The method of obtaining the (co)polymers 1,1,2-tripersonality-1,3


C08F36/16 - containing halogen

 

(57) Abstract:

Usage: obtain polymers based on 1,1,2-tripersonality-1,3. The inventive copolymers 1,1,2-tripersonality-1,3 with other monomers receive water-emulsion polymerization in the presence of emulsifier and initiator, and the initiator used complexes of alkylate (III) tridentate ligands alkyl{2-[(2-amino-ethyl)imino] -3-alkyl-Penta-3-EN-4-OST} (1,2-amandemen) cobalt (III) halides, where alkyl is a C1-C16the alkyl, alkyl is H1C2H5THE H7H15the halogen is iodine or bromine in the amount of 0.04 to 0.3 wt.h. on 100 wt.h. monomers, and the polymerization process is carried out at a temperature of 20oC and pH 3.5-7. 3 table.

The invention relates to the field of production of fluorinated polymers. Fluorinated polymers are widely used in various fields due to its thermal and hemosense, and resistance to climatic factors and high physical strength.

A method of obtaining copolymers 1,1,3-triptorelin (TSE) with other fluorinated danami method, emulsion, suspension and block polymerization in PR and within from 14 to 41 hours [1]

The closest in technical essence and the achieved result to the claimed technical solution is a method of producing copolymers of 1,1,2-tripersonality-1,3 method of emulsion polymerization in the presence of emulsifier and initiator, which represents a redox system [2] the disadvantages of the method include carrying out the process at elevated temperatures (25-50oC) and pressure.

An object of the invention is to reduce the temperature of the process, reducing its duration and carrying out the process at atmospheric pressure.

This result is achieved in that in the production method of (co)polymers 1,1,2-tripersonality-1,3-water emulsion polymerization 1,1,2-cryptosporidia and second co monomer in the presence of emulsifier and initiator as an initiator using the complexes of alkylate (III ) tridentate ligands of the General formula:

< / BR>
where R is alkyl containing C1-C16, R' H, C2H5the h7H15X 1, Br in the amount of 0.04 to 0.3 wt. hours at 100 wt.h. monomers, and the polymerization process is carried out at a temperature of 1-20oC and pH 3.5-7.

Comparative analysis with prototype called the new type of initiator complexes alkylate with tridentate ligands. Thus, the claimed technical solution meets the criterion of "novelty."

Analysis of the known technical solutions [1, 2] showed that the use of complexes of alkylate (III) tridentate ligands as initiators of water-emulsion polymerization allows to lower the temperature and pressure of the process, and to shorten the reaction time. Thus, the claimed technical solution meets the criterion of "inventive step".

These complexes - alkyl{2-[(2-amino-ethyl)imino]-3-alkylen-3-EN-4-OST} (1,2-amandemen)cobalt(III)halides (symbolic formula [RCo(3-R'-assep)(en)]X); a special case (R'= H) - alkyl-{2-[(2-amino-ethyl)imino]Penta-3-EN-4-OST} (1,2-amandemen)cobalt(III)halides ([RCo(acacen)(en)] X first synthesized by the authors according to the following method.

The synthesis is carried out in an argon atmosphere at a temperature of 15-25oWith constant stirring. In the reactor sequentially injected 430 ml of methanol, 12,C ml (120 mmol) of acetylacetone, 10.3 ml of a 70% aqueous solution of ethylene diamine (120 mmol), 14.1 g (60 mmol) douglasthe 6-water cobalt, 19,C ml of 50% aqueous solution Paon, 1 ml of 2% aqueous solution of PdCl2in 1M aqueous KCl solution, 21 ml (273 mmole) of ethylbromide. Is the termination of the gas evolution, the reaction mixture is stirred for 1 hour. Then it is filtered, the solution is evaporated to a volume of 100 ml at a residual pressure of 10-20 mm RT.article and the bath temperature not exceeding 40oC. Then add 20 g of NaBr and, when cooled, 100 ml of water, and the mixture evaporated in the same way up to a volume of 100 ml Crystallization was carried out at 0oC, the precipitate is filtered off, washed with 15 ml of ice-cold water and dried in air. Then it is washed with dichloromethane, portions (a total of 150-200 ml), until the disappearance of the green color wash liquid. Then dried the product on the air. The target product is a crystalline powder of red. If necessary, conduct a recrystallization from methanol with the addition of sodium bromide. To identify the use of ion-exchange TLC on SiO2(plate Silufol, eluent of 0.1 n sodium acetate solution in methanol-water 4:1 by volume). The purity criteria is the presence of one of the spots on the plate, and the almost complete decolorization of the solution of the complex adding hydrochloric acid. Output and the value of the separation factor Rfshown in table 1.

During the synthesis of the complexes listed in table 1, use the following halide alkali: methyliodide, ethylbromide, n-butylbromide, Isopropylamine, n-milbrae, n is alprostadi.

The structure of the complexes prove, on the basis of data1H-NMR, IR spectra and analysis products acidolysis. Spectra1H-NMR (solvent D2About or SD3OD, 200 MHz, internal standard sodium 2,2-dimethyl-2-silapentane-5-sulfonate) of the synthesized complexes alkylate similar to each other. Data for complex 2 (PL. 1) in the D2The following information (identified signal , memorial plaques multipletness): CH3CH2With, 0,60, t; CH3-C=N, 1,70, S; CH3-CO, 1,94, S; CH, 4,98, S. IR spectra of the complexes 1-11 have characteristic absorption bands in the region 3100-3260 cm-1(wide) and 3280-3350 cm-1(narrow), related to the stretching vibrations of N-h

Analysis of the products of acidalia synthesized complexes 1-11, were performed using gas-liquid and thin-layer chromatography, confirms the above structural formula. The structure of complexes was also confirmed by elemental analysis data (table. 2).

Complexes 1-11 in the solid state is stable in the dark and safe storage.

Example 1 (invention). In the reactor with stirrer mix 100 wt.h. TSE with an aqueous phase comprising 4 wt.h. alkylsulfonate Na (E-ZO) with the length of alkyl substituent WITH15, 0.1 wt.h. the INIC is ur +1oWith over 45 hours. The atmospheric pressure, pH 5, the conversion of monomer 58%

Example 2. In the reactor with stirrer mixing 75 wt.h. TSE and 25 wt.h. isoprene with an aqueous phase comprising C wt.h. E-ZO, of 0.04 wt.h. initiator complex N 2 (PL. 1), 0.1 wt.h. PA2NRA4, 1.7 wt.h. KH2PO4to maintain pH and 200 wt.h. water. The process is carried out under stirring in nitrogen atmosphere at atmospheric pressure and a temperature of 3oC for 5.5 hours. pH of 5.5, the conversion of monomers 76%

Examples 3-6. Perform analogously to example 2, with the change of the type of co monomer, temperature, medium pH, type of emulsifier, the concentration of the ingredients, the presence of buffer compounds, complexes of alkylate (W) with tridentate ligands with different structures. Since all processes copolymerization is carried out in a sealed reactor, while the temperature is raised to 20oWith excess pressure in the apparatus does not exceed C ATI.

Example 7 (prototype). In an autoclave with stirrer mixing 50 wt.h. TSE and 50 wt. hours of performativen-1,3 with an aqueous phase comprising 1 wt.h. initiator K2S2O8, 2 wt.h. emulsifier - Cl(CF2CFCI)3CF2COOK and 200 wt.h. water. The process is carried out with stirring, the polymerization Recipes and process parameters as well as some properties of the (co)polymers are shown in table 3.

In recipes copolymerization can be used monomers of different nature diene hydrocarbons, acrylic esters, chloroprene, Acrylonitrile, and fluorinated diene and vinyl monomers. As emulsifiers can be used anion active (E-30), kationaktivnaya (pyridinium chloride) and fluorinated surfactants, such as salts performancewas and preferredlanguage acids. To obtain unstitched copolymers should be applied to 0,C wt.h. regulators molecular weight type of mercaptans.

Lowering the process temperature is below the 1oSince it is impractical, because it leads to freezing of the aqueous phase. The increase in temperature above 20oWith the will require increased pressure in the reactor.

The use of initiator concentration less than 0.04 wt.h. slows down the polymerization. The increase in initiator concentration more than 0.3 wt.h. does not increase the speed of the process.

Homolytic decomposition of complexes of alkylate occurs under the action of a proton. Therefore, in alkaline medium (pH > 7) stable complexes and polymerization is hardly taking place. At pH <3,5 observed violation stabiles who is conducting the polymerization at a pH of 3.5-7.

Are given in table. 3 evidence suggests that the use of the synthesized complexes alkylate (III) tridentate ligands allows the process of emulsion (co)polymerization of triptorelin with other monomers at low temperatures with high speeds.

Literature

1. Patent Germany N 1089973, class C 07 C, publ. 6.04.61.

2. U.S. patent N 3398128, class C 07 C, publ. 20.08.68. TTT

The method of obtaining the (co)polymers 1,1,2-tripersonality-1,3 - water-emulsion polymerization 1,1,2-cryptosporidia and second co monomer in the presence of emulsifier and initiator, characterized in that as the initiator of the use complexes alkylate (III) tridentate ligands of General formula:

< / BR>
where R is alkyl containing C1-C16;

R' IS H, C2H5n-C7H15;

X I, Br in the amount of 0.04 to 0.3 wt.h. on 100 wt.h. /with/ monomers,

and the polymerization is carried out at a temperature of 1-20oC and pH 3.5-7.

 

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