcohols instead of the alcohols. Suitable primary or secondary amino-compounds are the alcoholamines such as mono-, di- or triethanol or propanolamine or N-ethanolaniline.  When the reaction products are likely to become too viscous the raw materials may be previously diluted with an inert solvent containing no free hydroxyl groups or other reactive groups such as dioxane.  In examples: (1) Dimethylolurea is added to a solution of urea nitrate in ethylene chlorhydrin, the resulting solution is neutralized with tertiary sodium phosphate and the condensation product precipitated with ethyl alcohol and washed with ethyl ether; the product is dissolved in ethylene glycol mono-methylether, the sodium soap of linseed oil fatty acids added to the solution and after heating precipitated sodium chloride is separated and the product carefully neutralized with glacial acetic acid; an excess of ethyl ether is added to precipitate the resin; urea and formaldehyde or paraformaldehyde may replace dimethylolurea as the starting material.  (2) The potassium soap of fatty acids obtainable by treating deresinified crude montan wax with chromic acid replace the sodium soap of linseed oil fatty acids in example 1; the product may be pressed with or without the addition of asbestos, sawdust, talcum, paper pulp or colouring matters and the addition of a suitable acid hardening agent such as glycollic acid facilitates the hardening of the pressed article.  (3) Adipic 1-1<1>-diglyceride is diluted with dioxane and treated with concentrated hydrochloric acid and dimethylolurea, the mixture is neutralized with tertiary sodium phosphate and precipitated with ethyl alcohol; the dried, pulverized product is suspended in pyridine and treated with benzoyl chloride, the whole being ice cooled; the product is poured into water to separate an oil product soluble in ethylene glycolmonomethylether.  (4) Dimethylolthiourea or dimethylolthiourea or a mixture thereof is added to a mixture of glycerol a -monochlorhydrin and hydrochloric acid and the mixture neutralized with tertiary sodium phosphate and precipitated as in Example 3; the product is fused with m-cresol and the product treated with phosphorus oxychloride with ice cooling and then freed from acid with aqueous sodium bicarbonate; the product is soluble in ethyl alcohol, acetone and ethylene glycolmonomethyl ether.  (5) Glycerine, oxalic acid and dimethylolurea are heated together and the pulverized product is dissolved in distilled commercial cresol and treated with phosphoric pentoxide; the product is washed with hot water and steam distilled; the final product is soluble in alkali and may be used for impregnating or sizing paper or pasteboard.  (6) A solution of sodium phenolate in ethylene glycol monomethyl ether replaces the sodium soap in Example 1; the product may be worked into lacquers or primers with cellulose esters.  (7) Dimethylolthiourea, ethylenechlorhydrin, and a solution of urea in ethyl alcohol are heated together and the product is neutralized with a solution of caustic soda in ethyl alcohol and precipitated by a mixture of ethyl alcohol and acetone; the product is dissolved in ethylene glycol monomethyl ether and treated with the potash salt of palm kernel fatty acids; potassium chloride is separated and the product is precipitated by ethyl ether; the resin has a high adhesive and a high electrical insulating power; the dimethylolthiourea may be replaced by a mixture of dimethylolurea and dimethylolthiourea.  (8) Dimethylolurea, glycollic acid and a solution of urea nitrate in ethyl alcohol are heated together and the solid product precipitated by ethyl ether; this product is dissolved in dioxane and ethylene oxide is introduced and the new product precipitated by ethyl ether to give a resinous product soluble in methyl or ethyl alcohol.  (9) Dimethylolurea is boiled with allyl alcohol and an ethyl alcohol solution of urea nitrate and the product is precipitated by ethyl ether; by reaction with benzol chloride in pyridine solution in presence of aluminium chloride it gives a resin soluble in glycol monomethyl ether.  Specifications 260,253, 261,029, 301,696, 308,996, 316,144, 319,251, 327,417, 327,673, 327,713, 332,634, [all in Class 2 (iii), Dyes &c.], 344,401, and 344,626 are referred to.  Adipic 1-1-<1>-diglyceride is prepared by the treatment of the sodium salt of adipic acid with glycerol-a -monochlorhydrin,