DE2326141A1 - METHOD OF MANUFACTURING NEW MONOMERS - Google Patents

Description

PATENT ADVOCATE

May 21, 1973 Application files: 75,582

PATENT APPLICATION

Applicant; Ceskoslovenskä akademie ve "d., Praha 1

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Title: Process for the preparation of new monomers

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The invention relates to a process for the preparation of new monomers.

For some technically important synthetic purposes it is useful to use polymerizable compounds = monomers - with specific to prepare reactive functions that can lead to precisely defined conversions in the polymers formed, tine such The function is the aromatic amino groups that allow diazotization and coupling reactions to be carried out on the polymers. However, since a free aromatic amino group would have a disruptive effect in the polymerization reactions due to its ability to free radicals to capture and thus an undesirable inhibiting effect it seemed necessary to use monomers. prepare, whose aromatic amino group is replaced by an essentially hydrolyzable one Amide group would be blocked.

According to the invention, important monomers of this type can also be used the general formula

CH ₂ = C - CO JO - CH ₂ - CH ₂ J _χ 0 - Ar NH - R ₂

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prepare in which R, a hydrogen atom or a methyl group, Ar is a divalent aromatic radical and R »is an acyl, carboxyalkyl or sulfo group. The education these new compounds takes place through reaction of the hydroxy compounds

R ₂ NH - Ar - 0 CH ₃ --CH ₂ - 0! _χ Η

with a methacryloylating or acryloying agent, such as methacrylic acid or acrylic acid, but especially acryloyl chloride, methacrylic anhydride or methyl methacrylate is. Some of the starting hydroxy compounds are already known. _{Its simplest representative is the p-acetaminophenol (R 2} = acetyl, Ar ^B p_phenylene, χ = 0) already prepared by "Morse (Ber. 11, 232). A whole range of different substitution derivatives have also been described, for example 2,6- Chlor-4-benzamine phenol (Raiford, Taft, Lankelma, J. Am · Chera. Soc. 46, 2055) or 4-acetan inobrenzcatechin-2-ihe thy lather (Fichter, Schwab, Ber. 39, 3340) The synthesis of the monomers of this series can also be hydroxy-amino compounds with two or more aromatic or, alternatively, heterocyclo-aromatic rings with a protected amino group (e.g. δ-acetaminonaphthol-l ^ '- acetamino-4-hydroxyd! phenyl / Tauber, Ber ..27, 2630 / or 5-ßenzaralno-e-hydroxychlnoUn (Gattennann, Ber. 27, 1939 /).

For the preparation of monomers of this series with an extended chain one starts from the same basic compounds as

309849/122 1

S3347-3- 2326H1

in the above examples, which are reacted with jithylene oxide before the acyl of the unsaturated acid is introduced. Depending on the molar ratio of the aminophenol to the ethylene oxide, an intermediate product with a shorter or longer ethylene oxide chain is obtained in the first synthesis. For example, from p-acetamine phenylene and ethylene oxide, one of the simplest representatives of this series is obtained according to Bayer (Frdl. 12, 687) at a molar ratio of 1: 1 (x = 1, R. - CH ₃ , Rg = p_phenylene).

Example 1.

^ »5 g of 2- (p-acetaminophenoxy) ethanol, prepared by heating p- ^ cetaninophenol with ethylene oxide to 150 C and recrystallization of the crude product from acetone, were stirred with 82 ml of dry pyridine. Then "the suspension under hollows and energetic Rehren was added during 30 minutes by 47 g Methacryloy! CHLORIDE, wherein the temperature of Geraisches did not exceed 25 ⁰ C. After e instund tgem standing, the reaction mixture was under vigorous agitation into 1000 ml ice ^ Lasser The fine crystalline precipitate which separated out was filtered off with suction and washed with 500 μl of ice water. After drying, it weighed 92 g. By recrystallization from acetone / Kasser treatment (3t2), completely pure is obtained with little loss -tidlprilMtovpiHfeig ^ äCnylmethacrylat of m.p. 118-119 ⁰ C

Example 2

In a pressure vessel made of alloy steel, 62 g Ethylene oxide and 26.4 g p-acetaminophenol for 10 hours

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am .. ^ T'.y .τ / Ι ".!, ^ 3098A3 / 122l

Z 3347-4-2326 H.

heated to 150 ^{° C.} The reaction product obtained after a small amount of unreacted ethylene oxide has been distilled off, according to gel chromatographic analysis, consists of a series of compounds which corresponds to the formula given above, in which R ^β CH-CO In this series of compounds the links with ^s 4 to χ = 12 occur in one Amount of 90 to 9% on, »obel In the largest amount the link with χ» is present. In the methacryloylation carried out similarly in Example 1, the relative occurrence of the individual members of this series is retained. Methacrylated polyethylene oxide derivatives obtained from DTe serve as a cheap raw material for the preparation of such carriers of biologically active substances whose reactive aromatic ligand is connected to the rigid matrix via a long arm.

0 9 8 4 9/1221

Claims (1)

Z 3347-5- '■ PATENT CLAIM Process for the preparation of new monomers of the general formula R ₉ -NH-Ar; 0 - CH. - CH ₉ Z _L ZZ In which R is a hydrogen atom or a methyl group, Ar is a divalent aromatic radical and R _{2 is} an acyl, carboxyalkyl or sulfo group, characterized in that one is a hydroxy compound the general formula - NH i- Ar 0-CH ₂ -CH ₂ I. old a methacryloylation or acryloylation unit, e.g. with methacrylic acid or acrylic acid and especially with their reactive derivatives, e.g. the halide, anhydride or ester, let it react. changed on 309849/1221 ORIGINAL INSPECTED