SU771084A1 - Method of preparing vinyloxyalkylmethacrylates - Google Patents

Description

transesterification congestion and polymerization inhibitor. A distinctive feature of this method is the use of the corresponding sodium vinyloxy alkylates of sodium as the transesterification catalyst, and the use of hydroquinone and phenyl-E-naphthylamine as inhibitors. The transesterification catalyst and polymerization inhibitor is desirable for sconing in a weight ratio of 1: 1 in the amount of 0.5-1.0% of the total reagent weight. The catalyst is usually supplied continuously (or in portions) throughout the process. Example. Synthesis of vinyloxyethyl methacrylate 1, CH, CH 2 CO, CH, OOS (CH 1. Preparation of the catalyst. Dissolve 0.6 g of NaOH (1.0% sodium vinyl ethoxide) in 25 ml of ethylene glycol monovinyl ether, slowly distilling at atmospheric pressure 15 0.4 g of gyroquinone and O, 4 g of phenyl-p-naphthyls are dissolved in the residue and 2 g of the rut from the rut. 2. Conducting the transesterification. (1.25 mol) of methyl methacrylate, 34.0 g (total amount 10.0 g + + 34.0 g F 44.0 g - 0.5 mol) of ethylene mono vinyl ether lycol, O, 4 g of hydroquinone and 0.4 g of phenyl-ft-naphthyl amine, total content of inhibitors is 1.0%. The mixture is heated with stirring until boiling () and the catalyst is slowly added, simultaneously the methanol formed is distilled off (mixed with methyl methacrylate) at 62 ° C. After 4 h, the process is terminated, the excess methyl methacrylate is distilled off, and the residue is distilled in vacuo to give 65.1 g of vinyloxyethyl methacrylaum (83.3%, calculated as monovinyl ether), b.p. .46 ° С (2 mm Hg), t) 1.4482 °,, 9973. Calculated,%: C, 61.52; H 7.75; MR 41.82 SdN O, Found,%: C 61.32; H 7.75; MRjj 41,, 97. In the low-boiling fractions by GLC, 4.6 g of unreacted ethylene glycol monovinyl ether were found. Thus, the yield of vinyloxy ethylFletacrylate based on ethylene glycol ethanol glycol reacted is 93.3%. EXAMPLE 2 Using the amount in the starting Example 1, 0.3 g of NaOH (0.5% sodium vinyloxyethylate from the reagents taken), 0.4 g of hydroquinone and 0.4 g of phenyl-p-naphtylamine (0 , 5% of the load), receive 62.2 g (79.6%) of vnloxyethyl methacrylate. Example 3 (Synthesis of vinyloxy propyl methacrylate CH CHO (CH) OCOCfcH g Ui y 17 Catalyst preparation. Dissolve 0.06 g of NaOH (1.0% sodium vinyloxypropate) in 3.2 ml of monovinyl ether 1,3-propylene glycol, slowly distill 1 , 5 ml of distillate and in the residue dilute 0.04 g of hydroquinone and 0.04 g of phenyl-p-naphtylamine. 2. Conducting the transesterification Under the conditions of example 1, to 4.5 g of 1,3-propylene glycol monovinyl ether and 10 , 0 g of methyl methacrylate in the presence of VII, 0.04 g of hydroquinone and 0.04 g of phenyl-f3-naphthylamine (total inhibitor content 1.0%), heated to boiling, are added Prepared catalyst solution for 3 hours After distillation, 6.8 g (80.0%) of vinyloxypropyl methacrylate are obtained, bp 65 ° C (2 mm Hg), -I, 4482, 0.9828. Found %: C 63.27; H 8.42; MRjj 46.38. Calculated,%: C 63.51; H 8.29; MRj, 46.37. EXAMPLE 4. Synthesis of Vinyloxybutylmethacrylate (CH- ). Essess,). ., 1. Preparation of the catalyst. 0.02 g of NaOH (6.5% sodium vinyloxybutylate) was dissolved in 1.6 ml of 1,4-butylene glycol monovinyl ether, 0.8 ml was distilled off, and 0.04 g of hydroquinone and 0.04 g of phenyl were dissolved in the residue. - f-naphtylamine, (total inhibitor content of 1.0%). 2. Conducting transesterification. Under the conditions of example 1, to 5.0 g of 1,4-butylene glycol monovinyl ether and 10.0 g of methyl methacrylate in the presence of 0.04 g of hydroquinone and 0.04 g of phenyl-fi-naphtylamine, (total inhibitor content 1%) heated to boiling, add the prepared catalyst solution over 3 hours. After distillation, 7.9 g (85.8%) of vinyloxybutyl methacrylate are obtained, i.e., kip 71C (2 MM.pT.cT.), t) l, 4508; di ° 0.9692-. Calculated,%: C b5,19; H 8.75 / MR 51.12, C AND 0 Found,%: C 65.04; H 8.72; MRjj 51.16; Example 5, When sodium methoxide is used as catalyst in methanol, the yield of vinyloxyethyl methacrylate is 50-67%, Example 6. Synthesis of vinyloxyethoxyethylmethacrylate -Sng 1. Preparation of the catalyst. 0.1 g of NaOH is dissolved in 5 ml of diethyleneglycol monovinyl ether. HEED released during the reaction is removed by vacuum distillation along with a small portion of the monovinyl ether used. In the remaining 4.1 g of a solution consisting of 0.4 g of catalyst and 3.7 g (3.6 ml) of diethylene glycol monovinyl ether, 0.1 g of hydroquinone and 0.1 g of phenyl / J-naphtylamine are dissolved .

2. Conduct of transesterification. Under the conditions of Example 1, a prepared catalyst solution was slowly added to a mixture of 9.2 ml of diethyleneglycol monovinyl ether and 26.7 ml of methyl methacrylate in the presence of 0.1 g of hydroquinone and 0.1 g of phenyl / 3-naphtylamine, heated to boiling. The methanol released is removed from the reaction by distillation in a mixture with methyl methacrylate at,

At the end of the reaction, the temperature is raised and an excess of methyl methacrylate is distilled off, and the residue is distilled in vacuo. 18.3 g of vinyloxyethoxyethyl methacrylate (91.5%, calculated on monovinyl ether) are obtained, b.p. 97C (3 MM.pT.cT.), TiD ° l, 4546, dJOi, oi72

Calculated,%: C 59.98, H 8.05; MR 52.90.

C JI ON FUNDED,%: C 59.76; H 8.13; Mrj 53.37.

In the low-boiling fractions by GLC, 0.6 g of monovinyl alcohol and diethylene glycol was found. Thus, the yield of vinyloxyethoxyethyl methacrylate based on the reacted diethylene gpicol monovinyl ether is 96.3%.

Claims (2)

Invention Formula The method of obtaining vinyl oxyalkyl methacrylates by transesterification of methyl methacrylate with monovinyl ethers of diols in the presence of a transesterification catalyst and polymerization inhibitor, characterized in that, to increase the yield and simplify the technology, the corresponding sodium vinyl oxy alkylates and phenyl are used as a transesterification catalyst -naphthylamine .V 2. Method POP.1, which differs from the fact that the transesterification catalyst and polymerization inhibitor are taken in a weight ratio of 1: 1, in an amount of 0.5-1.0% by weight of the reagent. Sources of information taken into account in the examination 1. US patent No. 692256, cl. 260-615В, published. 1954.