Complexes of alkylate (iii) tridentate ligands as initiators of water-emulsion polymerization and copolymerization of vinyl and diene monomers

 

(57) Abstract:

Usage: in synthesis of polymers. Product:

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[RCo(3-R'-aCasa((en)] X, where R is alkyl containing C1- C16, R' = H, C2H5n - C7H15X = J, Br. The output 44 of 66%. Reagent 1: acetylacetone in methanol. Reagent 2: aqueous solution of Ethylenediamine. Reagent 3: duplissy 6 - water cobalt. Reagent 4: ethylbromide. 3 table.

The invention relates to complex compounds of alkylate (III) tridentate ligands, which can be used as initiators for emulsion polymerization of vinyl and diene monomers.

Known ORGANOMETALLIC complexes of cobalt General formula K3Co(CN)5-C3H5and K3Co(CN)5-CH2C6H5used to initiate emulsion polymerization of isoprene and butadiene (1). However, these compounds have low efficiency of initiation: to achieve the conversion of butadiene 82% at 40oC requires 44 hours.

There are other more effective initiating system for emulsion polymerization, for example, the redox system (ROS). So, know the use of allied hydroperoxide ilen rubber (2). The disadvantages of this and similar initiating systems can be attributed to the complexity, which involves conducting a significant number of operations on the preparation and dosage of the ingredients of the allied forces. In addition, the command includes peroxide and hydroperoxide compounds that are explosive and Euroopassa during storage.

The aim of the invention is to obtain ORGANOMETALLIC complexes of cobalt, suitable for use as initiators for emulsion polymerization and copolymerization of vinyl and diene moments.

This goal is achieved by the new structure of the complexes of alkylate (III) tridentate ligands of the General formula:

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where R first - or second-alkyl from C1to C16, R' is H or alkyl (C2H5n-C7H15and X VG, J.

Comparative analysis with analogues leads to the conclusion that the authors synthesized a series of alkylate new structure. Thus, the proposed solution meets the criterion of "novelty".

These complexes - alkyl{2-[(2-amino-ethyl)imino]-3-alkyl-Penta-3-EN-4-OST} (1,2-amandemen)cobalt(III)halides (symbolic formula [RCo(3-R'-assep)(EP)] X); cha for the first time synthesized by the authors according to the following method.

Example 1 complex 2 (PL. 1). Synthesis of lead in the atmosphere of argon at a temperature of 15 25oC with constant stirring. In the reactor sequentially injected 430 ml of methanol, to 12.3 ml (120 mmol) of acetylacetone, 10.3 ml of a 70% aqueous solution of ethylene diamine (120 mmol), 14.1 g (60 mmol) dvuhgolosnogo 6-water cobalt, and 19.3 ml of 50% aqueous NaOH solution, 1 ml of 2% aqueous solution of PdCl2a 1 M aqueous solution Cl, 21 ml (273 mmole) of ethylbromide. Uniformly added dropwise a solution of 3.2 g NaBH4(85 mmol) and 25 ml of 5% aqueous NaOH solution for 5 hours. After 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 mm RT. Art. and the bath temperature not exceeding 40oC. Then add 20 g of NaBr and upon cooling, 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 (150 to 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 of crystallis is stinky Silufol, eluent of 0.1 n solution of sodium acetate in a mixture of methanol water 4 1 by volume). The purity criteria is the presence of one of the spots on the plate, and the almost complete bleaching of the complex adding hydrochloric acid. Output and the value of the separation factor Rf is given in table. 1.

Examples 1, 3 11. Complexes 1 and 3 of the 9 listed in table. 1, get analogously to example 1 with the difference that instead of ethylbromide use the following halide alkali: methyliodide, n-butylbromide, n-milbrae, n-activated, n-celibrated, ISO-propyl bromide, cyclohexylamine, second-activated. Complexes 10 and 11 receive, instead of using acetylacetone 3-ethyl - 3 n heptylphenol respectively.

The structure of the complexes proved on the basis of data1H-NMR, IR spectra and analysis products acidolysis. Spectra1H-NMR (solvent D2O, 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) below (identifiably signal , memorial plaques multipletness): CH3CH2Co., 0,60, t; CH3-C=N, 1,70, s; CH3-C=0, 1,94, s;SN, 4,98, s, IR spectra of complexes 1 11 have characteristic absorption bands in obelis products acidolysis synthesized complexes 1 11, were performed using gas-liquid and thin-layer chromatography, confirms the above structural formula. The structure of the complexes was confirmed also by the data of elemental analysis (table. 2).

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

Examples of complexes of alkylate as initiators for emulsion polymerization are shown in table. 3.

Are given in table. 3 evidence suggests that the synthesized complexes alkylate new patterns are an effective low-temperature initiators for emulsion polymerization of diene and vinyl monomers.

Complexes of alkylate (III) tridentate ligands of General formula

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where R is C1C16-alkyl;

R1H, C2H5H-C7H15;

X J, Br,

as the initiators of water-emulsion polymerization and copolymerization of vinyl and diene monomers.

 

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FIELD: organic chemistry.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazine of the general formula (I): wherein M means Cu, Co. These compounds can be used as dyes, catalysts in different processes and materials of sensitive members of gas sensor.

EFFECT: valuable properties of compounds.

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FIELD: chemistry of metalloorganic compounds.

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wherein M means Cu, Co. These compounds can be used as dyes, catalysts of different processes and material for sensitive members of gas pickups.

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4 fig, 1 dwg, 5 ex

FIELD: organometallic polymerization catalysts.

SUBSTANCE: invention relates to alkylcobalt(III) complexes with tridentate Schiff's bases wherein alkyl ligand contains functional group, notably hydroxyl, carboxyl, or amino group, in accordance with general formula:

(I),

in which W represents two-moiety unsaturated hydrocarbon bridge group expressed by formula =C(H)=C(CH3)- (propene-1,2-diyl) or o-C6H4 (o-phenylene); X is OH, NH2 or COONa; Y monovalent anion: Cl-, Br-, NO3- or ClO4-; and Z polymethylene bridge group (CH2)n, wherein n=3-11 when X = OH or NH2 and n=2-11 when X = COONa. The complex are used as initiators of emulsion polymerization and copolymerization of diene and vinyl monomers to produce reactive bifunctional oligomers and polymers with terminal functions, which oligomers and polymers are suitable for further conjugation with corresponding reagents.

EFFECT: extended choice of specific polymerization catalysts.

3 tbl, 30 ex

FIELD: organic chemistry, polymers.

SUBSTANCE: invention relates to low-branched high-molecular polyvinyl acetate, methods for its preparing and to polyvinyl alcohol prepared on its base. Invention describes low-branched high-molecular polyvinyl acetate prepared by aqueous-emulsion polymerization of vinyl acetate in the presence of emulsifier and initiating agent wherein complexes of alkylcobalt (III) with tridentate ligands of the general formula (I) are used as an initiating agent taken in the amount 0.04-0.2 mas. p., and the polymerization process is carried out at temperature 10-40°C. Polyvinyl acetate prepared by this method has molecular mass 850000 Da, not less, and degree of branching 0.39-0.7. Polyvinyl alcohol with the polymerization degree 6000 Da, not less, and the saponification degree 98-99.9% that is able for making high-module fibers is prepared by saponification of indicated low-branched polyvinyl acetate.

EFFECT: improved preparing method, valuable properties of product.

3 cl, 3 tbl, 10 ex

FIELD: organic chemistry.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazine of the formula (I): . These compounds can be used as dyes, catalysts in different processes and the material in sensitive members of gas transducers. Invention provides synthesis of compounds showing dyeing properties.

EFFECT: valuable properties of compounds.

5 dwg, 4 ex

FIELD: organic chemistry of complex compounds.

SUBSTANCE: invention relates to novel derivatives of metalloporphyrazine of the formula (I) that can be used as dyes, catalysts in different processes. Invention provides preparing compounds possessing with coloring properties.

EFFECT: valuable properties of complexes.

5 dwg, 4 ex

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