Method of producing monodispersed carboxylated polymer microspheres

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

 

The present invention relates to the field of macromolecular compounds, namely a method for producing monodisperse carboxylating polymeric microspheres, including latex, which can be used in biochemistry and medicine, in particular, for the creation of immunodiagnostics test systems.

Up to this time had developed a method of obtaining a polymer suspension containing carboxyl groups on the surface of particles, the method bisimulations copolymerization of styrene with methacrylic, acrylic, taconova acids (USP. 1991, CH, No. 2, str-429). The obtained latex was proposed to use as a media immunoreagents.

However, copolymerization of carboxyl group was distributed not only on the surface of the microspheres, but also in the amount that reduced the efficiency of immunochemical reactions. The elimination of this disadvantage demanded gradual addition of methacrylic acid in a reaction that, in turn, adversely affect the reproducibility of the results.

Known RF patent 2164919 1998, protecting the way of polymeric suspensions with carboxypropanoyl the surface of the particles by the method bisimulations polymerization of the vinyl monomer, of one or a mixture, in aqueous-alkaline medium in the presence of a carboxyl-containing initiator 4,4'-azo-bis-(4-cianfarano is Oh) acid (CEC). In the initial reaction mixture is additionally injected salt or mixtures thereof, contributing to the formation of the buffer solutions in the field of alkaline pH values at concentrations of 0.005-0,150 M calculated on the aqueous phase. The main objective of the invention is obtaining monodisperse polymer latex for use as a carrier of immunoreagents.

The latex obtained this way, contained polymer karboksilirovanie microspheres, however, the concentration of carboxyl groups on the surface was difficult to adjust because of the disordered orientation of end groups of the polymer. It should be noted the high cost of the Fairgrounds.

In Polish patent No. 162445 and No. 162446, published in the early 90-ies of XX century, protected methods of obtaining monodisperse polystyrene suspensions in the presence of the water-insoluble surfactant - di-n-tolyl-o-carbalkoxy-carbinol (DTK). The disadvantage of the method is the formation of stable suspensions of polystyrene is possible only with a very limited correlation of phases, which narrows the range of diameters of the obtained microspheres.

The use of organosilicon compounds, in particular water-insoluble oligodimetilsiloksana with one end carboxyaniline group, as surface-active stabilizer to obtain a stable polystyrene suspension refers to the beginning of the Lu 90-ies of XX century (Reports of the Academy of Sciences, 1994, t, No.1, p.57-59). According to the process described oligomer is dissolved in styrene and mix the solution with water with the formation of a direct emulsion. When initiating polymerization of styrene, for example, hydropredict of cumene get a stable suspension of the polymer, the dispersed particles which have a spherical shape, narrow distribution of particle sizes in the early stages of polymerization and almost not coagulated. The stability of the suspension is achieved by the formation of strong interfacial layer of molecules formed of polystyrene and silicone oligomer. However, synthesis of this surfactant as one of the reagents used substance, the technology of which is quite complex and requires the use of metallic sodium.

In 2010, published article in the journal "Molecular compound", series B, volume 52, No. 9, str-1695, with a description of the method of synthesis of polystyrene suspensions in the presence of water-soluble α,ω-bis-(10-carboxyethyl)-polydimethylsiloxane, containing 30 siloxane units, under the action of a radical initiator by heating to 80°C. the ratio of the dispersion and aqueous phase ranged from 1:2 to 1:9.

This method does not allow to regulate the concentration of carboxylic groups at a given diameter Polist the roller particles, and the maximum conversion of monomer 5 hours does not exceed 85% (see figure 2, 4). In addition, when a high ratio of monomer to water is 1:(2-4) observed the formation of coagulum.

The task of the invention is to develop an effective method of obtaining monodisperse functional microspheres adjustable diameter without the above disadvantages.

As a result of scientific research developed easy way of obtaining monodisperse carboxylating polymer microspheres based on vinyl monomers of methyl methacrylate (MMA), n-butyl acrylate, styrene, vinyl acetate and chloroprene). The process is carried out in the presence of the water-insoluble surfactant - α,ω-bis-(10-carboxyethyl)polydimethylsiloxane with a number of siloxane units from 6 to 60 or its mixture with polyoxoalkyleneamine formula

(where m=8-64, n=4-8, p=15-20, q=15-20)

when the content of the surfactant or mixture, respectively, of 0.5 to 1.9 and 0.9% to 2.6% by weight of the monomer and the volume ratio of the dispersed phase to bidistilled water 1:(2-9). The surfactant or mixture is dissolved in the monomer. The method is carried out under the action of a radical initiator, a mixture of potassium persulfate with dinitriles azo-bis-somaclonal acid or benzoyl peroxide in a quantity of 0.8 to 1.3% by weight of monomer in the atmosphere of inert gas while heating up to 50-75°C, intense the nom stirring with the formation of a direct emulsion, followed by polymerization for 2-5 hours under the action of the initiator drops of monomer in the polymer particles when the temperature increases by 10°C per hour until the end of the process to achieve complete conversion of the monomer. Get a stable suspension of polymeric microspheres with a diameter of 0.13-0.65 micron and a narrow distribution of particle size (coefficient of dispersion (Dw/Dn=1,008-of 1.027). The concentration of carboxyl groups on the surface of the microspheres is (3,4-138,1)×10-3mg-EQ./m2. The suspension is stable in physiological solutions (0,15-0,25 M).

Aggregate stability of polymeric microspheres is achieved through education Awami on the surface of particles of a dense adsorption layer, which concentrate almost all of the carboxyl groups, which provides a high concentration of functional groups on the surface of the microspheres, sufficient to create a diagnostic test-systems.

The particle size of the polymer suspensions was determined by the method of scanning electron microscopy on the device "S-570" Hitachi.

The content of carboxyl groups on the surface of the microspheres was determined after washing the latex from water-soluble impurities conductometric titration according to the method described in the journal J. Colloid. Polym. Sci. 1980, t.15, str.

Stability of polymer suspensions in electrolyte solutions was determined by titration method. The electrolyte concentration was changed in the range from 0.15 to 0.25 mol/L.

The specific implementation of the method illustrated in the following PR the measures.

Example 1.

In a reactor with a volume of 250 ml equipped with a mechanical stirrer, a thermometer and a capillary tube for blowing nitrogen, with vigorous stirring load 160 ml of bidistilled water, and 0.37 g of potassium persulfate and Tegaserod solution a stream of nitrogen for 15 minutes while it's heating up to 75°C, then add 40 ml of methyl methacrylate dissolved 0.11 g of dinitrile azo-bis-somaclonal acid, 0.52 g of α,ω-bis-(10-carboxyethyl)polydimethylsiloxane with a chain length 35 eloxatine. At the same time the volume ratio of monomer:water is 1:4. The polymerization is carried out at 75°C and vigorous stirring for 1 h, and then raise the temperature to 10°C and maintained the reaction mass at this temperature for 1 hour to achieve the conversion of MMA 100%. The formation of coagulum is not observed. Receive a suspension with a particle diameter of 0.50 μm and a coefficient of dispersion (Dw/Dn=1,019. The concentration of carboxyl groups on the surface of the microspheres is 35,8×10-3mg-EQ./m2.

In all subsequent examples, the conversion of monomer was 100%, and the formation of coagulum was observed.

Example 2.

In the reactor of example 1 with vigorous stirring load 160 ml of bidistilled water, 0.26 g of potassium persulfate and Tegaserod solution a stream of nitrogen for 15 minutes at the same time, the first heating it to 50°C, then add 40 ml of vinyl acetate with dissolved 0.04 g of dinitrile azo-bis-somaclonal acid and 0.37 g of α,ω-bis-(10-carboxyethyl)polydimethylsiloxane with a chain length 35 eloxatine. At the same time the volume ratio of monomer:water is 1:4. The polymerization is carried out at 50°C and vigorous stirring for 1 h, and then raise the temperature to 10°C and maintained the reaction mass at this temperature for 1 hour. Receive a suspension with a particle diameter of 0.40 μm and a coefficient of dispersion (Dw/Dn=1,010. The concentration of carboxyl groups on the surface of the microspheres is 21.2×10-3mg-EQ./m2.

Example 3.

In the reactor of example 1 with vigorous stirring load 160 ml of bidistilled water, 0.4 g of potassium persulfate and Tegaserod solution a stream of nitrogen for 15 minutes while it's heating up to 75°C, then add 40 ml of styrene dissolved 0.07 g 0.04 g of dinitrile azo-bis-somaclonal acid, 0,69 g of α,ω-bis-(10-carboxyethyl)polydimethylsiloxane with chain length 30 eloxatine and 0.25 g polyoxyethyleneglycol block copolymer of the formula

At the same time the volume ratio of monomer:water is 1:4. The polymerization is carried out at 75°C and vigorous stirring for 4 h, then raise the temperature to 10°C and vyd ribaut the reaction mass at this temperature for 1 hour. Receive a suspension with a particle diameter of 0.58 μm and a coefficient of dispersion (Dw/Dn=1,018. The concentration of carboxyl groups on the surface of the microspheres was 54.7×10-3mg-EQ./m2.

Example 4.

In the reactor of example 1 with vigorous stirring load 160 ml of bidistilled water, 0.35 g of potassium persulfate and Tegaserod solution a stream of nitrogen for 15 minutes while heating it to 50°C, then add 40 ml of n-butyl acrylate with dissolved 0.1 g of dinitrile azo-bis-somaclonal acid and 0.43 g of α,ω-bis-(10-carboxyethyl)polydimethylsiloxane with a chain length 45 eloxatine. At the same time the volume ratio of monomer:water is 1:4. The polymerization is carried out at 50°C and vigorous stirring for 2 h, and then raise the temperature to 10°C and maintained the reaction mass at this temperature for 1 hour. Receive a suspension with a particle diameter of 0.37 μm and a coefficient of dispersion (Dw/Dn=1,020. The concentration of carboxyl groups on the surface of the microspheres is 17.2×10-3mg-EQ./m2.

Example 5.

In the reactor of example 1 with vigorous stirring load 160 ml of bidistilled water, of 0.38 g of potassium persulfate and Tegaserod solution a stream of nitrogen for 15 minutes while heating it to 50°C, then add 40 ml of chloroprene rastvorennye in him 0.11 g of benzoyl peroxide, and 0.69 g of α,ω-bis-(10-carboxyethyl)polydimethylsiloxane with a chain length 35 eloxatine. At the same time the volume ratio of monomer:water is 1:4. The polymerization is carried out at 50°C and vigorous stirring for 2 h, and then raise the temperature to 10°C and maintained the reaction mass at this temperature for 1 hour. Receive a suspension with a particle diameter of 0.35 μm and a coefficient of dispersion (Dw/Dn=1,020. The concentration of carboxyl groups on the surface of the microspheres of 31.9×10-3mg-EQ./m2.

Example 6.

In the reactor of example 1 with vigorous stirring load 200 ml of bidistilled water, 0.25 g of potassium persulfate and Tegaserod solution a stream of nitrogen for 15 minutes while it's heating up to 65°C, then add 22 ml of methyl methacrylate dissolved in it, 0.02 g of benzoyl peroxide and 0.33 g of α,ω-bis-(10-carboxyethyl)polydimethylsiloxane with a length of chain 60 eloxatine. At the same time the volume ratio of monomer:water is 1:9. The polymerization is carried out at 65°C and vigorous stirring for 3 h, then raise the temperature to 10°C and maintained the reaction mass at this temperature for 1 hour. Receive a suspension with a particle diameter of 0.4 μm and a coefficient of dispersion (Dw/Dn=1,017. The concentration of carboxyl groups on the surface of the microspheres is 19.7×10-3mg-EQ./m2.

Example 7.

In the reactor of example 1 and the intensive stirring load 200 ml of bidistilled water, 0.14 g of potassium persulfate and Tegaserod solution a stream of nitrogen for 15 minutes while it's heating up to 75°C, then add 22 ml of styrene dissolved 0.02 g dinitrile azo-bis-somaclonal acid and 0.12 g of α,ω-bis-(10-carboxyethyl)polydimethylsiloxane with a chain length 40 eloxatine and 0.06 g polyoxyethyleneglycol block copolymer of the formula

At the same time the volume ratio of monomer:water is 1:9. The polymerization is carried out at 75°C and vigorous stirring for 4 h, then raise the temperature to 10°C and maintained the reaction mass at this temperature for 1 hour. Receive a suspension with a particle diameter of 0.40 μm and a coefficient of dispersion (Dw/Dn=1,014 registered. The concentration of carboxyl groups on the surface of the microspheres is 9.4×10-3mg-EQ./m2.

Example 8.

In the reactor of example 1 with vigorous stirring load 130 ml of bidistilled water, of 0.49 g of potassium persulfate and Tegaserod solution a stream of nitrogen for 15 minutes while it's heating up to 75°C, then add 65 ml of methyl methacrylate dissolved 0.12 g of dinitrile azo-bis-somaclonal acid, of 0.67 g of α,ω-bis-(10-carboxyethyl)polydimethylsiloxane with a length of chain 30 eloxatine and 0.06 g polyoxyethyleneglycol block copolymer forms the crystals

At the same time the volume ratio of monomer:water is 1:2. The polymerization is carried out at 75°C and vigorous stirring for 1 h, and then raise the temperature to 10°C and maintained the reaction mass at this temperature for 1 hour. Receive a suspension with a particle diameter of 0.65 μm and a coefficient of dispersion (Dw/Dn=with 1.009. The concentration of carboxyl groups on the surface of the microspheres is of 40.3×10-3 mEq./m2.

Example 9.

In the reactor of example 1 with vigorous stirring load 200 ml of bidistilled water to 0.19 g of potassium persulfate and Tegaserod solution a stream of nitrogen for 15 minutes while heating it to 60°C, then add 22 ml of methyl methacrylate dissolved 0.04 g of benzoyl peroxide and 0.39 g of α,ω-bis-(10-carboxyethyl)polydimethylsiloxane with a chain length 6 eloxatine. At the same time the volume ratio of monomer:water is 1:9. The polymerization is carried out at 60°C and vigorous stirring for 3 h, then raise the temperature to 10°C and maintained the reaction mass at this temperature for 1 hour. Receive a suspension with a particle diameter of 0.40 μm and a coefficient of dispersion (Dw/Dn=1,018. The concentration of carboxyl groups on the surface of the microspheres is 138,1×10-3mg-EQ./m2.

Note the R 10.

In the reactor of example 1 with vigorous stirring load 200 ml of bidistilled water, 0.21 g of potassium persulfate and Tegaserod solution a stream of nitrogen for 15 minutes while it's heating up to 75°C, then add 22 ml of methyl methacrylate dissolved 0.04 g of dinitrile azo-bis-somaclonal acid and 0.1 g of α,ω-bis-(10-carboxyethyl)polydimethylsiloxane with chain length 40 eloxatine, with a volumetric ratio of monomer:water is 1:9. The polymerization is carried out at 75°C and vigorous stirring for 1 h, and then raise the temperature to 10°C and maintained the reaction mass at this temperature for 1 hour. Receive a suspension with a particle diameter of 0.15 μm and a coefficient of dispersion (Dw/Dn=1,016. The concentration of carboxyl groups on the surface of the microspheres is 3.4×10-3mg-EQ./m2.

Example 11.

In the reactor of example 1 with vigorous stirring load 200 ml of bidistilled water, 0.21 g of potassium persulfate and Tegaserod solution a stream of nitrogen for 15 minutes while it's heating up to 75°C, then add 22 ml of methyl methacrylate dissolved 0.04 g of dinitrile azo-bis-somaclonal acid and 0.25 g of α,ω-bis-(10-carboxyethyl)polydimethylsiloxane with a chain length of 10 eloxatine. At the same time the volume ratio of monomer:water pillar is t 1:9. The polymerization is carried out at 75°C and vigorous stirring for 1 h, and then raise the temperature to 10°C and maintained the reaction mass at this temperature for 1 hour. Receive a suspension with a particle diameter of 0.13 μm and a coefficient of dispersion (Dw/Dn=1,011. The concentration of carboxyl groups on the surface of the microspheres is to 21.1×10-3mg-EQ./m2.

Micrograph of polymer particles obtained in examples 1-5 shown in Fig.1-5.

The method of obtaining monodisperse carboxylating polymeric microspheres in a water suspension, characterized in that the solution of the vinyl monomer surfactant - α,ω-bis-(10-carboxyethyl)polydimethylsiloxane containing from 6 to 60 siloxane units and taken in quantities of 0.5 to 1.9%, or its mixture with polyoxoalkyleneamine formula

where m=8-64, n=4-8, p=15-20, q=15-20 in the amount of 0.9 to 2.6% by weight of monomer, intensively stirred in bidistilled water in the atmosphere of inert gas by heating the mixture up to 50-75°C and a volume ratio monomer:water in the range of 1:(2-9), prior to adding to the reaction mass of 0.8-1.3% (by weight of monomer) of the radical polymerization initiators, a mixture of potassium persulfate with dinitriles azo-bis-somaclonal acid or benzoyl peroxide, to form the nternet emulsion, followed by polymerization for 2-5 h under the action of the initiator drops of monomer in the polymer particles, when temperature increases by 10°C per hour until the end of the process.



 

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14 cl, 1 tbl, 7 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: apparatus for producing polymer resin includes a polymerisation vessel, a support element, a protective element, a closed-cycle cooling apparatus, a starting material inlet channel and an element which defines the flow channel. The protective element forms a first flow channel between itself and the side surface of an axial mixer. The closed-cycle cooling apparatus includes a circulation inlet channel lying on the side surface of the protruding part opposite the protective element. The element which defines the flow channel lies between the support element and the protective element so as to close the side surface of the axial mixer and fix the support element and the protective element. Said element which defines the flow channel forms a second flow channel between itself and the side surface of the axial mixer, and a third flow channel for connecting the second flow channel with the starting material inlet channel. The flow channels from the first to the third make up a continuous flow channel, and the highest end of the first flow channel is open inside the protruding part. The gap, part of the first flow channel other than the highest end, the second flow channel and third flow channel are insulated from the inner zone of the protruding part. Disclosed also is a method of producing a polymer resin and a polymerisation vessel for the polymer resin.

EFFECT: obtaining resin of high transparency, ensuring complete and homogeneous mixing and polymerisation of the starting material, improved removal of polymerisation reaction heat.

14 cl, 1 tbl, 7 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polymer nanoparticle having a nucleus/shell configuration with an interphase region between the nucleus and the shell, which contains at least one polymerised monomer selected from a polymerised nucleus monomer and a polymerised shell monomer. The nucleus of the polymer nanoparticle is uniformly cross-linked by at least one cross-linking agent. The average diameter of the polymer nanoparticles can be less than 250 nm. Described also is a rubber composition containing polymer nanoparticles and use thereof to make tyres, as well as methods of producing polymer nanoparticles. To form a uniformly cross-linked nucleus, polymerisation of the nucleus is carried out through step-by-step addition in several loads or batching synchronised amounts of the nucleus monomer and the cross-linking agent. The size, composition and/or configuration of the interphase region is varied, thereby achieving desirable physical and/or chemical properties of the resultant polymer nanoparticles and compositions to which the nanoparticles are added.

EFFECT: improved physical and chemical properties.

45 cl, 6 tbl, 7 ex, 19 dwg

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