The method of obtaining full ethers of oligomers of 1,2 - oxirane

 

(57) Abstract:

The invention relates to methods of producing polyether of polyglycols (oligomers of 1,2-oxirane) and can be used in chemical industry for production of surfactants, plasticizers, binders, complexing agents, and so on, Get full ethers of oligomers of 1,2-oxirane by oxyalkylene complex alkoxyalkane with Lewis acid olefin oxide, and as alkoxyalkane use of dimethyl or diethyl ether at a molar ratio of ether and a Lewis acid is 1:0,03-0,05, the feed rate of the olefin oxide support in the range of 0.0004-0.0005-M/min, and the reaction is carried out at 10-30oC. technical result Achieved - simplifying the process, reducing energy and material costs.

The invention relates to the field of chemistry polyethers, in particular a process for the production of polyethers of polyglycols (oligomers of 1,2-oxirane), and can be used in chemical industry for production of surfactants, plasticizers, binders, complexing agents, etc.

There are many ways of practicalapplication (patent Germany 1129147, 1962), the interaction of mono - or polyethers with oxacillin in the presence of Lewis acid (patent GB 1574485, 1980).

These methods complete polyesters are either multi-stage, because first get diols or bifunctional derivatives, which are then alkylate, or, as in the latter case, to obtain oligomers higher homologous series (with a degree of polymerization of >4) repeated reaction with the obtained low molecular weight full esters.

The most common is the method of obtaining full ethers of glycols and polyglycols by oxyalkylene alcohols oxides of olefins in the presence of acid catalysts such as Lewis acids. According to this method first retrieves cellosolve, and when excess alcohol is full esters of glycols (O. N. Diment, K. S. Kazan, A. M. Miroshnikov "Glycols and other derivatives of oxides of ethylene and propylene" -M.: Chemistry, 1976, pp. 306-316). The disadvantage of this method of production is their low yield (20%), because the main product is monoether - cellosolve.

Closest to the proposed method according to the technical essence is a way of dimethyl esters of oligomers of 1,2-Okie esters of oligomers of 1,2-oxirane formed in one stage by oxyalkylene complex 1,2-dimethoxyethane with Lewis acid oxide olefin at a certain ratio of the components of the reaction system.

An important achievement of the prototype method is the ability to complete simple esters of oligomers of 1,2-oxirane including the degree of polymerization of >4 at one stage.

The disadvantages of the prototype method can include the inability to use, in this case, widely available tonnage of chemical reagents (e.g., methyl and ethyl esters) due to the high stability of its complex with the Lewis acid. In addition, used in the method-prototype 1,2-dimethoxyethan has a higher boiling point, which complicates the process and increases energy consumption at the stage of selection of the target product.

Object of the present invention is to provide a highly efficient one-step method of obtaining full ethers of 1,2-oxirane with a degree of polymerization greater than 4, allowing the use of widely available tonnage dimethyl (diethyl) ether and reduce energy and material costs.

The solution of this problem is achieved by the proposed method, complete the simple esters of oligomers of 1,2-oxirane by oxyalkylene complex alkoxyalkane with Lewis acid oxide olefin, in which Cuica, equal to 1:0.03 to 0.05, the feed rate of the olefin oxide support in the range of 0.0004-0.0005-M/min, and the reaction is carried out at 10-30oC.

From literature it is known that the Lewis acid forms with methyl and ethyl esters of a stable complex. For example, apirat boron TRIFLUORIDE is a common catalyst in the ionic polymerization of olefin oxides, which process is running at the active centre of zwitter-ionic nature of obtaining cyclic products (R. I. Kern, J. Organ. Chem. 1968. V. 33. P. 388-390).

Adding to the equimolar ratio of the ether-the Lewis acid is equal to the amount of olefin oxide is formed oxonium salt of the appropriate acid Lewis (H. Meerwein, E. Battenberg, H. Gold, J. fur Prakrische Chem. 1940. V. 154. P. 83). For example, in the case BF3and diethyl ether is formed Et3OBF4at which the polymerization of olefin oxides also occurs with formation of a cyclic product. The formation of low molecular weight linear products, the degree of polymerization not exceeding four in excess of these esters is possible (at a molar ratio of the ether-oxide olefin of 2-5:1, patent GB 1574485, 1980). Products of higher molecular mass in these conditions cannot be obtained.

Conducted and what Luisa able to dissociate on essential due to the formation of carbocation (detected by NMR spectroscopy), under certain conditions, can become an active centre for the disclosure of the cycle of olefin oxide and growth of the linear chain to degrees of polymerization of the big 4. Further studies showed that the complex of the Lewis acid with diethyl (dimethyl) ester can also dissociate with the formation of carbocation (detected by NMR). However, when you add in the oxide olefin she takes the Lewis acid itself with the formation of active centers zwicker-ionic nature, and the reaction quickly "falls" towards the production of cyclic products. To suppress competing processes and shift the reaction towards the formation of linear products, it is necessary to conduct the reaction so that the feeding speed of the olefin oxide is equal to the speed of its entry into the linear polymer. In this case, it becomes impossible to process with the formation of the active center zwicker-ionic nature.

As a result of experiments, it was found that this condition is confirmed by the lack of reaction products of cyclic oligomers) molar ratio of dimethyl (diethyl) ether and a Lewis acid is 1:0,03 - 0,05, and maintaining the feed rate ocisoC.

Examples of the method.

Example 1. In a flask with stirrer, filled with argon, loaded 0.74 g (0.01 M) of diethyl ether and 0.07 g (0,0005 M) BF3THF (tetrahydrofuran). Under stirring at 20oWith added dropwise 12 g of epichlorohydrin (ECG) at a rate of 0.0004 M/min for 4 hours At this temperature the reaction mixture should not exceed 30oC. Then stirring continued for a further 2 hours After 6 hours, the product yield 10.5 g (80 %). Catalyst - BF3neutralized Cao (2 g) under stirring for 30 min, then filtered. Next, unreacted ECG Argonauts under slight vacuum. The reaction product is a viscous colorless or light yellow substance with a degree of polymerization ~ 30 MM (about 3000), end C2H5-O-groups. By IR - and NMR-spectroscopy shows the absence of the polymer hydroxyl groups. Quantity (availability) of cyclic products cannot be determined by liquid chromatography.

Example 2. 1.2 g (0,26 M) dimethyl ether and 0.07 g (0,0005 M) BF3THF is added 15 g of epichlorohydrin for 4 hours at a temperature of 20+10oWith speeds of 0.0004 M/min. and the product Yield of 14.2, the Procedure selected is

Example 3. To a mixture of 0.7 g (0.02 M) of dimethyl ether and 0.13 g (0,0005 M) SnCl4added 12 g of epichlorohydrin for 4 hours at a temperature of 15+10oWith speeds of 0.0005 M/min. and the product Yield of 9.5, Neutralization of the catalyst was carried out by the water - to 10-fold excess and its subsequent filtering. Procedures for the isolation and analysis of polymer similar to example 1. The reaction product is a linear oligomer with MM about 1500 (n ~ 15).

Example 4. To a mixture of 0.95 g (0,0012 M) diethyl ether and 0.1 g (of 0.0004 M) SnCl4added 10 g of epichlorohydrin for 3.5 hours at a temperature of 20+10oWith speeds of 0.0005 M/min. and the product Yield of 9.1, the Procedure of washing the catalyst is similar to example 3, and the isolation and analysis of polymer example 1. The reaction product is a linear polymer with MM about 1500 (n ~ 15).

Example 5. To a mixture of 0.74 g (0.01 M) of diethyl ether and 0.07 g (0,0005 M) BF3THF at 20oWith added dropwise 10 g of propylene oxide with a speed of 0.0004 M/min. and the product Yield of 8.8, Procedures for the isolation and analysis of polymer similar to example 1. The reaction product is a linear oligomer with about 1200 MM (n ~ 20).

Example 6. To a mixture of 0.75 g (0.01 M) of diethyl ether and 0.07 g (0,0005 M) BF3THF at 10oWith added dropwise 10 g of oxide is 1. The reaction product is a linear oligomer with about 1000 MM (n ~ 30).

The method of obtaining full ethers of oligomers of 1,2-oxirane by oxyalkylene complex alkoxyalkane with Lewis acid oxide olefin, characterized in that as alkoxyalkane use of dimethyl or diethyl ether at a molar ratio of ether and a Lewis acid is 1: 0.03 to 0.05, the feed rate of the olefin oxide support in the range of 0.0004-0.0005-M/min, and the reaction is carried out at 10-30oC.

 

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