SU218163A1 - METHOD OF OBTAINING AMIDOESTERS OF METACRYLIC BOIL ACID - Google Patents

Description

The invention relates to a process for the preparation of new monomers with functional groups, in particular, to a process for the preparation of methacrylic acid amido esters.

These monomers can be used to polymerize or copolymerize with other monomers to produce polymeric materials with different properties. Methacrylic acid amide dosages are of particular interest as crosslinking agents containing several double bonds with different polymerizability, and the ester and amide functional groups.

Methods for preparing the amido esters of methacrylic acid are not described in the literature.

It is suggested (US Patent No. 2.593888) that during the synthesis of N (2-hydroxyethyl) methacrylamides from methacrylic acid chloride and aminoethanols, methacrylic acid amide esters can form as an impurity. However, there is no data on the release of amido esters. For information on the preparation of methacrylic acid amido esters by the interaction of lower alkylacrylates with alkanolamines containing a secondary amino group, there is no literature.

CH. ABOUT

SNS about

CH, with - with - ONCHS, - N - with - with SNO,

RR

where R is hydrogen or methyl, R is alkyl, alkenyl or methacryloxyalkyl.

The method consists in reacting mono- or dialkanolamines with a secondary amino group by heating with an excess of lower alkyl methacrylate, such as methyl methacrylate, in the presence of alkaline catalysts, such as sodium methoxide, and polymerization inhibitors with simultaneous distillation of the resulting lower alkane and subsequent isolation of amino esters from the reaction mixtures

The selection of monomers is carried out as follows.

The excess of lower alkyl methacrylate, for example methyl methacrylate, is distilled off under reduced pressure, the remaining amido ester is distilled under vacuum or purified, washed from impurities with an alkali solution and water. In this case, slightly colored monomers are obtained; however, according to the physicochemical constants, the analysis data and the ability to polymerize, they practically do not differ from the monomers separated by distillation. The molar ratio of methyl methacrylate to amino alcohol can be equal to from 2.5: 1 to 8: 1 (preferably from 3: 1 to 5: 1), the amount of catalyst is 0.1-10 mol. Vc (preferably 0.5-4 mol%), counted on the amino alcohol taken into reaction. Phenols, naphthols, aromatic amines, aminophenols and other compounds are used as polymerization inhibitors, for example hydroquinone, di-: 5-naphthol, cc-nitroso-p-naphthol, / g-oxydiphenylamine, fenthiazine. The best inhibitors are hydroquinone and α-nitrosor-naphthol in an amount of 0.01-3 wt. % (preferably 0.1 - 1% w / v), calculated as alkyl methacrylate. Example 1.-Butyl-K-2- (methacrylyloxy) ethylmethacrylamide. A. In a flask equipped with a thermal meter and attached to a distillation column, 23.4 g (0.2 g-lul) of dry 2-n-: butylamino-ethiol, 100 g (1 g mol) of dry methyl methacrylate and 1 g of a- nitroso-p-naphthol. The mixture is heated to boiling and 0.5 ml of a 25Vo-Horo solution of sodium methylate in dry methanol is injected with a syringe. Subsequently, the catalyst is added 0.1 ml every 5 minutes throughout the reaction. in the reaction, methanol is distilled off in a mixture with methyl methacrylate at a temperature of 65-67 ° C. After 50 minutes, 15.55 g of a mixture containing 73 / o is taken (I, 35 ) methanol (determined refractometrically), which, taking into account the methanol introduced with the catalyst, corresponds to a 81z / O conversion. After another 30 min, the conversion of the released methanol reaches & 7Vo. The reaction is stopped, the mixture is filtered, the excess methyl methacrylate is distilled off at a residual pressure of about 100 mmHg. Distillation of the residue in vacuo gives 37.1 g (73.4 Vc from theoretical, based on amino alcohol) N-n-butyl-1 -2- (meth: kryloxy) ethyl ethyl methacrylamide; m.p. 111 - 113 ° С (0.4 mmHg); on 1,4732; df 0.9960; MRo 71.28; calculated 71.19. Found, N 5.77; 5.78. Ci.HoaNOs. Calculated, o / o: N 5.53. B. 23.4 g (0.2 g-mol) of 2-butylamino-ethanol is reacted with 100 g (1.0 g-mol) of methyl methacrylate under test conditions A with the difference that hydroquinone is used as a polymerization inhibitor. After completion of the reaction, the mixture is washed with 20% sodium hydroxide solution (4 x 40 ml), then with water and dried over a lottery. Methyl methacrylate is distilled off in vacuum at a temperature not exceeding 50 ° C. 45 g (88.9 oz / o from theoretical) Mn-butyl-M-2- (methacrylyloxy) ethyl 1 methacrylamide are obtained in the form of a slightly short liquid; PP 1.4719. Example 2. K, 1 -Butyl-M-2- (methacryloxy) -propylmethacrylamide. In the device for transesterification, 13.1 g (0.1 giuyol) of 2-n-butylaminoisopropanol, 50 g (0.5 g-mol) of methyl methacrylate and 0.5 g of hydroquinone are placed. The mixture is heated to boiling and 0.5 ml of a 25% sodium methoxide solution is added. Subsequently, the catalyst was added 0.2 ml every 10 minutes during the whole reaction. After 140 minutes, 6.89 g of methanol is liberated, which, given the y of methanol, introduced with the catalyst, is 78.1? / O of the theoretical amount. The reaction mixture is filtered and the excess methyl methacrylate is distilled off. The residue is dissolved in 100 ml of diethyl ether, the ethereal solution is washed three times with 10% sodium hydroxide solution 50 ml each, then with a saturated solution of potash (50.il) and dried over anhydrous potash. The solvent is distilled off, the residue is kept in vacuo to remove light, persistent impurities. Get 18.7 g (70z / o from theoretical amidoether). Found,%: N 5.73; 5.82. CijHojNOs. It is calculated, s / (|: N 5.24. The washed product is distilled in 1 vacuum of in the presence of diphenyl-p-phenylenediamine. 16.9 g (61% of theoretical) pure, -butyl-1 -2- ( methacrylyloxy) ethyl methacrylamide; bp 107.5 ° C (0.4 mmHg); 1.4680; df 0.9762; MRo 76.12; MR 75.81 was calculated. Found, o / o: N 5.22; 5.28. CigHasNO; Calculated:%: N 5.23 Example 3. -alkyl-M-2- (methacrylyloxy) -ethyl methacrylamide From 20.2 g (0.2 g -mol) 2-allylaminoethanol and 100 g (1 g-mol of methyl methacrylate in the presence of 1 g of hydroquinone and sodium methylate under the conditions of example 2 are obtained 31.93 g (67.2% of theoretical) of washed or impurities am Found: N, 5.51; 5.65; C.HjoNOs. Calculated; e / o: N, 5.91. After distillation in vacuum, 28.7 g (60.5 e / o from the theoretical), pure N -allylG -2- (methacrylyloxy) -ethyl methacrylamide; bp 110-112 C (0.35 mm Hg.) n 1.4822; d | ° 1.0268; MRo, found 65.86; calculated 66.11. Found, o / (,: N, 5.75; 5.79. SiN in the Gum. Calculated, e / o: N, 5.91. Example 4. M, M-Di- 2- (methacryloxy) ethyl - methacrylamide. 21 g (0.2 g-mol) of diethanolamine, 150 g (,--mol of methyl methacrylate and 1.5 g of hydroquinone) are placed in a device for the transesterification. The reaction is carried out as described in Example 1, B. After 2.5 hours the conversion for the separated methanol is 93.7-J / o- The yield of the monomer is 46 g (72.09 / 0 of the theoretical, calculated as amino-alcohol); By 1.4869. Found, N4.18; 4.39. SyuNZKO Calculated, - / s: N 4.38. Subject of the invention. A method for producing methacrylic acid amido esters of the general formula CH 3 O II CH, C — C —OCHH, —N — s — with CH, CH 2 R where R is H or methyl. 5 10 15 R - alknl, alkenyl or methacryloxyalk sludge (CHO C — C — O — CH — CH.), characterized in that the mono- or dialkanolamine containing the secondary amino group is reacted with a lower alkyl methacrylate, taken up in excess when heated while simultaneously distilling off the lower alcohol in the presence of alkaline catalysts, for example sodium methylate, and polymerization inhibitors, followed by isolation of the target product by conventional methods.

Compiled by V. Andreev Editor L. G. GerasimovTechred L. Ya. Levin Corrector L. V. Yushshga