DE866094C - Process for the production of organic compounds, preferably polyether bodies, from aldehyde resins - Google Patents

Description

Process for the production of organic compounds, preferably polyethylene bodies, from aldehyde resins. Solid amorphous masses formed, for example, according to Patent 381 7: 2o, can be converted into novel bodies in a surprising manner by reaction with chemical agents. The Al & hyd resins are derivatives of acetylene and evidently contain chemically bound water in different proportions in connection with the polvethine nucleus formed by condensation of the acetylene. A partial or total replacement of this water is an issue in the newly discovered process. The derivatives resulting from these reactions should therefore be addressed as polyethine bodies with the composition (C2H2), 1 - K. Here, K means z. B. organic acid, inorganic acid, alcohol, water, halogen or other exchange compounds alone or as a mixture, and y varies from o to x.

For the sake of clarity, the examples started from the same resin product which was produced by thermal treatment according to Patent 38I (72o and sold under the name Wackerkunstschellack KR. Its elemental analysis is 68.5% C, 8.26% H .

Example ii [oo g of resin KR were dissolved in about 5ao g of hot glycine and about 1/2 cc of concentrated sulfuric acid was added dropwise to the hot solution with shaking. In the case of Schw-efelsä, urezils # etz, there was an immediate local reaction with the excretion of black chunks. The next day the contents of the flask were almost solid and there was only a little liquid left. Water was added to the reaction product and boiled. Repeated washing or boiling with water gave after drying on a clay plate in the air and in a drying cabinet at i zd '86 g of a coffee-brown powder. Its composition is 72.040 / OC, 7.55 '/ OH.

The product is partly soluble in alcohol and then results in a i,: 2o 'melting brown brittle resin. The alcohol-insoluble part is against solvents fairly stable and amorphous.

Example 2 of g of resin KR were dissolved in # 70 cc glycol in the heat. When a few drops of sulfuric acid were added to the hot solution, reactions with dark precipitates occurred immediately. On the next day, water was poured over the reaction product, triturated and boiled until the wash water ran off clear and, after drying at 1.2 ', about 7 g of a lion-brown powder were obtained. The elemental analysis resulted in 7, I, II '/ eC, 6.8, # - 9 VO H.

The product is partly soluble in alcohol and then gives a brown color echmelzemid resin. The alcohol-insoluble amorphous part is in other common solvents, such as acetone, benzene, etc., only partially to be brought into solution.

Example 3 10 g of resin KR were dissolved in 60 cc of hot formic acid and 4 to 5 drops of concentrated sulfuric acid were added to this hot solution. When the sulfuric acid was added to the hot solution, a slightly distinct reaction occurred. After 3 hours of heating, a dark resin was precipitated from the black-colored solution with 2ocr ccm of water, washed out with hot water and dried. 84 g were obtained. The combustion er, -ab 70 "-, 130 / OC, 7.1'7 # o / OH were found from 442 to saponification; 465 #.

The product is originally blackish and becomes a lion brown as it is boiled with water. It is partially soluble in alcohol. The alcohol-soluble part is a brown, brittle resin with good solubility in common organic solvents. It is only partially soluble in meffianol and tetrachloraffian, and only in traces in benzene. The alcohol-insoluble part is amorphous and sparingly soluble. In acetic acid, methylanone, the plasticizer known under the protected value PalatinülM and pyridine, it partially dissolves when hot. Example 4 30 g of resin KR were dissolved in 150 cc of hot glacial acetic acid. A mixture of: 2 cc of concentrated sulfuric acid was added to the cooled solution. added in 50 cc of glacial acetic acid. When the sulfuric acid solution was added to the cold batch, there was no noticeable reaction other than a dark color. A violent reaction did not take place until it was heated. The reaction mixture was kept at the boiling point of acetic acid for a few hours and the hot solution, which solidified under 100%, was poured into water, a black-brown hard powder separating out. Boiling with water and drying gave a coffee-e-brown powder which swelled profusely with water. Receive about 2.5 g.

The product is partially soluble in alcohol. The alcohol-soluble part resulted in the combustion of 73.34 '/ 0 C, 6.74 1/9 H and a VN of 2.46.

In the case of the alcohol-insoluble part, the following was found during combustion: 72.76 '/ o C, 7.1 o 04 H, and an VN of #: 2i31.

A polyether acetate of formula (C.H2) 4. C H, 3 H CO O, has the composition 73, 1 0/0 C, 7.3 1 / o H.

Example 5 50 g of resin KR were dissolved in 2 o cc of glacial acetic acid, and a mixture of 5 cc of concentrated sulfuric acid in 5 oc of glacial acetic acid was added to the hot solution. The reaction mixture was heated to the boiling point of glacial acetic acid for 3 hours and then the distillable material was distilled from the reaction flask in an oil bath. About 112 g of saponifiable esters were found in the acetic acid removed. After washing with water and drying, the solid reaction product gave a black-brown, hard powder. Receive 46 g. During the combustion, ',', 7-3.98 O / OC, 7.24 1 / o H and a VZ, of 2 # 9.7; -certainly.

However, this product is in contrast to, according to the reaction product Example 4 slightly soluble. It is cold and hot only slightly soluble in benzene, -Batyla, acetate, methylanone and tetrachloroethane.

B-eis-piel 6 5og of HarzKR were dissolved in 2ooccm of glacial acetic acid and a mixture of 2 ccm of concentrated sulfuric acid and 100 ccm of glacial acetic acid was added to this in the heat. This reaction table was kept boiling for 4 hours and the resulting dark solution poured into fuel. A dark sludge separated out overnight, which, boiled several times with iSprit, after drying at i - o 'turns out to be a lion-roasted powder.

This product yielded by the combustion 73.24 0/0 C, 7.36% H and had a VN of 3 16, so agrees with its composition corresponding to the formula set out in Example 4 a Polyäthina, cetats good agreement.

The filtrate, which was in suspension, was concentrated on a water bath and poured into water. The powder which separated out gave, after drying, a lion-brown powder with the composition 70.97 % C, 7.11% H and had a VN of 297.

It remains to be seen whether there is an acetate that is lower in acetic acid or a derivative of another accompanying component in the starting resin KR, primarily or as a result of the boiling with water. ZD Example 7 Resin KR were dissolved in 50ccm of hot glacial acetic acid and a few drops of concentrated sulfuric acid were added to the hot solution, a brief and vigorous reaction beginning in each case with a dark color. A voluminous black body was precipitated from the solution that had stood overnight by adding 15 ounces of water. Prolonged washing with water gave a brown product after drying at 1201, namely about 8 g. This product was particularly voluminous in relation to the other acetates prepared according to Examples 4 to 6.

The combustion resulted in 70.67 ° C., 7.03 % H. A VN of 263 was determined.

It remains to be seen whether this is only a partial product Esterification is present or a partially re-saponified acetate or a mixture of reaction products.

This product is very easily soluble. It's cold in acetone, benzene, Butyl acetate, chloroform, acetic acid, methanol, methylanone, Palatinol M, fuel, Tetrachloroethane partially soluble, in glycol and Tetraclil & rkühlenstoff cold only in traces; on the other hand, it is almost soluble in pyridine when cold.

When hot it is completely soluble in methylanone, palatinol M, pyridine, tetrachloroethane; it is almost entirely soluble in acetic acid.

In comparison to this then comes with regard to a solubility properties the product according to Example-4, which is generally in the solvents listed cold and hot is only partially soluble, in. methanol only traces.

The product according to Example 6 has a further reduced solubility. It is insoluble in acetone, benzene, turpentine oil, vinyl acetate, cold and warm; cold and hot it is somewhat soluble in C-chloronaphthaline, chloroform, dichloroethylene, Palatinol C and M and trichlorethylene; otherwise it is only soluble in traces.

The product according to lead example 5 shows the least tendency to dissolve. It is only slightly soluble in benzene, butyl acetate, methylanone and tetrachloroethane when cold and hot, and even insoluble when cold.

Examples 4, 5, 6 and 7 deal in more detail with the possible variations for a reaction with acetic acid, in order to show that, to a large extent, products with easy or difficult solubility in easily pulverizable or hard form, more or less voluminous "resinous meltable or amorphous un-Z> meltable and can be prepared colored differently, whereby these products is opened in a wide field for the usual for resins and other plastics applications. B EXAMPLE 8 50 g of resin KR were dissolved g in 450 g Eistssi Chlorine was passed into this solution at room temperature. The solution, which originally had the characteristic red-yellow color of the aldehyde resin, turned pale after an initial dark color. 'After the solution had absorbed 56 g of chlorine within 340 min The reaction product was precipitated with 3 liters of water and washed free of chlorine and acid with a further 9 liters of water Powder containing 46.0% carbon, 4.81% hydrogen, 34.3% chlorine. The yield was 88. The chlorination product is very easily soluble in almost all organic solvents, e.g. B. in acetone, butyl acetate, monochlorobenzene, benzene, chloroform, acetic acid, pyridine, Trichloräthyleii, The process and the form of the resulting products can ' through the choice of other solvents, other halogens, through the addition of halogen carriers, etc., also through variation the solvent, the temperatures and the like, the chlorinating agent can be varied. A further example of chlorination is therefore given below. Example # 9 5o g of resin were dissolved in 450 KR 9 glacial acetic acid. Phosphorus pentachloride passed so long while cooling to 00 chlorine, to Sun g weight gain was achieved - in this solution was, after addition of 7.5. By exposing the solution to light, the reaction of the chlorine-saturated system could be passed on in such a way that a light-colored reaction product precipitated which, after its isolation, had the saponification number 558 . A second, almost white reaction product with a saponification number of 573 was isolated by precipitation of the mother liquor with methanol. A third white reaction product with the saponification number # 72 i was obtained from the mother liquor thereof by adding water.

Similar compounds are obtained with other halogens.

One leaves, on a solution of K-R resin in glacial acetic acid BTom in glacial acetic acid react in solution, a weakly colored product containing broni is obtained.

The action of iodine in a solution of glacial acetic acid-alcohol precipitates a pale gray-green colored iodine- containing powdery product from an E-acetic acid solution of KR resin.

The present procedure opens up a new path to new ones organic compounds, preferably polyether bodies.

Their area of application lies among others. on; the level of the previously known Plastics, especially the known areas of application of the resins and polyvidyl compounds par excellence.

Claims (1)

PATENT CLAIM: Process for the production of organic compounds, preferably polyethylene bodies made from aldehyde resins, characterized in that the water component contained therein is wholly or partially replaced by others Chemical agents such as alcohols, acids, halogen and the like, or several of these Components replaced.