RU2610614C2 - Light-converting metal-containing polymerisable compositions and method for production thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry and technology of materials which convert electromagnetic radiation. It is used to obtain metal-containing polymer compositions which selectively absorb or transmit electromagnetic radiation and are luminescent for lighting engineering, opto- and microelectronics. Light-converting metal-containing polymerisable compositions contain sulphides of cadmium, lead, zinc and lanthanide salts of trifluoro- and/or trichloroacetic acid. Base compositions are styrene and/or (meth)acrylic acid ethers, in volume ratio of styrene to esters from 0 to 1. Method of producing compositions is based on reacting trifluoro-and/or trichloroacetates of cadmium, lead, zinc with thioacetamide in a medium of (meth)acrylic acid esters and/or styrene and introduction into solution, after formation of metal sulphides, lanthanide salts of trifluoro- and/or trichloroacetic acid simultaneously or successively.

EFFECT: provides technically simple method of producing compositions capable of selectively absorbing or transmitting electromagnetic radiation and luminesce in visible and near infrared spectrum.

2 cl, 3 dwg, 1 tbl, 6 ex

Description

The invention relates to the chemistry and technology of materials that convert electromagnetic radiation. It is used to obtain selectively absorbing or transmitting electromagnetic radiation and / or luminescent metal-containing polymer compositions for lighting, optoelectronics and microelectronics.

Known polymerizable compositions (Analog 1) to obtain transparent polymeric materials that convert electromagnetic radiation (Mayer R.A., Smagin V.P., Mokrousov G.M., Chupakhina R.A., Skivko G.P., Kushch N. P., Evdokimov A.P., Batalov A.P., Kostesha A.V. Polymerizable composition for producing luminescent transparent polymeric materials / RF Patent No. 2034896 C1, publ. 05/10/95, bull. No. 13).

The polymerizable compositions contain salts of haloacetic acids and their complex compounds, the method of preparation of which consists in dissolving metal haloacetates in (alkyl) acrylic monomers and / or styrene and its derivatives, introducing photoactive additives into the compositions, forming complex compounds with metal ions, polymerizing the resulting mixtures to glassy state. The interaction of metal salts with photoactive additives, including sulfur-containing organic compounds, is carried out at room temperature. Under these conditions, the interaction is limited by the complexation reaction, i.e., metal sulfide is not formed in the systems, which provides the compositions with light absorption at the border of the near ultraviolet and visible spectral regions (300-500 nm) and luminescence in the visible and near infrared spectral regions (600-900 nm) .

Known compositions (Analog 2) based on polymethyl methacrylate (PMMA) containing cadmium sulfide (L. Pedone, E. Caponetti, M. Leone Synthesis and characterization of CdS nanoparticles embedded in a polymethylmethacrylate matrix // Journal of Colloid and Interface Science. - 2005 . - V. 284. - P. 495-500). The method for preparing the compositions consists in transferring CdS particles previously synthesized in microemulsions to methyl methacrylate (MMA), followed by its polymerization. CdS particles are prepared by adding a stoichiometric amount of tetrabutylammonium sulfide to a microemulsion containing an aqueous solution of CdSO ₄ in n-heptane and sodium bis (2-ethylhexyl) sulfosuccinate (AOT) as a stabilizer. The chemical reaction is carried out at a temperature of 25 ° C. To stop the growth of nanoparticles, bis (2-ethylhexyl) amine is added to the reaction medium. As a result, CdS particles up to 5 nm in size are obtained. AOT stabilized CdS particles are transferred to MMA and photopolymerized. The result is PMMA-CdS nanocomposites.

The disadvantages of Analog 2 are: multi-stage; use of additional substances; low stability of the microemulsion formed during the evaporation of the solvent and the transfer of CdS particles from one medium to another; partial destruction of the protective shell of colloidal particles and their enlargement, which significantly complicates and increases the cost of the synthesis technique. The introduction of additional components increases the light absorption of the base, which leads to a decrease in light transmission in the transparency region of the compositions. The method does not provide for the introduction of lanthanide salts into the composition of the compositions, and therefore, the compositions obtained by this method do not have selective absorption and luminescence characteristic of Ln (III) ions in the visible spectrum.

Compositions (Analog 3) based on PMMA containing CdS obtained by the interaction of cadmium trifluoroacetate with hydrogen sulfide in MMA medium with possible subsequent curing of the compositions by polymerization (Biryukov A.A., Isaak T.I., Svetlichny V.A., Gotovtseva E .Yu. Synthesis and properties of composite materials based on CdS nanoparticles and an optically transparent polymer // News of Universities. Physics. - 2009. - V. 52. - No. 12/2. - P. 16-20; A.A. Biryukov, TI Isaac, E.Yu. Gotovtseva, I.N. Lapin, A.I. Potekaev, V.A. Svetlichny Optical properties of CdS / MMA dispersions and CdS / PMMA nanocomposites, obtained in a single-stage size-controlled synthesis // Izv. VUZov. Physics. - 2010. - No. 8 - P. 74-80). In the reaction medium, consisting of MMA and cadmium trifluoroacetate dissolved in it (Cd (CF ₃ COO) ₂ ), in an amount of up to 5 × 10 ^-3 mol / l, with constant stirring with a stirrer rotation speed (500 ÷ 2000 rpm) a solution of hydrogen sulfide in MMA is added in a molar ratio Cd (CF ₃ COO) ₂ / H ₂ S = (1: 0.34; 1: 1; 1:10), while irradiating the system with radiation of various spectral composition (365 nm, 405 nm, 440 nm). The synthesis of CdS particles is carried out at reaction temperatures: 10, 20, 45, 65 ° C. At the end of the reaction, excess hydrogen sulfide and volatile products are removed from the reaction mixture by purging with argon for 10 minutes. Further, MMA / CdS based dispersions are thermally polymerized into block materials. As an initiator, benzoin peroxide is used in an amount of 0.1% with respect to the mass of MMA.

The disadvantages of Analog 3 are: the use of toxic gaseous hydrogen sulfide, which requires the creation of special conditions for its supply to the solution and flow control, as well as the degassing of the mixture from excess hydrogen sulfide after the formation of metal sulfides. Monitoring the concentration of hydrogen sulfide and the products of its interaction is also a rather complicated process. The stabilization of CdS particles is ensured by the formation of a polymer film on their surface with additional UV irradiation of solutions, which requires the use of special equipment. The maximum attainable concentration of CdS, stabilized in this way without precipitation, corresponds to a concentration of Cd (CF ₃ COO) ₂ = 5 × 10 ^-3 mol / L, which does not exceed 0.1 vol.%. This significantly reduces the degree of filling of CdS compositions and narrows the scope of their practical application. Thus, the method is technically complex, the concentration of CdS particles in the compositions is low. The production method does not provide for the introduction of lanthanide salts into the compositions, therefore, they do not exhibit spectral properties characteristic of lanthanides.

Known compositions (Prototype) based on (poly) methyl methacrylate containing cadmium sulfide, as well as neodymium and holmium compounds that selectively absorb optical radiation (Biryukov A.A. One-step synthesis of dispersions and nanocomposites CdS / polyacrylate with optical irradiation // Diss. ... Candidate of Chemical Sciences, Tomsk: TSU, 2010.140 s.).

The luminescence of the compositions manifests itself in the spectrum as a wide band with a maximum in the region of 650 nm. It is associated with the presence of CdS particles in the compositions. The method for preparing the compositions is as follows: in a reaction medium consisting of 10 ml of methyl methacrylate and salts (Cd (CF ₃ COO) ₂ , Nd (CF ₃ COO) ₃ and Ho (CF ₃ COO) ₃ in an amount of 0.017, 0 dissolved therein , 15 and 0.2 g, respectively, with constant rotation of the stirrer at a speed of 2000 rpm, pour 80 μl of a solution of MMA saturated with H ₂ S with a concentration of about 0.65 mol / L. At the same time, a quartz vessel containing the reaction mixture is irradiated 1 kW xenon lamp with filtered radiation at a wavelength of 365 nm for 1 min at room temperature in darkened After completion of the reaction, insoluble synthesis by-products, if necessary, are removed by centrifugation, and volatile by-products are removed by purging with argon.Then, to obtain a dispersion (Nd ³⁺ , But ³⁺ ), CdS / MMA (PMMA), thermal polymerization is carried out.

The prototype is characterized by the same disadvantages as Analog 3. They are associated with the use of gaseous H ₂ S, irradiation of the compounds with UV radiation, the need to remove by-products of the synthesis. In addition, neodymium and holmium trifluoroacetates are introduced into solutions simultaneously with cadmium trifluoroacetate at the initial stage of synthesis. After that, hydrogen sulfide is introduced into the system, which reacts with cadmium, neodymium and holmium trifluoroacetates, forming products of complex composition. Thus, the composition of the products formed is uncertain, the concentration of cadmium, neodymium and holmium compounds in them is low. The compositions do not exhibit luminescence associated with the presence of lanthanides. They do not contain other lanthanides, including luminescent in the visible spectral region of europium (III) and terbium (III) ions. The method of obtaining the compositions is technically difficult.

The aim of the present invention is to develop metal-containing polymerizable compositions based on (meth) acrylic acid esters and / or styrene esters and their polymers simultaneously containing cadmium sulfide particles or a mixture thereof with lead and / or zinc sulfides and lanthanide trifluoro and / or trichloroacetates, soluble in methacrylic acid esters, styrene, and mixtures thereof, which provide compositions with the ability to selectively absorb or transmit electromagnetic radiation at certain wavelengths and to luminesce in the visible and near her IR spectral range and a technically simple way to obtain them.

This goal is achieved by the synthesis of cadmium sulfide or its mixture with lead and / or zinc sulfides directly in the environment of (meth) acrylic acid and / or styrene ethers, which are the basis of the composition, the interaction of cadmium, lead, zinc trifluoroacetates, soluble in the base compositions with thioacetamide when heated in the temperature range of 70-90 ° C for 5-20 minutes, providing a concentration of cadmium sulfide or its mixture with lead and / or zinc sulfides in the compositions to 0.10 mol / L, and then, after formation cadmium sulfide or a mixture thereof with lead and / or zinc sulfides, the introduction of one or more salts of trifluoro- and / or trichloroacetic acid soluble salts of (meth) acrylic acid, styrene and their mixtures into the composition, simultaneously or sequentially, according to the following formulation:

1. In a pre-purified monomer (esters of (meth) acrylic acid and / or styrene), which is both the reaction medium and the base of the compositions, a predetermined amount of cadmium trifluoro and / or trichloroacetate of cadmium or its mixture with lead trifluoro and / or trichloroacetates and / or zinc.

2. Thioacetamide is added to the solution obtained according to claim 1 in the amount necessary to establish a molar ratio of trifluoro- and / or trichloroacetic acid salts of not more than 1: 1.5.

3. The solution obtained according to claim 2 is heated in the temperature range of 70-90 ° C for 5-20 minutes, ensuring the formation of cadmium sulfide or its mixture with lead and / or zinc sulfides in the solution.

4. Into the solution obtained according to claim 3, solutions of the salts of trifluoro- and / or trichloroacetic acids of one or more lanthanides are introduced simultaneously or sequentially until their concentration in the composition does not exceed 0.2 mol / (l of the polymerized composition), mixing and heating solutions.

5. If necessary, a polymerization initiator is added to the solution obtained according to claim 4.

6. The solution obtained according to claim 5 is polymerized in a block using one of the known methods.

Significant differences in the proposed solution from the prototype in composition are: the use as trifluoro- and / or trichloroacetates of lanthanides of one or more salts of praseodymium (III), europium (III), terbium (III), erbium (III), ytterbium (III), or their mixtures with salts of neodymium (III) and holmium (III) in a concentration not exceeding 0.2 mol / (l of the polymerizable composition), which gives the polymerizable compositions the ability to selectively absorb electromagnetic radiation and luminesce in the visible and / or near infrared region of the electromagnetic spectrum; using, as a basis, the composition of styrene or its mixtures with esters of (meth) acrylic acid with a volume ratio in the mixture of styrene to esters of (meth) acrylic acid from 0 to 1.

Significant differences of the proposed solution from the prototype according to the method are: the introduction of salts of lanthanides (trifluoroacetates and / or trichloroacetates), soluble in esters of (meth) acrylic acid, styrene and their mixtures, after the formation of cadmium sulfide or its mixture with lead sulfides and / or zinc. This solution provides compositions with predictable composition and spectral properties. The second fundamental difference is the use of thioacetamide rather than gaseous hydrogen sulfide in the synthesis process, which simplifies the production technology and makes it more environmentally friendly.

In the practical implementation of the proposed method are used:

1) esters of (meth) acrylic acid and / or styrene as the basis of the compositions, simultaneously being a reaction medium in which a chemical reaction occurs between the cadmium, lead, zinc and thioacetamide trifluoro and / or trichloroacetates with the formation of cadmium sulfide or its mixture with sulfides lead and / or zinc;

2) metal trifluoro- and trichloroacetates as metal-containing compounds that are precursors of cadmium, lead, zinc sulfides or a mixture thereof;

3) thioacetamide as a source of sulfide ions;

4) trifluoro- and trichloroacetates of praseodymium (III), europium (III), terbium (III), erbium (III), ytterbium (III), neodymium (III) and holmium (III) - as soluble salts for the delivery of lanthanide ions to composition, after the formation of metal sulfides in them.

The choice of esters of (meth) acrylic acid and / or styrene as the basis of the compositions is due to their high transparency in the optical spectral region (250-1000 nm). They are monomers of the most transparent polymers (poly (alkyl) acrylates, polymethyl methacrylate, polystyrene). Methyl methacrylate is preferred as the monomer of the composition. Compared to the known optical monomers and polymers, methyl methacrylate and polymethyl methacrylate are characterized by the highest light transmission in the optical region of the spectrum. The use of these compounds minimizes the effect of the base of the compositions (monomer, polymer) on the spectral properties in the field of their transparency. Methyl methacrylate is commercially available, the technology for producing its polymers is well studied and widely used in industry. The use of alkyl acrylates, and in particular methyl methacrylate, makes it possible to obtain transparent metal-containing compositions.

The use of trifluoro- and / or trichloroacetic acid salts as metal-containing compounds is due to their good solubility in esters of (meth) acrylic acid, in styrene and in their mixtures (Smagin V.P., Mayer R.A., Mokrousov G.M., Chupakhina R.A. Polymerizable composition for the production of transparent polymeric materials / USSR Patent No. 1806152 A3, publ. 03.30.93, bull. No. 12). The choice of cadmium, lead and zinc trifluoro- and / or trichloroacetates, in addition to their good solubility in low-polar monomers of optical polymers, is related to their ability to form sulfides and sulfide-containing compositions exhibiting broadband absorption of electromagnetic radiation in the near UV and visible spectral regions (less than 500 nm) and broadband luminescence in the visible and near infrared spectral regions (greater than 550 nm).

Due to their good solubility in organic solvents, trifluoro- and / or trichloroacetates of lanthanides ensure the delivery and entry of lanthanide ions into the composition of these salts (Smagin V.P. Physicochemical Properties of Polymethyl Methacrylate Modified with Rare-Earth Salts // Diss. ... Cand. Chem. Chem. Chem. Science Tomsk: TSU, 1991). The choice of salts of praseodymium (III), neodymium (III), europium (III), terbium (III), holmium (III), erbium (III), ytterbium (III) or their mixtures is related to their ability to exhibit narrow-band absorption and narrow-band luminescence in visible and near infrared.

The choice of thioacetamide as a source of sulfide ions is due to its manufacturability (non-gaseous state), solubility in esters of (alkyl) acrylic acids and styrene, also associated with the ability to react with metal trifluoro and / or trichloroacetates in ethers (alkyl) acrylic acids and / or styrene at temperatures of 70-90 ° C for 5-20 minutes to form stable compositions containing metal sulfides in a colloidal state. The colloidal state of metal sulfides provides high transparency to metal-containing compositions. Thioacetamide is a commercially available compound. At ambient temperature it is in a solid state of aggregation. Its use allows to obtain transparent metal-containing compositions exhibiting broadband absorption of electromagnetic radiation and broadband luminescence.

Methyl methacrylate, solutions of cadmium, lead, zinc, and thioacetamide (TAA) trifluoro- and trichloroacetates in methyl methacrylate are transparent to electromagnetic radiation with a wavelength of more than 280 nm. Solutions of trifluoro- and trichloroacetates of lanthanides are characterized by narrow-band absorption of visible radiation.

Examples of the claimed light-converting metal-containing polymer compositions and the practical implementation of the method for their preparation:

Example 1

1. 0.0338 g of cadmium trifluoroacetate is dissolved in 9.0 ml of pre-purified methyl methacrylate.

2. In the solution obtained according to claim 1, add 0.0075 g of thioacetamide, providing a molar ratio with cadmium trifluoroacetate 1: 1.

3. The solution obtained according to claim 2, is heated at a temperature of 90 ° C for 20 minutes. Get a transparent metal-containing composition having a yellowish tint, in the UV spectrum of which there is an absorption band in the wavelength range of 300-460 nm.

4. To the solution obtained according to claim 3, add 1.0 ml of methyl methacrylate containing 0.246 g of europium trifluoroacetate, ensuring its concentration in the final solution equal to 0.050 mol / L (molar ratios (Cd (CF ₃ COO) ₂ : TAA: Eu (CF ₃ COO) ₃ = 1: 1: 5).

5. In the solution obtained according to claim 4, benzoyl peroxide is added in an amount of 0.10% by weight of the monomer.

6. The solution obtained according to claim 5 is thermally polymerized in a block. A clear composition having a yellowish tint is obtained in a glassy state. In the UV spectrum of the composition there is a wide absorption band in the wavelength range of 300-460 nm. The luminescence spectrum includes a broad band with a maximum in the region of 770 nm, characteristic of CdS luminescence, and a set of narrow bands with maximums of 592 nm, 615 nm and 698 nm, characteristic of luminescence of europium (III) ions (Fig. 1). Basic light transmission of the composition (light transmission of the base) in the region of more than 500 nm is 92%.

Example 2

1. 0.0338 g of cadmium trifluoroacetate is dissolved in 9.0 ml of pre-purified methyl methacrylate.

2. In the solution obtained according to claim 1, add 0.0075 g of thioacetamide (1: 1).

3. The solution obtained according to claim 2, is heated at a temperature of 90 ° C for 20 minutes. Get a transparent metal-containing composition having a yellowish tint, in the UV spectrum of which there is an absorption band in the wavelength range of 300-460 nm.

4. To the solution obtained according to claim 3, add 1.0 ml of methyl methacrylate containing 0.250 g of terbium trifluoroacetate, providing its concentration in the final solution of 0.05 mol / l (Cd (CF ₃ COO) ₂ : TAA: Tb (CF ₃ COO) ₃ = 1: 1: 5).

5. In the composition obtained according to claim 4, benzoyl peroxide is added in an amount of 0.10% by weight of the monomer and according to claim 6 of Example 1, they are thermally polymerized in a block.

A clear composition having a yellowish tint is obtained in a glassy state. In the UV spectrum of the composition there is a wide absorption band in the wavelength range of 300-460 nm. In the luminescence spectrum, a broad band with a maximum at 770 nm, characteristic of cadmium sulfide, and a set of narrow bands with maxima of 488 nm, 544 nm, 586 nm and 620 nm, characteristic of the luminescence of terbium (III) ions (Fig. 2). The base transmittance of the composition in the region greater than 500 nm is 92%.

Example 3

1. 0.0338 g of cadmium trifluoroacetate is dissolved in 9.0 ml of pre-purified methyl methacrylate.

2. In the solution obtained according to claim 1, add 0.0075 g of thioacetamide (1: 1).

3. The solution obtained according to claim 2, is heated at a temperature of 90 ° C for 20 minutes. Get a transparent metal-containing composition having a yellowish tint, in the UV spectrum of which there is an absorption band in the wavelength range of 300-460 nm.

4. To the solution obtained according to claim 3, add 1.0 ml of methyl methacrylate containing 0.483 g of neodymium trifluoroacetate, providing its concentration in the final solution equal to 0.10 mol / L (Cd (CF ₃ COO) ₂ : TAA: Nd (CF ₃ COO) ₃ = 1: 1: 10).

5. In the composition obtained according to claim 4, benzoyl peroxide is added in an amount of 0.10% by weight of the monomer and according to claim 6 of Example 1, they are thermally polymerized in a block.

A transparent composition is obtained in a glassy state, having a lilac hue characteristic of neodymium (III) compounds. The absorption spectrum of the composition contains a wide band in the wavelength range of 300–460 nm, characteristic of cadmium sulfide absorption, and a set of narrow bands in the visible region of the spectrum, characteristic of absorption of neodymium (III) ions (Fig. 3). The luminescence spectrum contains a broad band with a maximum in the region of 770 nm, characteristic of the luminescence of cadmium sulfide, with characteristic dips in the region of more than 700 nm, corresponding to the absorption of neodymium (III) ions. Basic light transmission of the composition (light transmission of the base) in the region of more than 500 nm is 92%.

Example 4

1. 0.0169 g of cadmium trifluoroacetate is dissolved in 9.0 ml of pre-purified methyl methacrylate.

2. In the solution obtained according to claim 1, add 0.0037 g of thioacetamide (1: 1).

3. The solution obtained according to claim 2, is heated at a temperature of 80 ° C for 10 minutes. Get a transparent metal-containing composition, in the UV spectrum of which there is an absorption band in the wavelength range of 300-450 nm.

4. To the solution obtained according to claim 3, add 1.0 ml of methyl methacrylate containing 0.0483 g of neodymium trifluoroacetate, providing a concentration in the final solution of 0.01 mol / l, and 0.246 g of europium trifluoroacetate, ensuring its concentration in a final solution equal to 0.05 mol / L (Cd (CF ₃ COO) ₂ : TAA: Nd (CF ₃ COO) ₃ : Eu (CF ₃ COO) ₃ = 1: 1: 2: 10).

5. In the composition obtained according to claim 4, benzoin peroxide is added in an amount of 0.10% by weight of the monomer and according to claim 6 of Example 1, they are thermally polymerized in a block.

A clear composition is obtained in a glassy state. The absorption spectrum of the composition contains a wide absorption band in the wavelength range of 300-450 nm, a set of narrow bands in the visible region of the spectrum, characteristic of the absorption of Nd (III) ions. In the luminescence spectrum, a broad band with a maximum in the region of 770 nm, characteristic of cadmium sulfide, and a set of narrow bands with maxima of 592 nm, 615 nm and 698 nm, characteristic of the luminescence of Eu (III) ions, with dips corresponding to absorption by Nd (III) ions ) The base transmittance of the composition in the region greater than 500 nm is 92%.

Example 5

1. 0.0169 g of cadmium trifluoroacetate is dissolved in 9.0 ml of pre-purified methyl methacrylate.

2. In the solution obtained according to claim 1, add 0.0037 g of thioacetamide (1: 1).

3. The solution obtained according to claim 2, is heated at a temperature of 80 ° C for 10 minutes. Get a transparent metal-containing composition, in the UV spectrum of which there is an absorption band in the wavelength range of 300-450 nm.

4. To the solution obtained according to claim 3, add 0.5 ml of methyl methacrylate containing 0.0483 g of neodymium trifluoroacetate, providing its concentration in the final solution of 0.01 mol / L (Cd (CF ₃ COO) ₂ : TAA : Nd (CF ₃ COO) ₃ = 1: 1: 2). The solution was stirred and continued to heat in accordance with paragraph 3.

5. To the solution obtained according to claim 4, add 0.5 ml of methyl methacrylate containing 0.250 g of terbium trifluoroacetate, providing its concentration in the final solution of 0.05 mol / L (Cd (CF ₃ COO) ₂ : TAA: Nd (CF ₃ COO) _3: Tb (CF ₃ COO) ₃ = 1: 1: 2: 10).

6. In the composition obtained according to claim 3, benzoyl peroxide is added in an amount of 0.10% by weight of the monomer and according to claim 6 of Example 1, they are thermally polymerized in a block.

A clear composition is obtained in a glassy state. The UV spectrum of the composition contains a wide absorption band in the wavelength range of 300-450 nm, a set of narrow bands in the visible region of the spectrum, characteristic of the absorption of neodymium ions. In the luminescence spectrum, there is a broad band with a maximum in the region of 770 nm, characteristic of cadmium sulfide, and a set of narrow bands with maxima of 488 nm, 544 nm, 586 nm and 620 nm, characteristic of the luminescence of Tb (III) ions with dips corresponding to ion absorption Nd (III). The base transmittance of the composition in the region greater than 500 nm is 92%.

Example 6

1. 0.0338 g of cadmium trifluoroacetate and 0.0291 g of zinc trifluoroacetate (1: 1) are dissolved in 9.0 ml of pre-purified methyl methacrylate.

2. In the solution obtained according to claim 1, add 0.0075 g of thioacetamide (1: 1: 1).

3. The solution obtained according to claim 2, is heated at a temperature of 90 ° C for 20 minutes. Get a transparent metal-containing composition having a yellowish tint, in the UV spectrum of which there is absorption in the wavelength range of 300-440 nm.

4. To the solution obtained according to claim 3, add 1.0 ml of methyl methacrylate containing 0.246 g of europium trifluoroacetate, ensuring its concentration in the final solution equal to 0.050 mol / L (Cd (CF ₃ COO) ₂ : Zn (CF ₃ COO ) ₂ : TAA: Nd (CF ₃ COO) ₃ : Eu (CF ₃ COO) ₃ = 1: 1: 1: 5).

5. In the solution obtained according to claim 4, benzoyl peroxide is added in an amount of 0.10% by weight of the monomer and according to claim 6 of Example 1, they are thermally polymerized in a block.

A transparent composition is obtained in a glassy state, in the UV spectrum of which there is a wide absorption band in the wavelength range of 300-440 nm. In the luminescence spectrum, there is a broad band with a maximum in the region of 760 nm, characteristic of CdS luminescence, and a set of narrow bands with maximums of 592 nm, 615 nm and 698 nm, characteristic of the luminescence of Eu (III) ions. The base transmittance of the composition in the region greater than 500 nm is 92%.

The table shows examples of other claimed compositions and characteristics of their spectral-luminescent properties. The compositions are obtained in accordance with the claimed method, the practical implementation of which is demonstrated by examples 1-6.

An analysis of the examples shows that the ability of liquid and glassy compositions to absorb electromagnetic radiation broadband at wavelengths less than 510 nm and broadband luminescence at wavelengths greater than 550 nm is associated with the occurrence of a chemical reaction between trifluoron during the heating of ethers of (meth) acrylic acids and / or styrene -, trichloroacetates of cadmium, lead, zinc and thioacetamide with the formation of cadmium sulfide or its mixture with lead and / or zinc sulfides in a colloidal state. The absorption and luminescence spectra before curing do not significantly differ from the corresponding spectra of the compositions in the glassy state. The basic light transmission of the compositions (light transmission of the base) at wavelengths greater than 500 nm is 92% with an absorbent layer thickness of up to 5 mm. Heating at temperatures greater than 90 ° C or less than 70 ° C does not produce the desired result. The compositions are destroyed or the desired reaction product is not formed. Heating solutions for less than 5 and more than 20 minutes does not lead to the desired result. In the first case, the desired product is not formed, in the second case, the heating is not effective or the composition is destroyed. When heating solutions containing trichloro- and / or trichloroacetates of cadmium, lead, zinc and / or thioacetamide in concentrations of more than 0.10 mol / L, metal sulfides are released in the form of a coarse-dispersed phase. Narrow-band absorption of electromagnetic radiation and narrow-band luminescence in the visible spectral region are associated with the introduction of lanthanide (III) ions into the composition.

Use for delivery of lanthanide (III) ions in a composition of salts of trifluoro- and / or trichloroacetic acid readily soluble in (meth) acrylic acid esters, styrene and their mixtures upon their simultaneous or sequential administration after the formation of cadmium sulfide or a mixture thereof with lead sulfides in the compositions and / or zinc allowed us to achieve a positive solution, consisting in the appearance in the compositions of selective absorption of electromagnetic radiation and luminescence in the visible and near infrared spectral regions associated with each of Qdim lanthanides in the composition (III). The introduction of trifluoro- and / or trichloroacetates of lanthanides in the composition simultaneously with cadmium, lead, zinc salts or their mixtures, as well as in a concentration of more than 0.2 mol / l, leads to the disappearance of the positive effect or to a decrease in the spectral-luminescent properties and light transmission of the compositions.

Examples of compositions of different composition and its effect on the observed effect are presented in the table and in the figures. The analysis of the results confirms the practical implementation of the proposed method for the preparation and composition of light-converting metal-containing polymer compositions. High light transmission of compositions emphasizes their uniformity. The constant spectral properties for a long time characterizes the stability of the compositions. The possibility of obtaining in a glassy state and manufacturing from them products of various shapes and sizes emphasizes their manufacturability. The availability of the starting compounds, low consumption per unit of production, the simplicity of the claimed production method, as well as the combination of the obtained properties make it possible to use transparent metal-containing polymer compositions as light-converting materials in lighting engineering, optoelectronics and microelectronics.

Claims (2)

1. Light-converting metal-containing polymerizable compositions intended for the conversion of electromagnetic radiation, containing the basis of the composition, cadmium sulfide, lead, zinc and lanthanide salts, characterized in that they contain one or more salts of trifluoro- and / or trichloroacetic acid lanthanides, namely praseodymium (III ), europium (III), terbium (III), erbium (III), ytterbium (III) or their mixture with salts of neodymium (III) and holmium (III) in an amount ensuring their concentration up to 0.20 mol / (l polymerizable composition), as the basis of compo itsii used styrene and / or esters of (meth) acrylic acid at a volume ratio of a mixture of styrene to esters of (meth) acrylic acid, from 0 to 1. 2. A method of producing light-converting metal-containing polymerizable compositions for converting electromagnetic radiation according to claim 1, characterized in that cadmium sulfide or a mixture thereof with lead and / or zinc sulfides is obtained by the interaction of trifluoro and / or trichloroacetates of cadmium, lead, zinc with thioacetamide, and lanthanide trifluoro and / or trichloroacetates are introduced into the composition after the formation of cadmium sulfide or a mixture thereof with lead and / or zinc sulfides, simultaneously or sequentially.

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