The method of obtaining polyalkyl(meth)acrylate

 

(57) Abstract:

Usage: polymers for the production of nonwovens, film-forming substances and modifiers of polymer materials. The essence: gaining polyalkyl(meth)acrylates by emulsion polymerization of alkyl(meth)acrylates in the presence of a catalyst complexes of alkylate (III) tridentate ligands - alkyl{2-[(2-amino-ethyl)imino-]-3-alkyl-Penta-3-EN-4-OST}(1,2-amandemen)cobalt (III) halide in an amount of 0.04 to 0.3 wt. hours at 100 wt.h. monomer, the process is carried out at 8-30oC and pH 3.5-7. 3 table.

The invention relates to the field of polymers based on esters of acrylic and methacrylic acids.

Acrylic latexes are widely used as non-woven materials, film-forming substances and modifiers of other polymers, for example polyvinyl chloride. Physico-mechanical properties of polyacrylates, including the strength of the coatings on their basis, the higher, the higher molecular weight polymers.

A method of obtaining acrylic copolymers by suspension polymerization in the presence as an emulsifier Poslednij N-alkylpyridine [1] However, in this case, the process is carried out at tempera is of polymethylmethacrylate (PMMA) suspension polymerization in the presence of a stabilizer sodium salt of a copolymer of methacrylic acid with methyl methacrylate [2] However, this method has the same disadvantages.

The closest in technical essence and the achieved result to the claimed technical solution is a method for PMMA emulsion polymerization in the presence of an emulsifier and a radical initiator is potassium persulfate [3] the disadvantages of the method include the inability to obtain ultra-high molecular weight polymer and a high temperature polymerization (60-70oC).

An object of the invention are to increase the molecular weight of polyacrylates and lowering the process temperature.

This technical result is achieved in that in the method of obtaining polyalkyl(meth)acrylate water-emulsion polymerization of alkyl(meth)acrylates 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, C2H5n-C7H15X 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 8-30oC and pH 3.5-7.

Comparative analysis of the prototype allows us to conclude that when carrying out emulsion polymerization of alkyl(meth)acrylates iesca solutions [1-3] showed the use of complexes of alkylate (III) tridentate ligands as initiators of water-emulsion polymerization allows to lower the temperature of the process and increase the molecular weight of the polymer. These complexes - alkyl{2-[(2-amino-ethyl)imino] -3-alkyl-3-EN-4-OST} (1,2-amandemen)cobalt (III) halides (symbolic formula [RCo(3-R'-acacen)(en)]X); a special case (R'= H) alkyl-[(2-amino-ethyl)imino]Penta-3-EN-4-OST}(1,2-amandemen)cobalt (III) halides ([RCo(acacen)(en)]X for the first time synthesized by the following method.

The synthesis is carried out in an argon atmosphere 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) douglasthe setevogo cobalt, and 19.3 ml of 50% aqueous NaOH solution, 1 ml of 2% aqueous solution of PdCl2in 1M aqueous KCl solution, 21 ml (273 mmole) of ethylbromide. Uniformly added dropwise a solution of 3.2 g NaBH4(85 mmol) in 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 10-20 mm R is 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-activated, n-celibrated, cyclohexylamine, Deut. activated, as well as acetylacetone or 3-ethyl and 3-n-heptylphenol.

The structure of the complexes prove, on the basis of data1N-Yarm, IR spectra and analysis products acetyl-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): 0,60, t; CH3-C= N, 1,70,S; CH3-CO, 1,94,S;CH, 4,98, S. IR spectra of complexes I-II 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 I-II, conducted by the methods of 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 I-II in the solid state is stable in the dark and safe storage.

Example 1 (invention). In the reactor with stirrer mix 100 wt.h. of methyl methacrylate with an aqueous phase comprising 4 wt.h. alkylsulfonate Na (E-30) with the length of alkyl substituent C15, 0.1 wt.h. initiator complex N 1 (PL. 1) and 200 wt.h. water. The process is carried out under stirring in nitrogen atmosphere at a temperature of 20oC for 60 minutes prior to the conversion of 94% pH environment 7.

Examples 2-11. Perform analogously to example 1, with the change-type (meth)acrylate, temperature, pH of the medium, the type of emulsifier, the concentration ingredientsyou patterns.

Example 12 (prototype). In the reactor with stirrer mix 100 wt.h. of methyl methacrylate with an aqueous phase containing 1% initiator - K2S2O8, 2 wt.h. emulsifier E-30 and 200 wt.h. water. The process is carried out in nitrogen atmosphere for 45 minutes prior to the conversion of 88% the pH of the medium 7. The polymerization recipes and process parameters, as well as some properties of the (co)polymers (characteristic viscosity) are shown in table 3.

It should be noted that in all the examples according to the invention the conversion is 88 - 97%

In polymerization recipes use the acrylates and methacrylates with long alkyl radical C1-C8, as well as acrylic and methacrylic acid. As emulsifiers used surfactants of different nature: the anion active alkylsulfonate Na, E-30, C15H31SO3Na, nonionic ethoxylated citylove alcohols, C-20, C16H33(OCH2CH2)20OH, kationaktivnaya - pyridinium chloride, CP, C21H38ClN. Can be used regulators pH environment.

Are given in table. 3 evidence suggests that the use of the synthesized complexes alkylate (III) tridentate ligands allows the process emulsion in Addition, formed polymer with very high molecular weight (characteristic viscosity), which allows to improve the strength properties of materials, manufactured on its basis. TTT

The method of obtaining polyalkyl(meth)acrylate-water emulsion (co)polymerization of alkyl(meth)acrylates 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 FROM1-C16;

R' IS H, C2H5H-C7H15;

X I, Br,

in the amount of 0.04 to 0.3 wt. hours at 100 wt. h (co)monomers and the polymerization process is carried out at a temperature of 8 30oC and pH 3.5 7.

 

Same patents:

The invention relates to the field of production of fluorinated polymers

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.

2 cl, 6 sch, 1 dwg, 5 ex

FIELD: chemistry of metalloorganic compounds.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazines of the general formula (I):

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

EFFECT: valuable properties of complexes.

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

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of platinum metal salts, in particular, palladium salts, namely, palladium (II) acetate. Method for synthesis of palladium (II) acetate involves dissolving metallic palladium in concentrated nitric acid, filtering and evaporation of palladium nitrate solution, its treatment with glacial acetic acid, filtration of formed sediment and its treatment with acetic acid ethyl ester and glacial acetic acid for its conversion to palladium (II) acetate followed by heating the prepared suspension for 6 h. Method provides preparing palladium (II) acetate with high yield in monophase state and without impurities of insoluble polymeric palladium (II) acetate.

EFFECT: improved method of synthesis.

3 cl, 2 tbl, 21 ex

FIELD: chemistry of metalloorganic compounds, chemical technology.

SUBSTANCE: invention relates to an improved method for synthesis of octa-4,5-carboxyphthalocyanine cobalt sodium salt, or 2,3,9,10,16,17,23,24-octacarboxylic acid of phthalocyanine cobalt (terephthal) of the formula (I) . Terephthal is a synthetic preparation used in catalytic ("dark") therapy of cancer based on generation of oxygen reactive species in tumor directly by chemical manner and in combination with ascorbic acid being without using the physical effect. Method for preparing octa-4,5-carboxyphthalocyanine cobalt sodium salt involves melting pyromellitic acid dianhydride with cobalt salt in the presence of urea followed by alkaline hydrolysis of prepared octa-4,5-carboxyphthalcyanine cobalt tetraimide. Salt formed after hydrolysis is purified from impurities, in particularly, from oligomeric compounds by column chromatography method on aluminum oxide, following precipitation of octacarboxylic acid, its, its washing out, concentrating and purifying from residual inorganic salts by washing out with distilled water and by neutralization with sodium hydroxide aqueous solution also, treatment with apyrogenic activated carbon, filtration and drying the end substance. Purification of octa-4,5-carboxyphthalocyanine cobalt from residual inorganic salt is carried out preferably by electrodialysis method after its partial neutralization to pH 5.2-5.5 at current density 0.15-0.25 A/dm2, temperature 20-35°C and the concentration 1.5-3.0% followed by complete neutralization to pH 8.7, treatment of obtained octacarboxy-PcCo salt solution with activated carbon, filtration and drying filtrate in a spray drier. Proposed method provides preparing octa-4,5-carbocyphthalocyanine cobalt salt of high purity degree and free of oligomeric compounds and residual chlorides.

EFFECT: improved method of synthesis.

5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to tetra-(5-acetylamino-7-hydroxy)anthraquinonoporphyrazines of copper and cobalt of formula

.

EFFECT: compounds can be used as dyes and catalysts.

4 ex, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to tetra-(5-acetylamino-7-heptyloxy)anthraquinonoporphyrazines of copper and cobalt of formula .

EFFECT: obtained compounds can be used as dyes and catalysts.

4 ex, 5 dwg,

FIELD: polymer materials.

SUBSTANCE: sheet organic glass is obtained by way of bulk (co)polymerization of (meth)acrylic acid esters in presence of UV absorber, radical polymerization initiator, and light-absorbing additive. Process involves monomer prepolymerization and subsequent final polymerization if mixture in flat-parallel mold. Methacrylic acid esters utilized are, in particular, methyl methacrylate or its mixtures with (meth)acrylic acid or (meth)acrylic acid esters. Light-absorbing additive is methane decomposition product obtained in high-voltage discharge plasma at atmospheric pressure and characterized by loose density 0.65-0.85 g/cm3 and specific pore volume 0.40-0.50 cm/cm3. Additive, taken in amount 0.001-0.01 wt parts per 100 wt parts monomer, is mixed with prepolymer. Resulting mixture is affected by ultrasound and then polymerized in mold until conversion is completed. Sheets manufactured according to invention are suitable for neutral light filters employed in instrumentation engineering, in personal protection devices, and in sporting airplane glazing operations.

EFFECT: improved optical characteristics of glass due to more uniform light transmission in visible spectrum region.

1 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: there is disclosed method of producing polymethyl methacrylate by polymerisation of methyl methacrylate with geminate bishydroperoxides added at higher temperature. Compared to the prototype, the disclosed method required fewer timetable and initiator amount.

EFFECT: developed method of producing polymethyl methacrylate with using technically available initiators.

1 cl, 1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a film which is resistant to adverse weather conditions for colouring reflective moulded articles yellow, e.g. road signs. The film has a polymethylmethacrylate (PMMA) layer coloured by a yellow anthraquinone dye containing (made from) moulding material. The moulding material consists of A) 10-90 wt % bonded solid phase with glass transition point over 70°C, containing a) 80-100 wt % (from A) methylmethacrylate and b) 20-0 wt % lower alkylacrylate, and B) 90-10 wt % viscous phase distributed in the solid phase with glass transition point below -10°C, average particle size of the viscous phase less than 130 nm and particle size inhomogeneity of the viscous phase less than 0.5. The viscous phase contains c) at least 50 wt % (from B) lower alkylacrylate, d) 0.5-5 wt % crosslinking monomer with three or more ethylene-unsaturated radically polymerisable residues. The cloured polymethylmethacrylate layer conforms to chromaticity coordinates (x; y) on the 1931 CIE standard colorimetric system preferably in the interval 0.4 ≤ x ≤ 0.54 and 0.44 ≤ y ≤ 0.54.

EFFECT: obtained film has higher weather resistance, excellent optical properties and is easy to manufacture.

13 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: method of producing monodispersed carboxylated polymer microspheres in form of an aqueous suspension is characterised by that a solution in a vinyl monomer of a surfactant - α,ω-bis-(10-carboxydecyl)polydimethylsiloxane, containing from 6 to 60 siloxane links and taken in amount of 0.5-1.9%, or mixture thereof with polyoxyalkylene polysiloxane of formula , where m=8-64, n=4-8, p=15-20, q=15-20, in amount of 0.9-2.6% of the weight of the monomer, is intensely stirred in bidistilled water in the atmosphere of inert gas while heating the mixture to 50-75°C and volume ratio of monomer to water in the range of 1:(2-9), with preliminary addition into the reaction mass of 0.8-1.3% (of the weight of the monomer) radical polymerisation initiators - mixture of potassium persulphate and dinitrile of azo-bis-isobutyric acid or benzoyl peroxide, to form an oil-in-water emulsion, followed by polymerisation for 2-5 hours under the action of the initiator of a drop of the monomer to polymer particles, while raising temperature by 10°C per hour until the end of the process.

EFFECT: method of producing monodispersed carboxylated polymer microspheres with concentration of carboxyl groups on the surface of the microspheres, which meets requirements for immunoreagent carriers; the suspension is stable in physiological solutions.

1 cl, 5 dwg, 11 ex

FIELD: chemistry.

SUBSTANCE: group of inventions relates to chemical engineering, particularly to methods of producing polyalkyl methacrylate additives for oil and oil products, paint compositions and adhesives with permanent tackiness. The method of producing polyalkyl methacrylate additives involves continuous production of alkyl methacrylates by re-esterification of methyl methacrylate with higher fatty alcohols in the presence of a catalyst and an inhibitor, followed by polymerisation of the obtained alkyl methacrylates in base oil. To obtain alkyl methacrylates, methyl methacrylate is inhibited and then mixed with a molten fraction of higher fatty alcohols in molar ratio 2-2.5:1 at temperature 65-70°. The obtained mixture is re-esterified in the presence of a heterogeneous catalyst to obtain alkyl methacrylates with simultaneous fractionation of the formed methanol in form of an azeotrope with methyl methacrylate. The obtained alkyl methacrylates are purified from residual methyl methacrylate and methanol by film evaporation. Methanol vapour and methyl methacrylate formed during re-esterification and film evaporation are cooled. The condensate obtained from cooling is mixed with ethylene glycol in order to dissolve methanol in it, with subsequent phase separation of the mixture into methyl methacrylate and ethylene glycol with dissolved methanol, after which methanol is separated from ethylene glycol and used as a ready product. Ethylene glycol is returned to the step for mixing with the condensate and methyl methacrylate is returned to the inhibiting step. To polymerise the purified alkyl methacrylates, a mixture of alkyl methacrylates and base oil is first prepared while stirring continuously at temperature 115-120°C. A suspension of a foaming agent in base oil is separately prepared and then continuously added to the hot reaction mixture for a period of time which enables polymerisation of alkyl methacrylates at temperature 115-120°C. After adding the foaming agent to the base oil, stirring of the reaction mixture continues until complete conversion of alkyl methacrylates to polymer to obtain a polymerisation product which is diluted with base oil to obtain polyalkyl methacrylate additives of given concentration. An apparatus for producing polyalkyl methacrylate additives is also disclosed.

EFFECT: obtained additives have high solubility in petroleum and synthetic oil, low volatility, non-toxicity, do not form ash when burnt and provide a high viscosity index and a low setting point of oil; also provided is a wasteless continuous technique for producing additives by continuous synthesis of alkyl methacrylates with extraction of an additional product - methanol, and polymerisation of alkyl methacrylates in base oil.

10 cl, 1 tbl, 1 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to fluorine-containing acrylic acid esters, in particular to a novel monomer - (perfluoro-2-trichloromethylisopropyl)acrylate, and polymer made therefrom - (perfluoro-2-trichloromethylisopropyl)acrylate, which can be most effectively used for making light-conducting strands and coatings of optical waveguides. Monomer (I) is obtained from hexafluoroacetone and acryloyl chloride. Reaction of hexafluoroacetone with sodium trichloroacetate in dimethyl formamide produces 1,1,1-trichloro-3,3,3-trifluoro-2-(trifluoromethyl)propan-2-ol, acylation of which in presence of triethylamine in a medium of acetonitrile yields desired perfluoro-2-trichloromethylisopropylacrylate with output of 75 %, wherein purity of produced monomer is 99.9 %.

EFFECT: polymer is obtained through radical polymerisation of said monomer in presence of a polymerisation initiator.

5 cl, 1 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: polymer can be used in the development of water quality and air quality control devices, where extraction and optical analysis methods are used. The method of producing polymethyl methacrylate is carried out by radical polymerization in a mass of methyl methacrylate in the presence of an initiating system, one of the components of which is benzoyl peroxide. The method is characterised in that calcium methacrylate is used as the second component of the initiating system, polyethylene glycol (PEG 400) is used as a plasticiser with a percentage of benzoyl peroxide: calcium methacrylate: polyethylene glycol (PEG 400) - (0.03):(0.5):(4÷1), the polymerization is carried out at 60-90°C.

EFFECT: production of a polymer material for solid-phase extraction with improved characteristics by the extraction ability of the polymer.

6 tbl, 6 ex

Up!