Svetopropusknaya polymer composition

 

(57) Abstract:

The invention relates to polymeric compositions based on thermoplastic polymers, which converts the UV component of sunlight or other light source in the radiation of the red region of the spectrum, and can be used in various fields, for example, for the production of films or glass, used in greenhouse farms, creating various decorative elements in advertising. The polymer composition comprises a thermoplastic (co)polymer and active additives A, B, C, D, where A is an organic and/or inorganic salt of europium, B is one or more compounds from the class - diketones, C - compound from the class of nitrogen and/or oxygen-containing heterocycles, or from a number of oxides, organic amines, phosphines or sulfides, D - salt alkaline, alkaline earth metal and/or ammonium and organic acids busy number and/or aliphatic amine, in the following ratio, wt.%: compound a is 0.001 - 5; compound B is 0.001 - 5; connection C is 0.001 - 5; compound D is 0.001 - 5; thermoplastic polymer else. Offer svetopropusknuyu polymer composition is an effective absorber of UV radiation and has the luminescence primesense thermoplastic polymers, converts the UV component of sunlight or other light sources in the radiation of the red region of the spectrum, and can be used in various fields, for example, for the production of films or glass, used in greenhouse farms, creating various decorative items, advertising, etc.

Known polymeric composition based polycarbonate containing as an active additive compound from a number of pyrazino applied to silicate glass, and converts the energy of the UV-component of the incident light in the emission of the blue range of the spectrum (Japan patent N 06-199814, CL 07 D 241/26, 1994).

The disadvantage of this arrangement is limited in its application, in particular in agriculture, its use is impractical because the radiation from the blue region of the spectrum not effectively stimulates the growth and yield of agricultural structures in comparison with the light red region of the spectrum.

Known polymer composition to obtain a film-based (co)polymer of ethylene containing as active additives one of the complex compounds Eu, in particular the complexes of the following structure: Eu(K)3HZ, where K - diketone, HZ - the 07, 5/32, 5/41, 5/45, 1981)

The specified polymer composition has the following disadvantages: first, the presence of synthesis supplements that it requires some effort and funds; the second complex compounds Eu specified structure, like most other complex compounds Eu, decompose at temperatures close to the melting point of the polymer. Therefore they should not be introduced in a film of polyethylene conventional scheme at the stage of obtaining a film or a polymer concentrate during extrusion. This resulted in the emergence of another additional and totally unacceptable when large-tonnage production stage impregnation of the pellets of the polyethylene solution supplements in acetone, followed by evaporation of the solvent. And the third, as pointed out by the authors of the invention, with increasing concentration of active additives increases the light diffusing films (reduced translucency), which reduces the effectiveness of their application.

Closest to the claimed invention is a known polymer composition to obtain a film-based (co)polymer of ethylene, including active additives. As an active additives it contains A, B, C, where A is the oxide, Arnie from the class of bidentate nitrogen heterocycles or one of a number of trialkyl(aryl)phosphine oxides (U.S. Pat. RF N 2132346, publ. 1999, BI N 18).

This composition has the disadvantage of low efficiency of svetopropuskanie UV component of light in the visible radiation range, which is manifested in low luminescence intensity of the coatings, and other products.

The task of the claimed invention is to provide such svetopropusknaya polymeric composition, which would provide a higher conversion efficiency of UV light in the red light range of the spectrum, would preserve the mechanical and optical (visible range) characteristics of the source of polymeric material and high manufacturability and ease of manufacture and application.

The solution of this problem is achieved by the fact that the proposed svetopropusknaya polymer composition comprises a thermoplastic (co)polymer and active additives A, B, C, D, where A is an organic and/or inorganic salt of europium, B is one or more compounds from the class - diketones, C - compound from the class of nitrogen and/or oxygen-containing heterocycles, or from a number of oxides, organic amines, phosphines or sulfides, and D - salt alkaline, alkaline earth metal and/or ammonium and organic acids NNT B - of 0.001-5

Component C is 0.001-5

Component D is 0.001-5

Thermoplastic (co)polymer - Rest

As a thermoplastic (co)polymer can contain high-pressure polyethylene or low density, polypropylene, copolymer of ethylene and propylene, a copolymer of ethylene and vinyl acetate, acetobutyrate cellulose, polystyrene, polyvinyl chloride, polycarbonate, polyacrylates, polyamides, polyesters.

As inorganic salts europium it may contain nitrate or halide europium, hydrated or anhydrous.

As organic salts of europium it can contain the connection of a number of europium salts with formic acid or its homologues to C18inclusive; with triperoxonane and perfluorinated homologues to C4inclusive; with mono-, di - and trichloroacetic acids; naphthyl-, phenyl - and diphenylalanine acids; benzoic acid and its substituted derivatives containing from one to five halogen atoms and/or from one to five alkyl or CNS groups from C1to C18inclusive, phenyl or benzoyloxy group; aromatic hydroxy acid containing from one to three hydroxy groups in the benzene or nadimi unsaturated mono - and dicarboxylic acids from the C3to C18inclusive, containing phenyl, nattily or purely Deputy; with aliphatic hydroxy acids from the C2to C6inclusive with one or two hydroxyl groups and containing in the molecule from one to three carboxyl groups; aromatic polycarboxylic acids rows of benzene, naphthalene, diphenyl and dinaphthyl containing from two to four carboxyl groups in the benzene nucleus, and one or two carboxyl groups in different positions in the naphthalene nucleus; with carboxylic acids, heterocyclic series, namely mono - and decolletage number of imidazole, pyridine, pyrazine, indole and quinoline.

As - diketones it can contain one or more compounds with the General formula R1C(O)CH2C(O)R, where R1and R2- different or identical residues, which represents a normal or branched alkyl from C1to C18, perfluoroalkyl from C1to C4inclusive, unsubstituted phenyl or containing from one to five halogen atoms and/or from one to five alkyl or CNS groups from C1to C18inclusive or performanceline group from C1to C4inclusive, 1 - or 2-Netwise residues; or one or more compounds from the series of 4-acyl-3-methyl-1-phenyl-2-pyrazolin-5-ones, where the acyl - from acetyl to stearoyl inclusive or benzoyl, unsubstituted or in which hydrogen atoms are partially or completely substituted by fluorine atoms and acetyl, or benzoyl also similar to chlorine atoms.

As compounds of the class of nitrogen-containing heterocycles can contain connection from a number of pyrazoline, pyridine, pyridazine, quinoline, isoquinoline, cinoxacin, cinnoline, benzoquinoline, unsubstituted or contains one to three metal groups from a number of 2,2'- or 4,4'-bipyridine, 2,2'- piperazine, 2,2'-dipyrimidine, 3,3'-dipyridine, 2,2'- dhenain, 1,1'- or 3,3'-diisoquinoline, 4,5-diazafluoren, 1,10-phenanthroline, 2,2'6', 2"-terpyridine, 2,4,6-three(2 - pyridyl)-1,3,5-triazine, 1,8-naphthiridine, 1,4,5,8 - decreasefontsize, unsubstituted or contains one or two atoms of halogen, nitro, amino, hydroxy, methyl-, methoxy - and/or phenyl groups.

As compounds of the class of nitrogen and/or oxygen-containing heterocycles she may contain the connection of a number of macrocyclic crown ethers or their nitrogen analogues, namely 15-crown-5, benzo-15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-crown-6, 2,2,1 - 2 is th acid under nitrogen atoms or carbon.

As the connection of a number of oxides, organic amines, phosphines or sulfides she may contain the connection of a number of N-oxides of pyridine, unsubstituted or contains one to three methyl groups, N-oxide, quinoline, unsubstituted or contains one to two methyl groups, N-oxide benzoquinoline, N-oxide-2,2'- bipyridine, N-oxide 1,10-phenanthroline, N,N'-dioxide, 2,2'- bipyridine, N, N'-dioxide 1,10-phenanthroline; the connection of a number of P-oxide trialkyl(aryl)phosphines containing alkyl groups of from C4to C8and/or phenyl group, unsubstituted or containing alkyl substituent on C1to C4or CNS Deputy from C1to C4or pentafluorophenyl; the connection of a number of S - oxides, dialkyl(aryl)sulphides, where the alkyl from C1to C8and aryl is unsubstituted phenyl or pentafluorophenyl.

As organic salts of alkali or alkaline earth metal and/or ammonium, it may contain salt Li+, Na+TO+, Mg+Ca+, NH4+, R1NH3+,

R1R2NH2+, R1R2R3NH+and R1R2R3R4N+where R1-R4- equal or UB>4to C18inclusive.

As an amine, it may contain the compound of General formula RNH2, R1R2NH or R1R2R3N, where R1-R3the same or different alkali from C4to C18inclusive or benzyl.

The proposed polymer composition is prepared as follows: components a, b, C, D mechanically stirred at room temperature with a thermoplastic polymer (pellets, powder) in amounts according to the invention and processed into products by the known methods: extrusion, injection molding, etc., Suggested composition can also be prepared in two stages, the most common in modern polymer industries. First mixing all of the components of the composition, followed by extrusion and granulation prepare a concentrate containing the active additive in concentrations up to 20%. Then, when the production of the concentrate is diluted with the original thermoplastic polymer. The concentration of the active additive is brought to the necessary for this particular product.

Measuring the luminescence of the obtained films and products was carried out on spectrofluorimeter L-3. The intensity of luminescence of itintensive luminescence in the table.

The invention is illustrated by the following examples.

Example 1. Components supplements: uranyl chloride europium (A), thenoyltrifluoroacetone (), trioctylphosphine (C) and sodium palmitate (D), taken in the mass proportion of 1:1,82:2,11:2,29, mechanically mixed with granules of polyethylene at room temperature in a total concentration of 0.3% by weight of the polymer. The resulting composition is processed by extrusion into a film thickness of 100 microns.

Example 1a. The same components active additives (A), (b) and (C) taken in the same mass proportion as in example 1, but without sodium palmitate (D), processed into a polymer film thickness of 100 microns.

Example 2. Components active ingredients: acetate europium (A), 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-he (), 1,10-phenanthroline (C) and 1-hexadecylamine (D), taken in the mass proportion of 1:2,53:0,55:2,2 mechanically mixed with pellets of a copolymer of ethylene with vinyl acetate in a total concentration of 10% by weight of the copolymer, receiving the concentrate by extrusion. Thus obtained concentrate is processed by the method of calendering at 100-fold dilution of the original copolymer in sheet material of a thickness of 500 μm.

Example 2A.hexadecylamine (D), processed in the same way with pellets of a copolymer of ethylene with vinyl acetate in the concentrate and forth in the sheet material of a thickness of 500 μm.

Example 3. Components supplements: thenoyltrifluoroacetone (In), 2,2'-dipyridine (C) and calcium stearate (D), taken in the mass proportion of 1: 0,23: 1,23, mechanically mixed with pellets of nylon-12 in total concentration of 6% by weight of the polymer. The resulting composition is processed by extrusion into pellets besmearing concentrate. The uranyl nitrate europium (A) mechanically mixed with the granules besmearing concentrate and pellets of the original polymer. The mass proportion of the concentrate and the original polymer 1: 20. The ratio of the mass fraction of salt europium (a) and thenoyltrifluoroacetone (C) is 1:1.5. The resulting composition is processed by the method of forcing through a Spinneret into a polymer thread.

Example 3A. Components active additives (b) and (C) taken in the same mass proportions as in example 3, but without calcium stearate (D), processed in the same way with pellets of nylon-12 in bezmetallny concentrate, and then with the component (a) and the starting polymer with the same mass proportions as in example 3, the polymer thread.

P is acetone (B2), 2,2'- dipyridine (C1), 1,10-phenanthroline (C2and tribenzylamine (D), taken in the mass proportion 1: 0,91: 0,92:0,21:0,25:2,35 mechanically mixed with granules of polystyrene in the total concentration of 0.1% by weight of the polymer. The resulting composition is processed by extrusion, receiving molded castings.

Example 4a. Components active additives (A), (B1), (B2), (C1), (C2), taken in the same mass proportions as in example 4, but without the component (D) is processed in the same manner with beads of polystyrene in slab casting.

Example 5. Components supplements: nitrate pentahydrate europium (A1), stearate europium (A2), thenoyltrifluoroacetone (In), 2,2'-dipyridine (C1), dibenzo-18-crown-6(C2) and N, N-dimethyloctadecyl (D), taken in the mass proportion 1: 1,8: 1,5:0,4:0,8:3, mechanically mix with pellets of polypropylene at room temperature in a total concentration of 0.5% by weight of the polymer. The resulting composition is processed by extrusion into a film thickness of 150 microns.

Example 5a. Components active additives (A1), (A2), (B), (C1), (C2), taken in the same mass proportions as in example 5, but without component.component supplements: hydrate acetate europium (A), dibenzoylmethane (In), N-oxide 1,10-phenanthroline (C), ammonium stearate (D1and dioctyladipate (D2), taken in the mass proportion 1:2:0,6:4:0,5, mixed with pellets of a copolymer of ethylene with propylene in a total concentration of 0.4% by weight of the copolymer. The resulting composition is processed by extrusion blown film thickness of 50 microns.

Example 6a. Components active additives (A), (B), (C), taken in the same mass proportions as in example 6, but without the component (D1) and (D2), processed in the same way with pellets of a copolymer of ethylene with propylene in a film thickness of 50 microns.

The tests showed that the polymeric materials obtained in accordance with examples 1-6, retain mechanical and optical (visible range) characteristics of the source of polymeric materials. They absorb at least 90% of incident UV radiation, effectively (ratio of not less than 60%) transforming it into the light red region of the spectrum. As can be seen from the comparative examples, in comparison with the known composition (prototype) of the proposed composition results in an increase in luminescence intensity in 2-5 times.

Thus, the proposed sweetopia imushestvenno in the red range and can be used as agricultural film for greenhouses, hotbeds and greenhouses, in the form of a block ceiling coverings for exhibition or recreation areas, dance halls, etc.), in the form of a block or articles of arbitrary shape in the manufacture of furniture, decorative items, etc. At this offer composition has a high adaptability and ease of manufacture and application.

1. Svetopropusknaya polymer composition comprising a thermoplastic (co)polymer and active additives a, b, C and D, where a is an organic and/or inorganic salt of europium, one or more compounds from the class-diketones, With connection from the class nitrogen and/or oxygen-containing heterocycles, or from a number of oxides, organic amines, phosphines or sulfides, and D - salt alkaline, alkaline earth metal and/or ammonium and organic acids busy number and/or amine in the following ratio, wt. %:

Component a IS 0.001 - 5

Component IS 0.001 - 5

The component IS 0.001 - 5

Component D is 0.001 - 5

Thermoplastic (co)polymer - Rest

2. Polymer composition under item 1, characterized in that as a thermoplastic (co)polymer contains a high-pressure polyethylene or low density polypropylene, a copolymer of ethylene and PR, the polyacrylates, polyamides, polyesters.

3. Polymer composition under item 1 or 2, characterized in that the inorganic salts it contains europium nitrate or halide europium, hydrated or anhydrous.

4. Polymer composition according to any one of paragraphs.1 to 3, characterized in that as the organic salts of europium it contains a connection from a number of europium salts with formic acid or its homologues to C18inclusive; with triperoxonane and perfluorinated homologues to C4inclusive; with mono-, di - and trichloroacetic acids; naphthyl-, phenyl - and diphenylalanine acids; benzoic acid and its substituted derivatives containing 1 to 5 halogen atoms and/or 1 - 5 alkyl or CNS groups1- C18, phenyl or benzoyloxy group; aromatic hydroxyacids containing 1 to 3 hydroxyl groups in the benzene or naphthalene cycle; with aliphatic saturated dicyclomine3- C10inclusive; with aliphatic unsaturated mono - and dicarboxylic acids WITH3- C18containing phenyl, nattily or purely Deputy; aliphatic hydroxyacids WITH2- C6with one or two acids of the benzene series, naphthalene, diphenyl and dinaphthyl containing 2 to 4 carboxyl groups in the benzene nucleus, and one or two carboxyl groups in different positions in the naphthalene nucleus: from carboxylic acids, heterocyclic series, namely mono - and decolletage number of imidazole, pyridine, pyrazine, indole and quinoline.

5. Polymer composition according to any one of paragraphs.1 to 4, characterized in that the as-diketones it contains one or more compounds with the General formula R1C(O)CH2C(O)R2where R1and R2- different or identical residues, which represents a normal or branched alkyl WITH1- C18, perfluoroalkyl1- C4, unsubstituted phenyl or containing 1 to 5 halogen atoms and/or 1 - 5 alkyl or CNS groups1- C18or performanceline group1- C4inclusive, 1 - or 2-naphthyl, 9-anthracene, 9-phenanthrene, 2-thenoyl, unsubstituted or partially or fully substituted by the above residues; or one or more compounds from the series of 4-acyl-3-methyl-1-phenyl-2-pyrazolin-5-ones, where the acyl - from acetyl to stearoyl inclusive or benzoyl, unsubstituted or in which hydrogen atoms are partially or wholly replaced by atoms of f the h PP.1 - 5, characterized in that compounds of the class of nitrogen-containing heterocycles it contains compounds from a number of pyrazoline, pyridine, pyridazine, quinoline, isoquinoline, cinoxacin, cinnoline, benzoquinoline, unsubstituted or contains 1 to 3 methyl groups; from a number of 2,2'- or 4,4'-bipyridine, 2,2'-piperazine, 2,2'-dipyrimidine, 3,3'-dipyridine, 2,2'-dhenain, 1,1'- or 3,3'-diisoquinoline, 4,5-diazafluoren, 1,10-phenanthroline, 2,2', 6', 2"-terpyridine, 2,4,6 - three (2-pyridyl) - 1,3,5-triazine, 1,8-naphthiridine, 1,4,5,8-decreasefontsize, unsubstituted or contains one or two halogen atom, nitro-, amino-, hydroxy-, methyl-, methoxy - and/or phenyl groups.

7. Polymer composition according to any one of paragraphs.1 - 6, characterized in that compounds of the class of nitrogen and/or oxygen-containing heterocyclic compounds it contains a connection from a number of macrocyclic crown ethers or their nitrogen analogues, namely 15-crown-5, benzo-15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-crown-6, 2,2,1 - and 2,2,2-cryptand, cyclen, cycles, doxycyclin, hexarelin, unsubstituted or containing 1 to 4 residue acetic acid under nitrogen atoms or carbon.

8. Polymer composition according to any one of paragraphs.1 to 7, characterized in that, as with the s pyridine, unsubstituted or contains 1 to 3 methyl groups, N-oxide, quinoline, unsubstituted or contains one to two methyl groups, N-oxide benzoquinoline, N - oxide-2,2'-bipyridine, N-oxide 1,10-phenanthroline, N,N'-dioxide, 2,2'-bipyridine, N,N'-dioxide, 1,10-phenanthroline; the connection of a number of P-oxides trialkyl(aryl)phosphines containing alkyl groups WITH4- C8and/or phenyl group, unsubstituted or containing alkyl substituent WITH1- C4or CNS Deputy1- C4or pentafluorophenyl; the connection of a number of S - oxides, dialkyl(aryl)sulphides, where the alkyl WITH1- C8and aryl is unsubstituted phenyl or pentafluorophenyl.

9. Polymer composition according to any one of paragraphs.1 to 8, characterized in that as the organic salts of alkali or alkaline earth metal and/or ammonium it contains salt Li+, Na+, K+, Mg+Ca2+, NH4+, R1NH3+, R1R2NH2+, R1R2R3NH+, R1R2R3R4N+where R1- R4the same or different alkali4- C18or benzyl, with an organic acid busy WITH some4- C18.

E. General formula RNH2, R1R2NH or R1R2R3N, where R1- R3the same or different alkali4- C18or benzyl.

 

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