A method of obtaining a macrocyclic polyester

 

(57) Abstract:

Usage: for the synthesis of macrocyclic polymers. The inventive spend cationic polymerization of substituted alpha-oxide from the group of the epichlorohydrin, nitrate pilgramage alcohol or propylene oxide in an environment of dry organic solvent and an atmosphere of dry inert gas at 0 to 20C in the presence of a catalyst tetrahydrofuranate boron TRIFLUORIDE. 2 C. p. F.-ly, 1 table.

The invention relates to polymer chemistry, in particular to methods of synthesis of macrocyclic polyethers (crown ethers).

A method of obtaining macrocyclic polyethers cationic polymerization of ethylene oxide initiated by the Lewis acid. The obtained target product is a cyclic polymer of General formula

where n=3-9 [1]

Closest to the invention to the technical essence and the achieved result is a way to obtain macrocyclic polyethers cationic polymerization of ethylene oxide in an environment of dry organic solvent, such as dioxane, benzene, methylene chloride in the atmosphere of dry inert gas at 0-20aboutWith the presence of the catalyst BF3[2] Get macrocyclic polyester with aranov this method ineffective, as in the solid phase polymer is practically absent. The method does not allow to obtain macrocyclic polyethers based replaced by oxiranes with the number of heteroatoms in the chain more than 11.

The objective of the invention is to obtain macrocyclic polyethers based replaced by oxiranes with functional groups in the structure of the crown ether with the number of heteroatoms in the chain more than 11.

To do this, hold the cationic polymerization of substituted alpha-oxide from the group of the epichlorohydrin, nitrate pilgramage alcohol or propylene oxide in an environment of dry organic solvent and an atmosphere of dry inert gas at 0-20aboutIn the presence of a catalyst of tetrahydrofuran boron TRIFLUORIDE. As a dry solvent used, the solvent basicity lower basicity of the monomer, such as methylene chloride (CH2Cl2) D=-12 cm-1or carbon tetrachloride (CCl4) D=-21 cm-1.

As a dry solvent used, the solvent basicity, higher basicity of the monomer, for example dioxane (C2H8O2) D=77 cm-1.

Introduction to reaction as a monomer substituted oxide allows to obtain macrocyclic polyethers of ekoobrazovanii.

Use as a catalyst tetrahydrofuranate boron TRIFLUORIDE allowed to obtain macrocyclic polyethers based replaced by oxirane (target product) with a specified molecular weight distribution and to increase the yield of the target product by eliminating the influence of eye-catching in the early stages of the reaction components with high basicity and include them in the response.

If used as a dry solvent, the solvent basicity lower basicity of the monomer, for example methylene chloride ( D=12 cm-1) or carbon tetrachloride ( Y=-21 cm-1), you can get a macrocyclic polyether (target product) on the basis of substituted oxiranes with the given number of heteroatoms in the chain with n=4-9 and increase the yield of the target product.

If used as a dry solvent, the solvent basicity higher basicity of the monomer, for example dioxane ( D=77 cm-1), it is possible to obtain the target product with the molecular weight cycles n11 and to increase the yield of the target product.

The invention is illustrated by the following examples.

The reaction was carried out in a solution of dry solvent in an atmosphere of dry argon in the presence of catalysis is effected to the temperature of melting ice, the mixture of the solvent with the catalyst is added slowly (added dropwise) a monomer substituted-oxide, stirred for 5-6 h

Next to water-soluble polyesters (based on propylene oxide (OP), L=48 cm-1) the reaction mixture was aged at room temperature for 10-12 h with constant stirring, followed by separation of the target product.

For water-insoluble polyesters on the basis of epichlorohydrin (ECG), L= 40 cm-1and nitrate gitignore alcohol (NGS), L=55 cm-1in the reaction mixture, water was added, and the mixture was mixed for 0.5-1 h, the aqueous phase was separated from polimersoderzhashchie the organic phase, followed by the separation of the target product.

The obtained products were characterized on the content of macrocycles and their molecular weight distribution by the methods of liquid chromatography at critical conditions and gel permeation chromatography.

IR spectroscopic analysis of the target product confirms its purity by foreign functional groups.

Examples of specific implementation method and classification of the target product are listed in the table.

C-CH-CH2ONO2glycidyl nitrile

In examples 1-4 are shown obtaining the target product with low molecular weight cycles (n=4-9) with osnovnom the cm-1), ECG ( L=40 cm-1), NGS ( L=55 cm-1). The yield of the target product is 955% when the content of low-molecular-weight cycles with functional groups 70-90%

In examples 5, 7 obtained target product with high molecular cycles (n 11). The method was carried out using a solvent WITH4H8ABOUT2with basicity ( G cm-1), higher than the basicity of the monomer OP ( D=45 cm-1), ECG ( L=40 cm-1). The yield of the target product is 955% when the content of high molecular weight cycles with functional groups 70-90%

Example 6 the process was carried out on the prototype with the use of substituted oxiranes. In this case, the yield of the target product is very low (about 0.2 g) and almost no cyclic products such as low-molecular and high-molecular.

In example 8 the process is carried out the method prototype obtain macrocyclic polyethers, content and yield of cyclic products, about 90%, However, these products do not contain functional groups.

The above examples show that this method for the synthesis of macrocyclic polyethers universal for the class of 1,2-oxirane. In all cases, the process according to the invention, leads to brasota showed no functional groups, not contained in the structure of the monomer. Compared with the prototype of the proposed method obtained macrocyclic polyethers based replaced by oxiranes with a specified molecular weight distribution, namely the molecular cycles n=4-9 and macromolecular cycles n 11.

The yield of the target product is 955% when the content of cycles with functional groups 955% that cannot be obtained by the method prototype (examples 6, 8).

1. A method of OBTAINING a MACROCYCLIC POLYESTER cationic polymerization of oxirane in an environment of dry organic solvent and an atmosphere of dry inert gas at 0, 20oIn the presence of a catalyst complex compounds of boron, characterized in that as oxirane use of substituted alpha-oxide, selected from the group comprising epichlorohydrin, nitrate pilgramage alcohol or propylene oxide, as well as complex compounds of boron tetrahydrofuranate boron TRIFLUORIDE.

2. The method according to p. 1, wherein the organic solvent is used as a compound with a basicity lower basicity of substituted alpha-oxide.

3. The method according to p. 1, wherein as the organic

 

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