RU2525908C1 - Photopolymerised composition for single-stage obtaining of polymer nanoporous material with hydrophobic pore surface, nanoporous polymer material with selective sorbing properties, method of obtaining thereof, method of single-stage formation based thereon of water-separating filtering elements and method of purifying organic liquids from water - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention deals with elaboration of a photopolymerised composition for obtaining a polymer material, which possesses the three-dimensional nanoporous structure with hydrophobic surface of pores, a single-stage method of its obtaining and the porous polymer material with selective sorbing properties and a single-stage formation based on it water-separating filtering elements with the specified geometry and required mechanical strength, applied in devices for purification of organic substances, mainly hydrocarbon fuels, oils, oil products, from emulsified water and mechanical admixtures. The photopolymerised composition contains oligoetheracrylate, a light-sensitive component, as such used is 1,1,7-trimethylbicyclo[2.2.1]heptanes-2,3-dione (camphorquinone) or ortho-quinone or their mixture, a reducing agent, for instance, amine, a functionalising monomer of vinyl series, solidified in accordance with the radical mechanism, less reactionable in comparison with oligoetheracrylate and a forming hydrophobic polymer, and a non-capable of polymerisation component, dissolving composition monomers and compatible in a restricted way with the final polymer. The method of the single-stage obtaining of the polymer nanoporous material with the functionalised surface of pores, as well as methods of the single-stage obtaining of products, water-separating filtering elements with the specified geometry and increased mechanical strength, is elaborated on the basis of the composition.

EFFECT: nanoporous polymer water-separating filtering elements with the specified geometry and increased mechanical strength have been for the first time obtained by the single-stage photopolymerisation method; selectively sorbing properties of filtering elements have been experimentally proved at the example of purification of benzene from water.

15 cl, 1 tbl, 8 dwg, 6 ex

Description

The claimed invention relates to the chemistry of macromolecular compounds, nanotechnology and photochemistry, and relates to the development of a photopolymerizable composition to obtain a polymeric material having a three-dimensional nanoporous structure with a hydrophobic pore surface, a one-step method for producing a porous polymeric material with selective sorbing properties, and one-stage formation of water-separating filtering elements based on it given geometry and required mechanical strength used in troystvah for purification of organic liquids, preferably hydrocarbon fuels, oils, petroleum products, of emulsified water and solids.

Polymeric materials with a three-dimensional nanoporous structure are widely used in science and technology. Basically, porous polymeric materials having the above structure are monolithic, i.e. produced and used as a single unit. In contrast to layered structures, porous materials are more technologically advanced in manufacturing and application. The monolithic design improves the functional properties of the material, greatly simplifies the control of structural parameters and provides ease of replacement of waste blocks. Porous systems have a large contact surface, which determines the high sorption, filtering, exchange, separation properties of such materials.

Known photopolymerizable composition to obtain a three-dimensional porous polymeric material, including oligoester acrylate, for example oligocarbonate dimethacrylate, photoinitiator and non-polymerization component (M.A. Batenkin, A.N. Konev, S.N. Mensov, S.A. Chesnokov // High Molecular Compounds, Ser . A. 2011. T. 53. No. 7. pp. 1033-1043). In the mentioned source, α, ω-bis- (methacryloyloxyethylene-hydroxycarbonyl-oxy) ethyleneoxyethylene (OKM-2) was used as an initiator as oligocarbonate dimethacrylate. - photoinitiating system, turn on th substituted ortho-benzoquinone as a photosensitive component and an N, N-dimethylethanolamine as a reducing agent and as a component used nepolimerizatsionnosposobnogo dinonyl- ester of phthalic acid, or methanol.

The same source describes a method for producing a nanoporous polymeric material by photopolymerization of a composition. The method includes mixing the components of the composition until they are completely dissolved, placing the mixture in the mold cavity formed by two silicate glasses with a damping pad between them, irradiating with scattered polychromatic light, extracting the obtained material from the mold, washing it in an organic volatile solvent, followed by pumping it out.

When the composition, which is a true solution of oligoester acrylate OKM-2 and a non-polymerization component, is irradiated, it is turbid in some cases using methanol as an example, which indicates the phase separation of the components of the composition inside its volume at nanoscale during polymerization, namely, the formation of submicron pore volumes occupied non-polymerization component in the volume of a three-dimensional polymer. After polymerization is completed, the non-polymerization-capable component is removed from the pores of the polymer monolith. The presence of pores and their size both on the surface and in the volume of the sample were diagnosed by atomic force microscopy (AFM). The presence of bound open pores in the obtained nanoporous material was proved by sorption. The synthesized nanoporous polymers equally adsorb both polar and nonpolar solvents, respectively, they do not have selective sorption with respect to aqueous-organic mixtures.

The described photopolymerizable composition and a method for producing a nanoporous polymeric material by photopolymerization of the composition are taken as a prototype.

The disadvantage of the prototype is that the obtained porous material does not have selective sorption with respect to aqueous and organic liquids, which does not allow it to be used for the separation of aqueous-organic mixtures, for example for cleaning water from automobile fuel (gasoline, diesel fuel).

It is known that for the practical use of monolithic porous materials it is necessary that the pore surface has certain functional properties, in particular hydrophobic. The introduction of the finished functionalizing substance into the composition of the polymerizable medium at the initial stage of polymerization is not possible, because they can be encapsulated by a polymer (O. Okay // Prog. Polym. Sci., 25, 711, 2000), or they can lose their activity during polymerization when it is thermally initiated (T.I.Izaak, O.V. Vodyankina / / Advances in Chemistry, 78 (1), 80, 2009). Therefore, in most cases, the modification of the pore surface is carried out by grafting compounds containing functional groups to the surface of ready-made porous monoliths (G.V. Lisichkin, A.Yu. Fadeev, A.A. Serdan, P.N. Nesterenko, P G. Mingalev, DB Furman. Chemistry of grafted surface compounds. Fizmatlit, Moscow, 2003). The granular sorbents modified in this way are widely used, for example, in chromatography (Q. Luo, H. Zou, X. Xiao, Z. Guo, L. Kong, X. Mao // J. Chromatogr., A, 926, 255 (2001 ), S. Xie, F. Svec, JMJ Frechet // Biotechnol. Bioeng., 62, 30, 1999). The technologies for their preparation, which consist in fixing the grafted compound with anchor groups located on the surface and forming a chemical bond with the functional group, can be transferred to monolithic materials (73 B. Preinerstorfer, W. Bicker, W. Lindner, M. Lammerhofer / / J. Chromatogr., A, 1044, 187, 2004).

The problem to which the claimed invention is directed is to create a photocurable composition for producing a nanoporous material with a functionalized pore surface, in particular hydrophobic, to develop a one-step method for producing a nanoporous polymeric material based on it by photopolymerization, which has selective sorption to aqueous and organic liquids, and to obtain water-separating filter elements with a given geometry and the required mechanical strength, the development of a method for cleaning webs of organic liquids from water using the proposed water separating filter elements.

This problem is solved due to the fact that the inventive photopolymerizing composition for one-stage production of a porous material with a hydrophobic pore surface contains oligoether acrylate, a photosensitive component, which is used as 1,1,7-trimethylbicyclo [2.2.1] heptane-2,3-dione ( camphorquinone) or ortho-quinone, or a mixture thereof, a reducing agent, for example, an amine, functionalizing a vinyl monomer, curing by the radical mechanism, less reactive compared to oligoester acrylate and forming a hydrophilic a different polymer and a non-polymerization component that dissolves the monomers and is partially compatible with the final polymer, the composition comprising:

oligoester acrylate - in the amount necessary for the formation of a monolithic porous polymer, the polymer matrix of which has a three-dimensional structure;

photosensitive component - in the amount necessary for photoinitiation of the polymerization reaction of monomers;

reducing agent - in the amount necessary for the photoreduction of the photosensitive component;

functionalizing monomer - in the amount necessary to isolate it during the polymerization from the polymer network to the pore surface with the formation of a hydrophobic polymer layer on it;

non-polymerization component - in the amount necessary for its release into the heterophase with the polymer formed during photopolymerization from oligoester acrylate.

As the oligoester acrylate, you can use dimethacrylic or diacrylic esters of polyethylene glycols, for example, triethylene glycol dimethacrylate, or triethylene glycol diacrylate, or carbonate dimethacrylates, for example, α, ω-bis (methacryloyloxyethylene-hydroxycarbonyloxy) -methoxy-ethylethoxy-ethylethoxy-ethylethoxy-ethylethoxy-ethylethoxy-ethyl for example, α-methacryloyl-ω-methacryloyl diethylene glycoloxy olig (diethylene glycol phthalate) (MDF-2), or mixtures thereof, as available and conventionally used compounds. Along with the mentioned oligoester acrylates, others can also be used that form a monolithic polymer, the polymer matrix of which has a three-dimensional structure, for example, α, ω-tetramethacryloyoligo (glycerolphthalate), or α-methacryloyl-ω-trimethacryloylpentaerythritol-ethyryl dipentryl dimethryl dimethryl dimethryl dimethryl dimethryl dimethryl dimethryl dimethryl dimethryl dimethryl dimethryl dimethryl dimethryl dimethryl dimethrylo di

As a photosensitive component, ortho-quinones can be used. It is known [A.E. Chichibabin. The main principles of organic chemistry, sixth edition, Moscow, “GOSHIMIZDAT”, 1958, p. 335], that “quinones are compounds having the structure of diketones, which are derivatives, in fact, of benzene itself, but of dihydrobenzene. Such substances may contain keto groups in the para and ortho positions, but not in the meta position. Thus, quinones are divided into two classes: para-quinones and ortho-quinones. " The molecular structure of unsubstituted ortho-benzoquinone is given below.

To achieve the objectives of the invention as ortho-quinones, you can use ortho-benzoquinones of the formula:

where R ₁ = H, alkyl C ₃ , alkyl C ₄ , alkyl C ₆ , Cl, Br, NO ₂ ; R ₂ = H, alkyl C ₁ -C ₄ , alkyl C ₆ , Ph, MeO, F, Cl, Br, NO ₂ , CN; R ₃ = H, F, Cl; R ₄ = H, alkyl C ₃ , alkyl C ₄ , alkyl C ₆ .

or ortho-benzoquinones of the formula:

where R ₁ = H, t-Bu; R ₂ = H, MeO; R ₃ = H, MeO; R ₄ = H, t-Bu.

or oxantrenquinone of the formula

or a tetrahydronaphthoquinone derivative of the formula:

or a mixture thereof.

Amines can be used as a reducing agent, for example, as aliphatic dimethyl-iso-propanolamine, and as aromatic, for example, N, N-dimethylaniline. You can also use N, N-dimethylcyclohexylamine, or para-bromo-N, N-dimethylaniline and other amines.

As a functionalizing monomer, a vinyl series monomer can be used that cures by the radical mechanism, is less reactive than oligoester acrylate and contains hydrophobic groups that provide hydrophobic properties of polymers, for example, fluorine-containing (meth) acrylic monomers, such as 1,1,3-trihydrotetetrafluoro or 1,1,5-trihydrooctafluoroamyl methacrylate, or 1,1,7-trihydrodoctofluoroheptyl methacrylate, or 1,1,5-trihydrooctafluoroamyl acrylate, etc., or higher alkyl (meth) acrylates, such as odetsilmetakrilat, 2-ethylhexyl acrylate, lauryl methacrylate, octyl methacrylate, etc., or mixtures thereof. Moreover, the monomers mentioned are available and manufactured by industry.

As a non-polymerization component, organic solvents can be used that dissolve the monomers of the composition and are partially compatible with the final polymer, which include, for example, phthalic acid dinonyl ether, methanol, ethanol, butanol, carbon tetrachloride, etc., or mixtures thereof.

The components that make up the claimed composition, namely oligoester acrylate, which forms a three-dimensional polymer matrix in an amount necessary to form a monolithic porous polymer, a photosensitive component, which is used 1,1,7-trimethylbicyclo [2.2.1] heptane-2, 3-dione (camphorquinone), or ortho-benzoquinones of the formula:

where R ₁ = H, alkyl C ₃ , alkyl C ₄ , alkyl C ₆ , Cl, Br, NO ₂ ; R ₂ = H, alkyl C ₁ -C ₄ , alkyl C ₆ , Ph, MeO, F, Cl, Br, NO ₂ , CN; R ₃ = H, F, Cl; R ₄ = H, alkyl C ₃ , alkyl C ₄ , alkyl C ₆ .

or ortho-benzoquinones of the formula:

where R ₁ = H, t-Bu; R ₂ = H, MeO; R ₃ = H, MeO; R ₄ = H, t-Bu.

or oxantrenquinone of the formula

or a tetrahydronaphthoquinone derivative of the formula:

or a mixture thereof, a reducing agent, for example, an amine, in an amount necessary for the photopolymerization of monomers to proceed, a functionalizing monomer, in an amount necessary to isolate it from the polymer network to the surface of the pores and their hydrophobization, and a non-polymerization component, which is a pore former, in the amount necessary for its release into the heterophase with the polymer formed during the photopolymerization from oligiracrylate, are essential features, because each of them is necessary, and together they are sufficient to create a photopolymerizable composition, on the basis of which a polymeric nanoporous material with a hydrophobic pore surface is obtained in a one-step way.

A new and essential feature of the claimed composition is the presence of a functionalizing monomer. During photopolymerization due to lower reactivity compared with oligoether acrylate, the functionalizing monomer is concentrated in the pore volumes formed due to the microphase separation of the non-polymerization component and the three-dimensional polymer (the product of the polymerization of oligo ether acrylate). In this case, the polymerization of the functionalizing monomer due to the free radicals present on the pore surface leads to the formation of a functionalizing polymer on the pore surface, which imparts hydrophobic properties to the nanoporous polymer material.

Confirmation of the formation of pores with hydrophobic surface properties is that the resulting porous polymer acquires the property of selectively sorbing the organic medium and water. Namely, the sorption of such a porous benzene polymer exceeds the sorption of water by 14-59 times. The porous polymer obtained by the prototype without the addition of a monomer with a hydrophobic group (that is, only from oligoester acrylate and non-polymerization component) does not possess such properties. It is characterized by approximately the same sorption of both water and the organic phase, i.e. lack of selective sorption. For example, in the prototype [M.A. Batenkin, A.N. Konev, S.N. Mensov, S.A. Chesnokov // High-molecular compounds, Ser A. 2011. V. 53. Number 7. p.1033-1043] the characteristics of porous polymers obtained without the introduction of a monomer with a hydrophobic group are given, in which the ratio of benzene sorption to water sorption for the same content of non-polymerization component is 1.2-2.0. A positive effect (extremely high sorption of benzene and sorption of water close to zero) is achieved by introducing vinyl monomers into the composition, which cure like oligoester methacrylate by the radical mechanism, but are less reactive than oligoester acrylate and contain hydrophobic groups that provide pore hydrophobic properties . Such monomers are fluorine-containing (meth) acrylic monomers or higher alkyl (meth) acrylates. Obviously, the introduction of such monomers into the composition leads to the formation of a hydrophobic pore surface, as evidenced by a drastic decrease in the sorption of water by the polymer with a consistently high (maximum) sorption of benzene (table in Example 2).

The quantitative values of the mentioned ingredients of the composition are selected depending on the nature of the oligoester acrylate, the photosensitive component and the reducing agent, the functionalizing monomer and the non-polymerization component. (See examples below.)

This problem is also solved due to the fact that a method has been developed for a single-stage production of a porous polymer material with a hydrophobic pore surface. The method includes mixing the components of the photopolymerizable composition described above, placing it in a mold cavity, at least one side of which is transparent to actinic radiation, irradiating the composition through a transparent mold surface with actinic radiation having a spectral radiation density in the range of 350-650 nm with an intensity and the time required for the formation of a porous polymeric material, extraction of the obtained material from the mold, washing it in an organic volatile solvent, followed by her pumping it.

We propose the use of substituted ortho-benzoquinones in which the substituents may be in the 3, 4, 5 or 6 position of the ortho-benzoquinone ring, and in addition, we propose the use of substituted ortho-benzoquinones in which the substituents are hydrocarbon rings or heterocycles attached to the ortho-benzoquinone ring at positions 4, 5 (specifically, these are derivatives of 2,3-naphthoquinone and oxantrenquinone, which are named according to IUPAC nomenclature 5,6,7,8-tetrahydronaphthalene-2,3-dione and 1,4,6,9- tetra-tert-butyldibenzo [b, e] [1,4] dioxin-2,3-dione, co tvetstvenno). The spectral radiation density in the range 350-650 nm is determined by the absorption region of the photosensitive component 1,1,7-trimethylbicyclo [2.2.1] heptane-2,3-dione (camphorquinone) and ortho-benzoquinones of the formula:

where R ₁ = H, alkyl C ₃ , alkyl C ₄ , alkyl C ₆ , Cl, Br, NO ₂ ; R ₂ = H, alkyl C ₁ -C ₄ , alkyl C ₆ , Ph, MeO, F, Cl, Br, NO ₂ , CN; R ₃ = H, F, Cl; R ₄ = H, alkyl C ₃ , alkyl C ₄ , alkyl C ₆ .

or ortho-benzoquinones of the formula:

where R ₁ = H, t-Bu; R ₂ = H, MeO; R ₃ = H, MeO; R ₄ = H, t-Bu.

or oxantrenquinone of the formula l, 4,6,9-tetra-tert-butyldibenzo [b, e] [l, 4] dioxine-2,3-dione

or a tetrahydronaphthoquinone derivative of the formula

5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene-2,3-dione

Irradiation of the composition with light with a wavelength of more than 650 nm does not lead to its polymerization. When irradiated with light with a wavelength of less than 350 nm, the radiation is completely absorbed by the components of the composition, while the polymerization takes place in a thin layer and does not lead to the formation of a porous polymer. The intensity and duration of exposure to actinic radiation are determined by the photopolymerization kinetics of the oligoester acrylates and functionalizing monomer in the composition in the presence of a non-polymerization component, on the one hand, and, on the other hand, by diffusion processes that occur in the composition and ensure the formation of a nanoporous polymer structure. Namely, phase separation of the polymerizable system during the polymerization should occur at the nanoscale. The specific values of the intensity of actinic radiation and the duration of exposure depends on the nature and quantitative proportions of the components that make up the composition and are determined empirically (see examples below).

This problem is also solved due to the fact that according to the method described above, a nanoporous material has been developed with the ability to selectively sorb with respect to aqueous-organic mixtures. The said material is a three-dimensional polymer matrix in which bound open pores of submicron size (hundreds of nanometers) having a hydrophobic surface are uniformly distributed. The pore size was determined by atomic force microscopy (AFM), the specific surface area of the pores was determined by the low-temperature nitrogen sorption method, the selective sorption of the material was controlled by the gravimetric method.

This problem is also solved due to the fact that a method has been developed for a one-stage production of a nanoporous polymer water-separating filter element with a given geometry. The method includes mixing the components of the photopolymerizable composition described above, placing it in the cavity of the mold defining the geometry of the article, at least one side of the mold is transparent to actinic radiation, irradiating the composition through the transparent surface of the mold with actinic radiation having a spectral radiation density in the range of 350 -650 nm with the intensity and time required for the formation of a porous polymeric material, extracting the obtained product from the mold, washing it into organic skom volatile solvent with subsequent pumping.

This problem is also solved due to the fact that according to the method described above, in the process of one-stage formation of a porous polymer material, a porous polymer water separating filter element with a given geometry is simultaneously formed. Said filter element is a three-dimensional polymer matrix in which bound open pores of submicron size (hundreds of nanometers) having a hydrophobic surface are uniformly distributed and has a geometry defined by the shape during its preparation. Accordingly, a filter can be created with flat and / or curved surfaces and with the desired cross-sectional shape (circle, polygon, etc.).

The obtained nanoporous water separating filter element with a given geometry allows you to clean organic liquids from water. Water separation occurs due to the fact that water from the filtered mixture does not pass through the filter, which leads to a change in the ratio of the components of the filtered mixture at the inlet and outlet through the filter element. The ability of the filter element to separate aqueous-organic mixtures was controlled by chromatography to separate the aqueous-organic mixture passed through the filter element (see examples below).

This problem is also solved due to the fact that a method has been developed for one-stage production of a porous polymer water separating filter element with a given geometry and increased mechanical strength. The method involves mixing the components of the above photopolymerizable composition, placing it in the cavity of the form defining the geometry of the product, while one side of the form is transparent to actinic radiation, placing also in the cavity of the form of reinforcing elements, for example, using a metal mesh, irradiating the composition through transparent the surface of the form with actinic radiation having a spectral radiation density in the range of 350-650 nm, with intensity and for the time required to form the porous polymeric material, removing the obtained product from the mold, washing in an organic volatile solvent, followed by pumping it out.

As reinforcing elements, along with reinforcing nets of metal, it is also possible to use reinforcing nets of fiberglass, or polymer, or filaments of the above materials, or a fabric of needle-punched polymer non-woven material.

This problem is also solved due to the fact that, according to the method described above, in the process of one-stage formation of a porous polymeric material, a porous polymer water separating filter element with a given geometry and increased mechanical strength provided by reinforcing elements located in the volume of the claimed product is simultaneously formed.

Said water-separating filter element is a polymer product that contains a three-dimensional polymer matrix, in which related open pores of submicron size (hundreds of nanometers) are uniformly distributed with a hydrophobic surface, as well as reinforcing elements that are in the volume of the inventive product, while the geometry of the filter element is determined by the geometry the form in which the synthesis is carried out by photopolymerization. The obtained nanoporous water separating filter element with a given geometry and increased mechanical strength allows the separation of aqueous-organic mixtures. In this product, the separation occurs due to the fact that the water component of the filtered mixture does not pass through the filter, which leads to a change in the ratio of the components of the filtered mixture at the inlet and outlet through the filter element. The ability of the filter element to purify organic liquids from water was monitored by chromatography to separate the aqueous-organic mixture passing through the filter element (see examples below). The increased mechanical strength is ensured by the fact that the reinforcing elements located in the volume of the filter element have greater strength than a three-dimensional polymer matrix with a nanoporous structure.

This problem is also solved due to the fact that a method has been developed for purifying organic liquids from water using the aforementioned filters, both with a given geometry and with a given geometry and increased strength. The method consists in the fact that the separated mixture of organic liquid and water is placed on one side of the filter element, while the excess pressure of the water-organic mixture ensures that the organic component of the mixture passes through the filter element. The excess pressure of the aqueous-organic mixture on the surface of the filter can be provided either by the method of pumping the mixture or by the pressure of the column of the liquid being cleaned.

The invention is illustrated by drawings, which depict the following.

Figure 1 - implementation of a one-stage method for producing a porous polymer material with a functionalized pore surface. In the cavity of the mold 1, at least one side of which 2 is transparent to actinic radiation 3, a photopolymerizable composition 5 is placed with a damping pad 4 and irradiated. As a result of polymerization and subsequent washing, a porous polymer material with a functionalized pore surface is formed.

Figure 2 - structure of a nanoporous material with the ability to selectively sorb with respect to water-organic mixtures. The material is a polymer three-dimensional matrix 6 with uniformly distributed connected open pores of submicron size 7, the surface of which is covered with a layer of functionalizing polymer 8.

Figure 3 - implementation of the method of one-stage production of nanoporous polymer water-separating filter element with a given geometry. To implement this method, a split mold is used, the cavity of which 9 is formed by two surfaces of a given geometry, for example spherical, at least one side of which 10 is transparent to actinic radiation 3. The mold surfaces are separated by a damping pad 4, the size and shape of which determines the cross section of the filter. The photopolymerizable composition 5 is placed in a detachable form and irradiated. As a result of polymerization and subsequent washing, a nanoporous polymer filter element is formed with a given geometry and a functionalized pore surface.

Figure 4 is a view of a nanoporous polymer water separating filter element with a given geometry. It includes a polymeric three-dimensional matrix 6, in which connected open pores 7 of a submicron size (hundreds of nanometers) with a functionalized surface 8 are uniformly distributed, and surfaces defining the geometry of the filter element 11.

Figure 5 - implementation of the method of one-stage production of nanoporous polymer water-separating filter element with a given geometry and increased mechanical strength. A split mold is used, the cavity 9 of which is formed by two surfaces of the required geometry, for example, spherical, at least one side of which 10 is transparent to actinic radiation 3. The mold surfaces are separated by a damping pad 4, the size and shape of which determines the cross section of the filter. A photopolymerizable composition 5 is placed in the mold, reinforcing elements 12, and the composition is irradiated through the transparent surface of the mold. As a result of polymerization and subsequent washing, a nanoporous polymer filter element of increased strength with a given geometry and a functionalized pore surface is formed.

Figure 6 is a view of a nanoporous polymer water separating filter element with a given geometry and increased mechanical strength. It includes a polymeric three-dimensional matrix 6, in which connected open pores 7 of submicron size (hundreds of nanometers) with a hydrophobic surface 8, surfaces defining the geometry of the filter element 11 and the reinforcing element 12 are uniformly distributed.

On figa and 7b - options for implementing methods of purification of organic liquids from water using the above filters. On figa excess pressure of the water-organic mixture 13 on the surface of the filter element 14 is created by injection. The organic component of the aqueous-organic mixture passes through the filter element and the purified organic liquid 15 accumulates on the other side of the filter element. On figb excess pressure of the water-organic mixture 13 on the surface of the filter element 14 is created by the pressure of the column of the cleaned liquid with a height h. The organic component of the aqueous-organic mixture passes through the filter element and the purified organic liquid 15 accumulates on the other side of the filter element.

Example 1

A photopolymerizable composition was prepared by mixing 2.5 g of oligoester acrylate, which was used as α, ω-bis- (methacryloyloxyethylene-hydroxycarbonyloxy) ethyleneoxyethylene (commercial grade OKM-2), 0.0025 g of the photosensitive component, which was used as 3.6-di tert-butyl-4-ethylbenzoquinone-1.2, 0.05 g of a reducing agent, which was used dimethyl-iso-propanolamine, 0.5 g of a functionalizing monomer, which was used as 1,1,5-trihydrooctafluoroamyl acrylate and 2 g non-polymerization to mponenta, as which used methanol. The finished composition was placed in a mold cavity formed by two flat silicate glasses with a 1.5 mm thick damping pad between them, as shown in FIG. Irradiation was carried out with the light of a KGM-220-1000 lamp, the illumination in the plane of the form was I = 50 klx, the exposure time was 60 minutes. After irradiation, a sample of the polymer material was removed from the mold, washed in isopropyl alcohol, which was then removed by pumping. The result was 3.04 g of polymeric material. To obtain a different amount of material, the amount of the starting components of the composition must be proportionally changed. The finished sample is a cloudy, opaque polymer plate with plane-parallel sides with a thickness of 1.5 mm. Using the method of low-temperature sorption of nitrogen, it was found that the obtained polymer material has open pores with a specific surface area of 35.7 m ² / g. Using atomic force microscopy (NT-MDT Smena-A and Solver P47ACM microscopes), it was established that the average pore size in the obtained polymer material is 600 nm. To analyze the sorption ability of the obtained nanoporous polymer material with respect to water and benzene, samples of the material were placed for 24 hours in water and benzene. Sorption capacity (N) was calculated as the ratio of the volume of water or benzene absorbed by the polymer to the limiting pore volume in the sample, which was defined as the volume of the non-polymerization component in the initial composition. Sorption of water was 0.09; benzene sorption 1.26. Thus, the sorption of benzene by the obtained polymer material is 14 times greater than the sorption of water.

Example 2

A photopolymerizable composition was prepared by mixing 3 g of a mixture of oligoester acrylates consisting of triethylene glycol dimethacrylate (industrial grade TGM-3) and α-methacryloyl-ω-methacryloyl diethylene glycoloxy olig (diethylene glycol colthalate) (commercial grade 2, mass 2, MDF 2, g of a photosensitive component, which was used as the ortho-benzoquinones listed in table 1, 0.06 g of a reducing agent, which was used dimethyl-iso-propanolamine, 0.75 g of a functionalizing monomer, as 2-ethylhexyl acrylate was used, and 2.25 g of the non-polymerization component, which was used butanol. The finished composition was placed in a mold cavity formed by two flat silicate glasses with a damping pad between them 1.5 mm thick (Fig. 1). The irradiation was carried out with the light of a KGM-220-1000 lamp, the illumination in the mold plane was I = 150 klx, the exposure time for each composition was shown in Table 1. After irradiation, samples of polymer materials were removed from the mold, washed in isopropyl alcohol, which was then removed by pumping. The result was 3.8 g of polymeric material. To obtain a different amount of material, the amount of the starting components of the composition must be proportionally changed. The finished samples were turbid, opaque polymer plates with plane-parallel sides with a thickness of 1.5 mm. The sorption capacity of the material was determined as described in example 1. Data on sorption by water and benzene samples are shown in the table. Sorption of benzene by obtained polymer materials is 48-59 times greater than sorption of water.

Table 1 No. ortho-quinone exposure time, min Water sorption Benzene sorption one 4,5-dimethoxybenzoquinone-1,2 45 0,021 1.16 2 3,6-di-tert-butyl-4-methylbenzoquinone-1,2 90 0,022 1.18 3 3,6-di-tert-butyl-4- 85 0.02 1.15

propylbenzoquinone-1,2 four 3,6-di-tert-butyl-4-cyclohexylbenzoquinone-1,2 120 0,022 1,2 5 3,6-di-tert-butyl-4-phenylbenzoquinone-1,2 one hundred 0,023 1,1 6 3,6-di-tert-butyl-4-methoxybenzoquinone-1,2 130 0,021 1.15 7 3,6-di-tert-butyl-4-fluorobenzoquinone-1,2 60 0.02 1.14 8 3,6-di-tert-butyl-4-chlorobenzoquinone-1,2 70 0,022 1.16 9 3,6-di-tert-butyl-4-nitrobenzoquinone-1,2 140 0,021 1.17 10 3,6-di-tert-butyl-4-nitrile benzoquinone-1,2 140 0,021 1.15 eleven 3,6-di-tert-butyl-4,5-difluorobenzoquinone-1,2 65 0,021 1.17 12 3,6-di-tert-butyl-4,5-dichlorobenzoquinone-1,2 70 0,022 1.16 13 3,6-di-tert-butylbenzoquinone-1,2 70 0,022 1.15 fourteen 3-chloro-4,6-di-tert-butylbenzoquinone-1,2 110 0,023 1.18 fifteen 3-bromo-4,6-di-tert-butylbenzoquinone-1,2 120 0,021 1.17 16 3-nitro-4,6-di-tert-butylbenzoquinone-1,2 130 0,021 1.15 17 3,4,6-tri-iso-propylbenzoquinone-1,2 60 0,022 1.18 eighteen 3,6-di-cyclo-hexylbenzoquinone-1,2 60 0.02 1.19 19 3-tert-butyl-6-methylbenzoquinone-1,2 80 0,021 1.18 twenty 3-tert-butyl-6-phenylbenzoquinone-1,2 70 0,021 1.17 21 3-tert-butyl-6-iso-propylbenzoquinone-1,2 80 0,021 1.18 22 4-tert-butylbenzoquinone-1,2 90 0,022 1.15

Example 3

A photopolymerizable composition was prepared by mixing 4 g of a mixture of oligoester acrylates consisting of polyethylene glycol dimethacrylate-550 and triethylene glycol diacrylate in a weight ratio of 3: 1, 0.003 g of the photosensitive component, which was used 3,6-di-tert-butyl-4,5-dimethoxybenzoquin 1.2, 0.06 g of a reducing agent, which was used para-bromo-N, N-dimethylaniline, 0.6 g of a functionalizing monomer, which was used isodecylmethacrylate, and 1.4 g of a non-polymerization component, as e is used dinonyl phthalate. The finished composition was placed in a mold cavity formed by two flat silicate glasses with a damping pad between them 1.5 mm thick (Fig. 1). Irradiation was carried out with the full light of a KGM-220-1000 lamp (sample 1), light with a wavelength of less than 650 nm using a ZS-6 light filter (sample 2), and with light with a wavelength of more than 650 nm using a light filter KS-15 (sample 3) . In all cases, the illumination in the plane of the form was 100 klx without filters, the exposure time was 25 min. After irradiation, samples of polymeric materials No. 1 and 2 were removed from the mold, washed in isopropyl alcohol, which was then removed by pumping. Sample No. 3 was not obtained, since irradiation of the composition with the light flux of the indicated spectral range did not lead to its polymerization and it remained liquid. The result was 4.83 g of polymeric material No. 1 and 4.78 g of polymeric material No. 2. To obtain a different amount of material, the amount of the starting components of the composition must be proportionally changed. The finished samples were turbid, opaque polymer plates with plane-parallel sides with a thickness of 1.5 mm. It was found that materials No. 1 and 2 have open pores with a specific surface area of 62.4 and 58.8 m ² / g, and the average pore size is 300 and 320 nm, respectively. The sorption capacity of the material was determined as described in example 1. In samples No. 1 and 2, the sorption of water was 0.021 and 0.024; benzene sorption 1.1 and 1.2; that is, the sorption of benzene by the obtained polymer material is 52 and 50 times greater than the sorption of water, respectively. Thus, the porous polymeric materials obtained using the full light of the KGM-220-1000 lamp and the light flux extracted from its light flux with a wavelength of less than 650 nm are close or coincide. A polymer material using light with a wavelength of more than 650 nm is not formed.

Example 4

A photopolymerizable composition was prepared by mixing 4.5 g of oligoester acrylate, which was used as α-methacryloyl-ω-methacryloyl diethylene glycoloxy olig (diethylene glycol tertalate) (industrial grade MDF-2), 0.005 g of the photosensitive component, which was used as a mixture of 1.4, 6,9-tetra-butyldibenzo [b, e] [1,4] dioxin-2,3-dione and 5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene-2,3-dione in a ratio of 1: 4, 0.1 g of a reducing agent, for which triethylamine was used, 1.5 g of a functionalizing component, and polzovali 1,1,3-trigidrotetraftorpropilmetakrilat and 4 g nepolimerizatsionnosposobnogo component as methanol is used. The finished composition was placed in a mold cavity formed by two silicate glasses with spherical surfaces with a damping gasket in the form of a circle with a diameter of 5 cm with a gap for filling the composition, as shown in figure 3, and a thickness of 3 mm Irradiation was carried out with the full light of a KGM-220-1000 lamp, the illumination in the plane of the form was I = 20 klx, the exposure time was 100 min. After irradiation, the filter element was removed from the mold, washed in methylene chloride, which was then removed by pumping. The finished filter element has the shape of a sphere segment, which was set during its formation. The said element has a diameter of 5 cm with parallel surfaces, the distance between which is 3 mm. The convex shape of the filter element allows you to increase its performance compared to flat due to the increase in surface area. The specific pore surface, characteristic pore size, sorption of water and benzene were determined as described in example 1. These parameters were 2.4 m ² / g; 5 microns; 0.08 and 1.41, respectively. To determine the filtering ability of the product, the applicant made a water separating system, shown in figa. A mixture of water and benzene with a water content of 0.21 mass% was passed through the system. Analysis of the mixture passing through the filter showed that the water content decreased to 0.03 wt.%. Thus, the use of the obtained nanoporous polymer filter element reduces the water content in the water-benzene mixture passed through it by 7 times.

Example 5

A photopolymerizable composition was prepared by mixing 6 g of oligoester acrylate, which was used as α-methacryloyl-ω-methacryloyl-diethylene glycoloxy-olig (diethylene glycolphthalate) (industrial grade MDF-2), 0.005 g of the photosensitive component, which was used as 3.6-di-tert -butyl-4-nitrobenzoquinone-1,2, 0.14 g of a reducing agent, which used N, N-dimethylaniline, 1 g of a functionalizing component, which was used 1,1,5-trihydrooctafluoroamyl acrylate, and 3 g of non-polymerization component as methanol is used. The finished composition was placed in a mold cavity formed by two silicate glasses with spherical surfaces with a damping gasket in the form of a circle with a diameter of 5 cm with a gap for filling the composition, as shown in figure 3, and a thickness of 3 mm Irradiation was carried out with the full light of a KGM-220-1000 lamp with a focusing device, illumination in the plane of the form was I = 50 klx, exposure time 70 min. After irradiation, the filter element was removed from the mold, washed in methylene chloride, which was then removed by pumping. The finished filter element has the shape of a sphere segment, which was set during its formation. The said element has a diameter of 5 cm with parallel surfaces, the distance between which is 3 mm. The convex shape of the filter element allows you to increase its performance compared to flat due to the increase in surface area. The specific pore surface, characteristic pore size, sorption of water and benzene were determined as described in example 1. These parameters were 12 m ² / g; 2.8 microns; 0.02 and 1.25, respectively. To determine the filtering ability of the product, the applicant made a water separating system, shown in figa. A mixture of water and benzene with a water content of 0.21 mass% was passed through the system. Analysis of the mixture passing through the filter showed that the water content decreased to 0.02 wt.%. Thus, the use of the obtained nanoporous polymer filter element reduces the water content in the water-benzene mixture passed through it by 10.5 times.

Example 6

A photopolymerizable composition was prepared by mixing two oligoester acrylates, which were used as 4 g of α, ω-bis- (methacryloyloxyethylene-hydroxycarbonyloxy) ethyleneoxyethylene (commercial grade OKM-2) and 1.3 g of α-methacryloyl-ω-methacryloyl-diethylene glycol-ethylene-olig ( ) (industrial brand MDF-2), 0.007 g of the photosensitive component, which was used camphorquinone (1,1,7-trimethylbicyclo [2.2.1] heptane-2,3-dione), 0.12 g of a reducing agent, as which was used dimethyl-cyclohexylamine, 1.2 g function naliziruyuschego monomer is used as a mixture of 2-ethylhexyl acrylate and isodecyl methacrylate in a ratio of 1: 2, and 3.5 g nepolimerizatsionnosposobnogo component, which was used as a mixture of butanol and carbon tetrachloride in a weight ratio of 4: 1. The finished composition was placed in a mold cavity formed by two silicate glasses with spherical surfaces with a damping gasket in the form of a circle with a diameter of 5 cm with a gap for filling the composition, as shown in figure 3, and a thickness of 3 mm Previously, a metal mesh with a square mesh of 1.5 mm and a wire thickness of 0.2 mm was placed in the mold cavity. Irradiation was carried out with the full light of a KGM-220-1000 lamp, illumination in the plane of the form I = 100 klx, exposure time 65 min. After irradiation, the polymer sample was removed from the mold, washed in methanol, which was then removed by pumping. The finished filter element has the shape of a sphere segment, which was set during its formation. The said element has a diameter of 5 cm with parallel surfaces, the distance between which is 3 mm. The specific pore surface, characteristic pore size, sorption of water and benzene were determined as described in example 1. These parameters were 8.4 m ² / g; 3.4 microns; 0.018 and 1.24, respectively. The resulting filter element was placed in the housing of the water separation system, similarly to that described in Example 4. A mixture of water and benzene with a water content of 0.21 wt.%, Under a pressure of 1.25 atm was passed through such a water separation system. Analysis of the mixture passing through the filter showed a decrease in the outlet water content to 0.016 wt.%. The filter element without reinforcement is destroyed at a pressure of the feed mixture of more than 0.5 atm. Thus, the use of the obtained nanoporous polymer filter reduces the water content in the water-benzene mixture passing through it by 13.1 times at a mixture pressure of up to 1.25 atm.

In the claimed invention, a photopolymerizable composition is developed, on the basis of which a method is developed for a single-stage production of a polymer nanoporous material with a functionalized pore surface, as well as methods for a single-stage production of articles - water-separating filter elements with a given geometry and increased mechanical strength. A nanoporous polymeric material is obtained, the selective sorbing properties of which are confirmed experimentally. Using the single-stage photopolymerization method, nanoporous polymer water separating filter elements with a given geometry and increased mechanical strength were first obtained. Selective sorbing properties of filtering elements have been experimentally proved by the claimed method of purification of organic liquids from water.

Claims (15)

1. A photopolymerizable composition for one-step production of a porous material with a functionalized pore surface, containing oligoether acrylate, a photosensitive component, which is used as 1,1,7-trimethylbicyclo [2.2.1] heptane-2,3-dione (camphorquinone) or ortho-quinone or a mixture thereof, a reducing agent, for example an amine, a functionalizing vinyl monomer, curable by a radical mechanism, less reactive than oligoester acrylate and forming a hydrophobic polymer, and non-polymerization a non-capable component that dissolves the monomers of the composition and is partially compatible with the final polymer, while the composition contains:
oligoester acrylate - in the amount necessary for the formation of a monolithic porous polymer, the polymer matrix of which has a three-dimensional structure;
photosensitive component - in the amount necessary for photoinitiation of the polymerization reaction of monomers;
reducing agent - in the amount necessary for the photoreduction of the photosensitive component;
functionalizing monomer - in the amount necessary to isolate it during the polymerization from the polymer network to the pore surface with the formation of a hydrophobic polymer layer on it;
non-polymerization component - in the amount necessary for its release into the heterophase with the polymer formed during photopolymerization from oligoester acrylate. 2. The photopolymerizable composition according to claim 1, characterized in that it contains dimethacrylic or diacrylic esters of polyethylene glycols, for example triethylene glycol dimethacrylate or triethylene glycol diacrylate, or carbonate dimethacrylates, for example α, ω-bis- (methylene-ethylene-ethylene-ethylene-methylene) 2) or phthalic acid ester dimethacrylates, for example α-methacryloyl-ω-methacryloyl diethylene glycoloxy oligo (diethylene glycol phthalate) (MDF-2), or a mixture thereof. 3. The photopolymerizable composition according to claim 1, characterized in that as the ortho-quinone it contains ortho-benzoquinones of the formula

where R ₁ = H, alkyl C ₃ , alkyl C ₄ , alkyl C ₆ , Cl, Br, NO ₂ ; R ₂ = H, alkyl C ₁ -C ₄ , alkyl C ₆ , Ph, MeO, F, Cl, Br, NO ₂ , CN; R ₃ = H, F, Cl; R ₄ = H, alkyl C ₃ , alkyl C ₄ , alkyl C ₆ . 4. The composition according to claim 3, characterized in that as the ortho-benzoquinone it contains ortho-benzoquinones of the formula

where R ₁ = H, t-Bu; R ₂ = H, MeO; R ₃ = H, MeO; R ₄ = H, t-Bu. 5. The composition according to claim 2, characterized in that as the ortho-quinone it contains an oxantrenquinone of the formula

or a derivative of tetrahydronaphthoquinone of the formula

or a mixture thereof. 6. The photopolymerizable composition according to claim 1, characterized in that it contains amines as a reducing agent, for example, as aliphatic dimethyl-iso-propanolamine, and as aromatic, for example, N, N-dimethylaniline. 7. The photopolymerizable composition according to claim 1, characterized in that it contains monomers with hydrophobic groups as a functionalizing monomer, for example fluorine-containing (meth) acrylic monomers, for example 1,1,5-trihydrooctafluoroamyl methacrylate or 1,1,5-trihydrooctafluoroamyl acrylate, or higher alkyl (meth) acrylates, for example isodecyl methacrylate or 2-ethylhexyl acrylate, or a mixture thereof. 8. The photopolymerizable composition according to claim 1, characterized in that as a non-polymerization component, it contains an organic solvent, for example, methanol or carbon tetrachloride, or phthalic acid dinonyl ether, or a mixture thereof. 9. The method of one-stage production of a porous polymeric material with a hydrophobic pore surface, comprising mixing the components of the photopolymerizable composition according to claims 1-8, placing the composition in a mold cavity, at least one side of which is transparent to actinic radiation, irradiating the composition through a transparent mold surface with actinic radiation having a spectral radiation density in the range of 350-650 nm, with intensity and for the time required for the formation of a porous polymeric material, material from the mold, washing it in an organic volatile solvent, followed by pumping it out. 10. The method of one-stage production of a porous polymer water separating filter element with a given geometry, comprising mixing the components of a photopolymerizable composition according to claims 1-8, placing the composition in a cavity of the form defining the geometry of the product, at least one side of which is transparent to actinic radiation, irradiating the composition through a transparent surface of the form with actinic radiation having a spectral radiation density in the range of 350-650 nm with intensity and for the time required to form Risto polymeric material, recovering the product from the mold, washing it in an organic volatile solvent with subsequent pumping. 11. The method of one-stage production of a porous polymer water separating filter element with a given geometry and increased mechanical strength, comprising mixing the components of a photopolymerizable composition according to claims 1-8, placing the composition in a mold cavity that defines the geometry of the product, while one side of the mold is transparent to actinic radiation, a reinforcing element is also placed in the mold, for example, a metal mesh is used, after which the composition is irradiated through the transparent surface of the actinium form nym radiation having a spectral radiation density in the range 350-650 nm, with an intensity and time that are required for forming the porous polymeric material, then the resulting product is removed from the mold and washed in a readily volatile organic solvent with subsequent pumping. 12. A porous polymeric material capable of selective sorption with respect to aqueous-organic mixtures, obtained according to claim 9, contains a three-dimensional polymer matrix in which bound open pores of submicron size (hundreds of nanometers) having a functionalized surface are uniformly distributed. 13. A porous polymer water separating filter element having the ability to selectively adsorb with respect to aqueous-organic mixtures, obtained according to claim 10, contains a porous polymer material according to claim 12 and has a geometry defined by the shape during its manufacture. 14. A porous polymer water separating filter element having the ability to selectively sorb the components of an aqueous-organic mixture obtained according to claim 11, contains a porous polymer material according to claim 12, reinforcing elements located in its volume, and has a geometry defined by the shape in the process its manufacture. 15. A method of purifying organic liquids from water, characterized by placing a shared mixture of organic liquid and water under pressure on one side of the water separating filter element according to item 13 or 14 and passing through the water separating filter element the organic component of the mixture.

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