FI81820C - POLYMERT MATERIAL FOER TAECKNING AV DRIVHUS. - Google Patents

Description

1 81820

This invention relates to agriculture and relates primarily to greenhouse equipment; more specifically, it relates to polymeric materials for coating greenhouses.

In order to accelerate the growth and development of plants and to improve farm yields in greenhouses, polymeric materials are required, which are manufactured especially as greenhouse coatings. The film-like polymeric materials intended for this purpose should meet the following requirements: they must be transparent in the visible region of the spectrum; they must be able to absorb sunlight υνί 5 component; they must have good heat retention properties; i. the ability to absorb and reflect soil infrared radiation; they must not contain or develop toxic substances.

From the spectrum of sunlight, a wavelength range of 450-750 nm can be selected, which is most advantageous for plant growth and development. The most efficient in this range is the orange-red band with a wavelength of 580-750 nm. Green light at 25-550 nm is less efficient. In such light, plants require higher energy consumption. Plants are adversely affected by UV rays, while IR rays (750 to 1,000 nm) are not absorbed by them.

Intensive research is currently being conducted in many countries to develop polymeric materials for greenhouse coatings. By introducing chemical additives into the polymers, the polymeric materials are imparted with optical properties that are most advantageous under natural lighting conditions, in a protected ground, i. plant-35 for the growth and development of plants grown in rooms.

2,81820

Numerous polymeric materials for greenhouse coatings are known in the art, which are based on polyethylene (PE), polypropylene (PP), polystyrene (PS), polymethyl methacrylate (PMMA) and copolymers thereof, and which contain various additives which give the polymeric material certain properties which are essential. for growth and development (cf. Encyclopedia of Polymers, vol. 2, 1974, "Sovetskaya Encyclopedia" Publishing House, Moscow, p. 950).

10 It is known that polymeric materials for greenhouse coatings partially penetrate the UV component of sunlight, which has a detrimental effect on plants.

Numerous methods have been proposed in some publications for "cutting" UV radiation by introducing additives that absorb this radiation into the polymer. Accordingly, JA Patent No. 53-136050, Cl. 25 (I) H 296, Int. Cl. C 08 K 5/34 discloses polymer coatings which retain UV radiation and which are used in agriculture to coat greenhouses. In the process for preparing such polymeric materials, film-forming resins are mixed with plasticizers, heat-resistant substances such as TiO 2, CaCO 3, pigments such as carbon black and dyes such as phthalocyanine blue and green. Polyvinyl chloride, poly-25 styrene, polypropylene, polymethyl methacrylate are used as film-forming resins. Derivatives of phthalic, maleic, citric and other acids are used as plasticizers. This mixture is compressed into a 100 film which absorbs the UV component in the wavelength range of 350 to 380 nm. The absorption efficiency of the polymer coating is 30 to 90%. Although such film coatings effectively absorb UV radiation, they nevertheless have a low transparency in the visible range of 40-50%, which has a detrimental effect on the development of farm crops. Furthermore, such a polymeric material cannot convert the absorbed UV component into a red component and therefore cannot use sunlight effectively.

U.S. Patent No. 4,081,300 to Cl. 156/71, Int. Cl. E 04 F 13/00 discloses a polymer blend into which additives are absorbed which absorb UV radiation in the wavelength range 5,200-380 nm. The absorption of UV radiation is 90%. This polymer film also effectively absorbs UV radiation from sunlight, but is insufficiently transparent in the visible light region and cannot turn the absorbed UV component red, so that it cannot use the energy of sunlight 10 to the maximum.

Polyolefin films used in agriculture are known in the art, which are prepared from a mixture of 80% by weight of polyolefin, for example polyethylene or a copolymer of ethylene and vinyl acetate, and 1-15% by weight of an alkali metal sulfate of Al (OH) 3 and alunite of the formula (S04) 4M3M3. 120H, where M3 is a trivalent metal, M1 is a monovalent metal alloy. 0.05 to 2% by weight of a UV-absorbing additive, for example benzophenone or benzotriazole, is added to the combination. The final polymer film has a low transmittance, between 7 and 17 μm and good light scattering properties, although it can change the absorbed UV radiation to red (FR Patent Application No. 2,419,955 Cl. A 01G69 / 14, 13/02, published October 12, 1979). ).

Also known in the art is a polymer combination for the production of agricultural films which contains by weight: polyethylene or ethylene copolymer with 15-20% vinyl acetate - 73-94, kaolin 5-20, a wetting agent such as diethan-30 for the acids of the C10-C16 fraction. liamide - 0.5 to 5.0, the reaction product of sorbitol and stearic acid - 0.5 to 2.0. The film is transparent in the visible light range 380-780 nm: full - 90%, straight - 45% (cf. USSR Inventor's Certificate No. 711061 Cl. C 08L23 / 06, C 08L23 / 08, published January 26, 1980). With all its positive properties, this film cannot change the absorbed UV component to orange-red, i. it cannot promote * 81820 plants more complete utilization of sunlight.

U.S. Patent No. 4,220,736 Cl. C 08L61 / 02, C 08L31 / 04, published on 2.9.1980, discloses a combination for forming films or sheets, which combination contains 5 parts by weight of low density, heat-resistant polyethylene, a copolymer of ethylene with 5-20% vinyl acetate or a mixture of both - 100, polyacetal - 1-20. Films made from this blend have good transparency, mechanical strength, and flexibility that reaches the same properties as films made from low density polyethylene. When the films thus prepared are used for covering plants of growing plants (greenhouses, heating media, etc.), the air temperature on the surface of the film is 0.9 to 1.3 ° C higher than in the case of the low-density polyethylene film. Such a film cannot effectively absorb UV radiation.

JA Patent Application No. 54-105187 Cl. 25 (9) A II, B 32 B 27/32, filed February 6, 1978 (No. 53-12169, published August 17, 1979) discloses the manufacture of laminated films, 20 which have good heat retention. Polymers (polyethylene, polypropylene, etc.) modified (0.01 to 1%) with unsaturated carboxylic acids (such as acrylic, methacrylic, maleic, fumaric, itaconic, etc.) acids are used to make polymeric laminated films. anhydrides, esters, amides or a mixture of modified and unmodified polymer.

Such a film has good heat retention properties, but it insufficiently absorbs the UV component of sunlight and is unable to convert it to a red-orange component.

A weather-resistant film for agricultural applications is also known in the art (cf. JA Patent Application No. 54-159481 Cl. 25 (9) A II, B 32 B 27/32, filed June 6, 1978, No. 53-67976, published December 17, 1979). . This transparent, weather-resistant, dust- and cold-water-resistant film has three layers: the outermost is low-density polyethylene 5,81820 (density 0.925), the middle layer is a copolymer of ethylene with 14-28% vinyl acetate and / or a copolymer of vinyl alcohol. % olefin (ethylene) and the inner layer is low density polyethylene, copolymer of ethylene with vinyl acetate or a mixture thereof.

However, this film insufficiently absorbs the UV component of sunlight and cannot convert it to an orange-red component.

JA Patent Application No. 52-1182558 Cl. C 08L23 / 2, published March 24, 1978, describes the production of a film for greenhouse coating, which film is formed from a mixture consisting (by weight) of: polyolefin 100, ionomeric resin - 0.1-5, surfactant - 1- 5. The ionomeric resin preferably contains 15 sodium ions. The resulting film has good anti-adhesive properties that remain throughout its service life (about 2 years). The transport of the surfactant to the surface of the film allows the anti-adhesion properties of the film to be maintained for a long time and thus prevents the accumulation of water droplets on the inner walls of the greenhouses.

However, despite its good anti-adhesion properties, this film is not able to convert the absorbed UV light into a red component. Therefore, the introduction of various additives into the polymer or copolymer makes it possible to modify both the mechanical and heat-retaining properties of the polymeric material and the optical properties, in particular the transition spectrum in the UV region.

Thus, the addition of additives has yielded materials that absorb up to 90% of the radiation in the UV region of the spectrum.

The red component of sunlight is the most important factor for plant growth. For this reason, greenhouse polymer coatings should have maximum transmission of the red component of the 35 spectra of sunlight and, in addition, should have the ability to convert the absorbed UV component into the red component of sunlight. Thus, in order to achieve efficient growth and development of plants grown in protected soils and to achieve early ripening of their fruits, materials are required that absorb the UV component of sunlight and turn it red. Polymeric materials for greenhouse coatings having these properties are not known to date.

This invention relates to a polymeric material for greenhouse coverings which would ensure accelerated plant development, ensure faster ripening of crops and higher yields as a result of more efficient use of sunlight energy.

This object is achieved by a polymeric material for greenhouse coatings 15 comprising a visible polymer and an additive which absorbs the UV component of daylight and is characterized in that it contains as additive at least one f-element compound capable of absorbing the UV component of daylight and 20 luminescent spectra. within the precincts of.

According to the present invention, the polymeric material contains, as an additive, a f-element compound having the general formula:

25 Me-X, Yn.A

wherein Me is Sm, Tb, Dy or UO 2; n is 2 or 3; m is 0 or 1; k is 0-3; X and V represent chlorine ions or nitrate ions; An anion of a monocarboxylic acid such as benzoylbenzoic acid or anthranilic acid; or the anion of β-diketone such as acetylacetone, benzoylacetone, dibenzoylmethane, benzoyl trifluoroacetone, tenoyl trifluoroacetone or hexafluoroacetylacetone; li 7 81820

R RO R

L = R - ^^ P = 0, RO - ^> P = 0, ^> S = 0,

Vs VO 'R

(o) - (o) (^ ^ ~ (o) or (qX j * \ N7 'N _ / \ -N7 \ N / N____ CH = CH2 and R is alkyl or aryl; or wherein Me is Eu; is 3, m is 0 or 1, k is 0-3, X and Y represent chlorine ions or nitrate ions, an anion of a monocarboxylic acid such as benzoylbenzoic acid or anthranilic acid, and L is as defined above, or X and Y are β-diketone such as anions of acetylacetone, benzoylacetone, dibenzoylacetone, dibenzoylmethane, benzoyl trifluoroacetone, tenoyl trifluoroacetone or hexafluoroacetylacetone;

RO X

3 ”to-N-CH = CH2 and R is alkyl or aryl.

The content of the additive specified above in the polymer is between 0.001 and 5% by weight.

In particular, the following compounds of element f can be used as additives: tris (trioctylphosphine oxide) trichlorouropium (III); 35 tris (dihexyl sulfoxide) trichlorouropium (III); ♦ 8,81820 tris (tributyl phosphate) trinitrateeuropium (III); 1.10-phenanthroline trinitrate toeuropium (III); triphenylphosphine oxide bis (hexafluoroacetylacetonate) uranyl 2,2'-dipyridyl-tris (benzoyl trifluoroacetonate) samarium (III); bis (triphenylphosphine oxide) tris (acetylacetonate) terbium (III); 1.10-Phenanthroline tris (benzoyl trifluoroacetonate) -dysprosium (III).

As the polymers, various photo-transparent polymers can be used, such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, polycarbonate, and other acceptable polymers and copolymers.

The process for preparing the polymeric materials of this invention essentially comprises disintegrating the starting polymer and the above-mentioned additive, i. the addition of the f-element compounds of the above formula in an amount of 0.001 to 5% by weight. The components are mixed thoroughly and the resulting mixture is formed into a film by compression.

In another embodiment of the present invention, 0.001 to 5% by weight of the above-mentioned additive is added to the liquid monomer. The mixture of components is thoroughly mixed and when the additive is dissolved in the monomer, the reaction mixture is block polymerized.

As previously mentioned, the amount of additive in the polymer or monomer may vary from 0.001 to 5% by weight. This amount is selected on the basis that at an additive content of less than 0.001%, the ability of the material to absorb the UV component is reduced. An additive content of more than 5% by weight is not recommended because it does not lead to an increase in the positive effect.

The polymeric materials for greenhouse coatings 35 of the present invention have the advantage of having better optical properties compared to known polymeric materials intended for the same purpose.

The materials of this invention absorb up to 98% of the UV component of daylight in the range of 200-450 at 5 nm; up to 80% of the absorbed UV light is converted to an orange-red component. This results in an increase in the light transmittance of the material in the region of the orange-red component (580-750 nm) by 50-81%.

The above-mentioned polymeric materials used for greenhouse coatings enable more efficient cultivation of farm crops on protected soil. The material of this invention has a positive effect on plant growth and development. Plants grow faster and have a higher ripening rate. The ripening period of the plants and the conditions of massive fruit formation become 3-14 days earlier. This can be explained by the fact that the polymeric material, due to the presence of the additive of the present invention, has the ability to turn the UV component absorbed from sunlight into orange-red and thus provides conditions for plants to use sunlight more extensively.

The polymeric material of this invention has been used to coat greenhouses where farm crops (radish, lettuce, cabbage, tomatoes, eggplants, cucumbers, pepper) were grown. Depending on the plant species and varieties, 10-90% higher yields have been observed compared to the yields of crops grown under cover without f-element compounds as additives.

Under the materials of this invention, more favorable thermal conditions are achieved for plants in greenhouses. The air temperature in such greenhouses is 3-5 ° C higher compared to the control. The materials of this invention reveal their heat retention properties during early frost periods. Thus, as the temperature dropped in the open to -5 ° C, the same temperature was observed in the control 81 820 roll greenhouse, where the plants were completely destroyed. Under the materials of this invention, the temperature dropped to only 0 ° C and no damage was observed in the plants.

Depending on the type of polymer used, additive 5 and its amount, a wide range of polymeric materials to be used for greenhouse coatings is possible. The term "greenhouse" is understood to mean heating media, greenhouses and other equipment in which vegetables and other farm crops are grown in daylight, on protected land.

The process for preparing the polymeric materials of this invention is simple, i. it does not require any special equipment or special conditions, so that it can be easily implemented on a commercial scale using conventional equipment used in the production of polymeric materials.

It has been found that vegetables grown in greenhouses coated with the materials of this invention grow faster and give a higher yield. Thus, the tomato yield increases by 50-90%, cucumber yield by 15-50%, radish by 20-25%, lettuce by 15-20%, pepper by 15-20%, eggplant by 10-15% compared to vegetable crops grown in greenhouses covered with known polymeric materials which do not contain E-element compounds as additives.

All of the above advantages allow the polymeric material of this invention to be considered commercially effective.

The f-element compounds of the above general formula used as the additive of the present invention are non-toxic compounds. They are known and described in the literature.

Compounds of Europium with a nitrate group and 1,10-phenanthroline are described in the Journal of Inorganic Chemistry, 1965, Vol. 10, No. 4 ("Nauka" Publis-35 Hing House, Moscow); MY. Lobanov, V.A. Smirnova, "Complex Compounds of Rare-Earth Elements with 1,10-Phenanthroline," 81820 p. 840).

Nitrate complexes of Europium with tributyl phosphate, dihexyl sulfoxide and triphenylphosphine oxide are described in "Journal of Inorganic Chemistry", 1981, Vol. 26, No. 3 ("Nauka" Publishing House, Moscow); Yu. I. Murinov, V.T. Danilov, G.G. Bekbayeva, Yu. E. Nikitin, "Synthesis and Properties of Different-Ligand Complexes of Rare-Earth Elements with Dihexylsulfoxide and Tributylphosphate," p. 596.

The preparation of rare earth chloride complexes with sulfoxides of petroleum origin is described in "Newsletters of the USSR Academy of Sciences, Chemical Series", 1977, No. 12 ("Nauka" Publishing House, Moscow): Yu. I. Murinov, Yu. B. Monakov, Z.G. 15 Shamayeva, N.G. Marina, V.S. Kolosnitsyn, Yu. E. Nikitin, S.R. Rafikov, "Preparation of Complexes of Sulphoxides of Petroleum Origin and Tributylphosphate with Chlorides of Rare-Earth Elements", pp. 2790.

The synthesis of β-diketo-20s of europium, samarium and dysprosium with neutral ligands such as 1,10-phenanthroline, 2,2'-dipyridyl, phosphine oxides, etc. is reported in the Journal of Amer. Chem. Soc. 1964, vol. 86, No. 23 (1155 Sixteenth St. Washington, L.R. Melby, No. 1, Rose, E. Abramson, J.C. Caris, 25 "Synthesis and Fluorescence of Some Trivalent Lanthanide Complexes", p. 5117.

The synthesis and properties of uranyl β-diketonate compounds with nitrogen- and oxygen-containing ligands are described in "Journal of Inorganic Chemist-30 ry", 1983, vol. 28, No. 9 ("Nauka" Publishing House, Moscow): V.E. Karasev, I.V. Schukina, R.N. Schelokov, "Ad- .- ducts of Uranyl β-Diketonates," pp. 2321.

The synthesis of terbium complexes with anthranilic acid and various ligands is described in "Inor-35 ganic Chemistry", 1981, vol. 26, No. 2 ("Nauka" Publishing House, Moscow): V.E. Karasev, N.I. Stablevskaya, I.V.

12 81 820 chukina, N.F. Zhelonkina, “Compounds of Terbium with Anthranylic Acid and Neutral Ligands,” p. 350.

In accordance with the present invention, a wide range of materials is proposed for greenhouse coatings. However, the 5 most effective of these are materials to which f-element compounds corresponding to the general formula are added as additives:

Men + X, Yn., P. 10 wherein Men * is Eu3 *, Tb3 *, X, Y-benzoyl trifluoroacetone anion, benzoylbenzoic acid, nitrate ion; L = 2,2'-dipyridyl, 1,10-phenanthroline, triphenylphosphine-15-oxide, n = 3, m 0.1; k * 1-2.

Materials with this additive have an absorbency with respect to the UV component of sunlight of 90-99% and a high quantitative yield of fluorescence, allowing the conversion value of the absorbed UV component to be adjusted to 70-85% at the expense of light loss. Furthermore, materials with the additives of this invention are less likely to degrade over time when exposed to sunlight, thus allowing a longer shelf life of the polymeric material compared to other compounds.

As polymers, products such as polyethylene, polypropylene, polyvinyl chloride, polycarbonate can be used. Growing plants under coatings made of these materials ensures the highest possible effects compared to materials containing other f-element compounds.

-. In order that the invention may be better understood, the following are some specific examples; of which Examples 1-172 illustrate a polymeric material, its preparation and optical properties, Examples 173-177 illustrate the use of this material as greenhouse coatings for growing agricultural crops.

Example 1 100 kg of granulated polyethylene are placed in a blender. To the same mixer is added 100 g of the europium compound of the formula EuCl3.3TOPh0, where TOPhO is trioctylphosphine oxide in the form of a fine, dry powder. The components are mixed thoroughly and the resulting mixture is processed in an extruder into a skull 0.1 to 0.15 mm thick. The obtained material contains 0.1% by weight of the above-mentioned europium compound. The material thus prepared has the following optical properties: the absorption of the UV component of daylight in the range of 200-450 nm is 97%; The conversion of the absorbed UV component (due to light scattering) to an orange-red component is 35%; the light transmittance of the material in the range 580-750 nm is 75%. This material is in the form of a transparent film ready for use in agriculture for coating greenhouses 20.

Examples 2-70 are shown below. These examples illustrate a polymeric material prepared in the same manner as described in Example 1 above, with the exception that other f-element compounds are used according to the general formula given above; their amount and the nature of the polymers used are also different. The following symbols for compounds are used in Table 1: TOPhO - trioctyl phosphine oxide DHSO - dihexyl sulfoxide 30 DMSO - dimethyl sulfoxide TBP - tributyl phosphate

PhEN - 1,10-Phenanthroline HFAA - Hexafluoroacetylacetone TTA - Tenoyl trifluoroacetone 35 BTFA - Benzoyl trifluoroacetone VBI - Vinylbenzylimidazole 14 81 820 BBA - Benzoylbenzoic acid TBT-anthranilic acid , 2'-dipyridyl PSO - petroleum sulphoxides 10

table 1

Ex. No. Polymer Base Additive Formula 12 3 15 ----------------------------------------- -------

2 Polyethylene EuCl3.3TOPhO

3 "EuC13.3TOPhO

4 "EuC13.3DHSO

5 "20 6 7" Eu (DBM) 3.2DHS0 8 ""

9 M M

10 "EuCl3.3PSO

• 25 11 12 13 "Eu (N03) 3.3TBPh 14 15" Eu (N03) 3.3TBPh

30 16 "Eu (NO3) 3.PhEN

17 18 19 Polyethylene Eu (BBA) 3.2DP:

Eu (N03) 3. PhEN:

35 Eu (TTA) 3. Phen

1: 1: 1 li 81820 20 Polyethylene Eu (BBA) 3.2DP: '\

"Eu (NO3) 3. PhEN: L

"Eu (TTA) 3. PhEN J

1: 1: 1 5 21 Polyethylene Eu (BBA) 3.2DP: "" Eu (NO3) 3. PhEN: »” Eu (TTA) 3. PhEN j 1: 2: 3 22 Polyethylene Eu (BBA) 3.2DP: Λ 10 "Eu (N03) 3. PhEN:» "Eu (TTA) j. PhEN ^ 1: 2: 3 23 Polyethylene Eu (NO3) 3.3DHSO

24 ”Eu (BBA) 3. PhEN

15 25 "Eu (BBA) 3. PhEN

26 "Eu (TTA) 3.DMSO

27 "Tb (HFAA) 3. PhEN

28 "Sm (TTA) 3. PhEN

29 "U02 (TTA) 2.DHS0

20 30 "U02 (HFAA) 2. PhEN

31 Polyvinyl chloride EuCl3.3TOPhO

32 "" 33 34 "EuC13.3DHS0 ·. 25 35 36 37" Eu (DBM) j. 2DHS0 38 39 ""

30 40 "EuC13.3PSO

41 42 43 "Eu (N03) 3.3TBPh 44" «35 45 ie 81820

46 "Eu (NOj) a. PhEN

47

48 "Eu (NO3) 3. PhEN

5 49 "Eu (BTFA) 3. PhEN

Tb (BTFA) 3. PhEN J 1: 1 50 51 "Eu (BTFA) 3. PhEN:")

10 Tb (BTFA) 3. PhEN J

1: 1

52 Polypropylene EuCl3.3TOPhO

53 54

15 55 "EuC13.3DHSO

56 57

58 "Eu (DBM) 3.2DHSO

59 20 60 61 Polypropylene Eu (NO3). (BTFA) 2.

.2PhPhO

62 63 25 64 Polypropylene Eu (NO3). (TTA) 2.

.2TBPhO

65 66

67 "Eu (NO3) 3.PhEN

30 68 "" 69

70 "Dy (BTFA) 3rd PhEN

ti 35 17 81 820

Table 1 (continued)

Additive- Material- Absorbed UV Content of material 5, UV absorption% migration (light transparency va-% by weight in the range of scatter due to orange-200-450 mm) red% in the range 580-750 mm 10 ----- -------------------------------------------------- - 1 4 5 6 7 2 1,0 86 44 76 3 0,4 91 38 79 15 4 1,0 99 33 75 5 0,1 85 39 76 6 0,6 93 36 78 7 1,0 98 68 77 8 0.01 89 78 78 20 9 0.6 96 71 81 10 1.0 99 37 71 11 0.1 93 42 70 12 0.5 97 40 72 13 1.0 97 40 71 25 14 0.01 88 54 70 15 0.06 94 45 73 16 5.0 99 62 74 17 0.01 90 71 74 18 0.2 97 69 78 30 19 220-380 nm 0.1 92 75 78 20 220-380 nm 0.03 95 75 92 21 220-380 nm 35 0.15 98 79 90 1β 81820 22 220-380 ran 0.24 100 78 81 23 2.0 99 40 5 24 0.05 89 - 25 0.5 92 26 0.05 90 27 0.05 90 - 28 0.05 87 10 29 0.05 88 - 30 0.05 89 - 31 1.0 97 37 75 32 0.1 82 46 77 33 0.4 91 40 79 15 34 0.5 95 38 78 35 0.1 89 43 76 36 1.0 99 34 75 37 0.5 99 70 79 38 0.2 96 72 82 20 39 0.05 91 76 78 40 0.5 97 37 73 41 0.1 92 42 70 42 1.0 99 35 67 43 0.5 94 44 72 25 44 0.1 90 48 69 45 1.0 98 40 68 46 0.4 96 69 79 47 0.1 93 72 73 48 0.8 98 65 76 30 49 5.0 99 76 77 50 0.5 92 88 78 51 0.1 96 82 81 52 1.0 98 34 74 53 0.5 92 39 77 35 54 0.1 85 43 74

II

19 81 820 55 1.0 99 34 74 56 0.5 94 37 77 57 0.1 89 39 75 58 1.0 99 67 79 5 59 0.01 92 77 79 60 0.5 97 72 83 61 1.0 99 36 67 62 0.5 98 38 71 63 0.1 95 44 68 10 64 1.0 98 39 68 65 0.01 85 51 67 66 0.04 93 43 71 67 1.0 99 64 74 68 0.01 91 72 73 15 69 0.15 98 68 75 70 0.06 94 66 81

Example 71 20 Styrene is added to a 100 kg reactor and 50 g of the europium compound are added? EuCl3.3TOPhO and Sm (BA) 3. lTBPhO, where TOPhO = trioctylphosphine oxide, TBPhO = tributylphosphine oxide. The mixture of components is thoroughly mixed, and when the additive is completely dissolved in the monomer, the composite segment is polymerized. The material obtained has the form of an organic glass (thickness 3 mm) and contains 0.5% by weight of the Europium compound. The material thus prepared has the following optical properties: the absorption of the UV component of 30 daylight in the range of 200 to 450 nm is 98%; the conversion of the absorbed UV component to the form of fluorescent radiation in the orange-red region of visible light is 37%; The transparency of the 35 material to light in the range 580-750 20 8 1 8 2 0 nm is 77%. This material is ready to use as a greenhouse coating.

Examples 72-172 are given in Table 2 below.

These examples illustrate polymeric materials prepared in the same manner as described in Example 71, except that compounds of the f-element of the general formula above have been used, other amounts and other polymers have also been used. Table 2 uses the same abbreviations for compound names 10 as in Table 1 above.

Table 2

Eg Polymer Matrix Additive Formula 15 No. 12 3 72 Polystyrene EuCl -, * 3T0Ph0: Sm (BA) j * 2TBPhO (1: 1) 73 20 74 75 EuCl * 3DHS0: Tb (AA) ^ * DHSO (1: 1) 76 77 78 Eu (TTA) * DP: Tb (AA) * DP (1: 1)

25 79 J

80 81 Eu (DBM) * 2DHS0: Tb (ANT)., * 2DHS0 (1: 1) j> 82 83 30 84 EuCl * 3PS0: Sib (BTPA) ^ * DP (1: 1) 85 86

II

35 2i 81820

Table 2 (continued) 12 3

5 87 Poly styrene 3u (NO 2) ^ 3 TBPb: ^ b (AA) ^ * 2TPhPhO

(1: 1) 88 89 90 3u (N0 ^) ^ * pbJEN: Dy (BTFA) ^ * Ph £ N 10 (1: 1) 91 92

93 Polycarbonate Su (HFAA) * Ph.EN: Tb (HFAA) _ · PhEN

3 (1: 1) 3 15 94 „_ rt _ n_ 95“ “96 Eu (TTA) • PhEN: Tb (AA) 3'PhEN (l: l) 97 98 2o 99 Eu (BTPA) 3 * PhEN: Tb (BTPA) 3, PhEN (1: 1) 100 101 -, r- 102 Polyethylmethacetone EuCl.'3TOPtxO: Tb (AA), * 2TPtLPh (1: 1) rylate 3 $ 103 -M-25 104 105 Polymethylmethacetone EuClo ^ DHSOsOib'AA) * 2TPhPhO (l: l) alkylate 3 3 106 107 30 108 Polymer 1 acrylic - Eu (TTA) ^ * DP: Tb (TTA), * DP (l: l) prepared 3 3 · '109 110 111 Eu (DBM) * 2DH30: Sm (DBf / l) 3 * 2DHSO (l: 1) 35 112 113 -: I-

Table 2 (continued) 22 81 820 12 3 5 114 Polyethyl acrylate L EuCl ~ * 3PS0: Dy (BTPA) ^ * TPhPh0 (l jl) 115 116 117 Eu (N0 ^) ^ * 3TBPhsTb (AA) ^ * PhENCl: l) 118 10 119 120 Eu (H03 *) • PhEN: U02 (HFAA) 2, TPhPh0 (l: 4) 121 122 Polymethylmethac- Eu (N0.i),> * PbEN: U0o (HFAA V TPhPhC (l: 4) radylate J 3 ^ 15 123 Eu (HFAA) * PhEN: Tb (HFFA) 3 * PhEN (lii) 125 126 Eu (TTA) * PhEN: Tb (AA) 3ePbEN (l: l) 127 - - 20 128 129 E u (B TFA) 3 · PhEN; UO ^ (H FAA) 2 * TPbPhO (1: 1) 130 131

132 Eu (TTA> 3 * VBI

25 133 Eu (NO3) ‘3DHS0

134 Polymethylmethane - Eu (BBA) -, · 2DP

grate · *

135 2u (BBA) 3’PhEN

136 Tb (TTA) * DMSO: Eu (TTA) -DiiISO (li2) 3Q 137 - · »- Tb (ANT)« DKSOiEu (BA) ^ .DH30 (1: 2) 138 Tb (AA) 33.PbEN: Eu (BTFA) 3 * PbEN (li2) 139 Tb (HFAA) 'PhEN: Eu (HFAA) 3 * PhEN (1: 2) 140 U02 (TTA) 2-DHSO0: Eu (TTA) 3 * 2DHS0 (1: 2) 141 UO2 (HFAA) 2ePhEN: Eu (BTFA) * PhEiJ (1: 2) 142 Copolymer with 35% 30% polystyrene and 70% polymethyl methacrylate EuCl3 * 3TOPbO: Tb (AA) -j * 2TCPhO (1; 1) 143 144 23 81 820

Table 2 (continued) ~ I 2 ~ ~ 3 ^ 145 Copolymer with 30% polystyrene and 70% polymethyl methacrylate

EuCl 3 * 3DHSO: Tb (31; PA) 3e2DHSO

(1: 1) 10 146 147 148 * 'Eu (TTA) ^ * 2DP: Tb (AA) * Pb.EN (1: 1) 149 150 ^ 151 Copolymer with 30% polystyrene and 70% polymethyl methacrylate

Eu (DBM) 2 · 2DHS0; Sm (DBM) y • 2DHS0 (1: 1) 20 152 153 154 EuCl3 * 3PoO: Tb (AiNT) y Diaso (lsl) 155 156 -M- 25 157 Eu (NO ^) ^ * 3TBPti: Sm (BTFA) ^ '* DP (1: 1) 158 159 30 160 Eu (NO ^) ^ · ρϋΕΝϊDy (eTP k) y • PhEN (lsl) Lei 162 i. *: 163 Eu (HFAA) ^ * PhEN: Tb (HPAA) ^ * 35 * PhEN (l: 1): 164 165 24 81 820

Table 2 (continued) 12 3 ^ 166 Copolymer of 30% polystyrene and 70% polymethyl methacrylate

Eu (BA) ^ * PhEN Sm (BA) ^ * PhEN (lii) 10 167 168 169 Eu (B TFA) PhEN: Ί

Tb (B TFA} PhEN: 1 (1: 1: 1) U02 (HFAA) 2 (TPhPhO) 15 170 171 172 3m (B TFA) 3 PhEN:

Eu (BTFAK PhEN: L (1: 1: 1)

Dy (B TFA) ^ PhEN J

20 li

Table 2 (continued) 25 81 820

Eg Additive- UV material- Absorbed Materials No. Concentration Iin absorption UV radiation transparency% by weight in the range of 20C-% of migration to light orange- 450 mm (with light-red% of light in the range of 580-k) 750 mm% of · 10 ”1 4" 5 6 7 ~ 72 0.5 98 37 77 15 73 0.25 91 40 81 74 0.01 87 43 76 75 0.1 90 39 78 76 0.8 94 37 81 77 2.0 99 34 77 20 78 0.1 92 76 79 79 0.15 97 72 82 80 0.25 99 68 78 81 0.01 90 78 79 · · 82 82 0.16 95 73 83; 80/84 0.1 93 44 70 V 85 0.6 98 39 73: · '86 1.0 99 35 68 87 0.1 90 45 68 30 88 0.7 93 42 72 89 1.0 96 37 09 90 0.1 99 63 70 91 0.01 93 74 71 92 0.05 99 69 73 35 93 0.01 90 77 78 94 0.03 94 72 83 95 0.05 98 67 79 96 0.1 -6 70 77 26 81 820

Table 2 (continued) 1 4 '5 6 7 5 97 0.025 88 79 79 98 0.05 93 73 83 99 0.1 88 75 79 100 0.2 93 71 84 101 0.35 97 68 80 10 102 0.01 87 44 77 103 0.23 92 39 80 104 0.5 98 37 77 105 0.1 89 39 78 106 0.9 95 36 81 15 107 2.0 99 33 73 108 0.05 96 87 82 109 0.001 87 76 81 no 0.02 93 71 86 or 0.05 99 71 81 20 112 0.001 91 78 82 113 0.025 96 74 86 114 0.1 94 45 72 115 0.7 98 40 76 25 116 1.0 99 36 66 117 0 , 1 84 46 66 118 0.4 91 40 70 119 1.0 96 37 67 120 0.05 99 68 72 30 121 0.01 94 72 66 122 0.1 99 63 63 123 0.05 99 70 83 Γ: 124 0.001 90 78 83 V 125 0.02 95 73 88 35 126 0.05 98 70. 80 127 0.001 89 78 82 · *: 128 0.02 96 74 92 li

Table 2 (continued) 27 81 820 14 5 6 7 5 129 0.05 97 66 80 130 0.001 88 75 81 131 0.02 93 70 83 132 0.2 98 80 80 133 0.04 97 - 10 134 0.015 96 - 135 0.01 96 - 136 0.05 - 85 137 1.0 88 138 0.02 82 - 15 139 0.02 83 - 140 0.02 87 - - 141 0.02 89 - 142 0.01 87 43 77 143 0.3 92 39 80 20 144 0.5 98 36 76 145 0.1 89 38 77 146 1.0 94 36 81 147 '2.0 99 33 76 148 0.1 98 67 79' -.f 25 149 0.001 90 74 80 150 0.06 95 72 83 '151 0.1 99 70 30 152 0.001 91 76 81 153 0.06 95 73 84 30 154 0.1 94 43 71 155 0.6 98 39 74 156 1.0 99 37 70:: 157 0.1 37 44 68 158 0.5 92 41 71 35 159 1.0 97 37 67 160 0.1 99 62 84 28 81 820

Table 2 (continued) 1 4 5 ^ 6 7 5 161 0.05 99 68 73 162 0.01 92 71 65 163 0.05 98 70 81 164 0.001 90 79 82 165 0.03 94 73 35 10 166 0.1 97 58 82 167 0.001 88 76 80 168 0.04 94 73 86 169 0.1 98 66 81 170 0.001 86 76 81 15 171 0.04 93 70 84 172 0.05 92 55 73

Examples 173-177 are given in Table 3 below. These examples illustrate the use of the materials of this invention to coat greenhouses. 20 plants are presented from each greenhouse (test). For comparison purposes, 20 plants were used as a control, but they were grown in greenhouses under a conventional polymer film 25 with no f-element compounds as additives.

Data describing the growth characteristics of the plant are presented in Table 3 below.

Table 3 30 No. The material combination is the cucumbers in question, kg test control according to the example Ϊ 2 ~~ 3 4 173 Eg 16 101.4 87.9: · '25 174 Eg 19 102.4 87.2 175 Eg 80 102 , 9 88.0 176 Ex. 126 103 ° 177 Ex. 127 102.9 87.7 li 29 81820

Table 3 (continued)

Tomatoes, kg Cabbage seedlings, g (per 100 plants)

No. ______________________________________________ 5 test control test control 1 5 6 7 8 173 59.4 46.6 1.071 559 10 174 59.6 46.5 1.065 558 175 60.1 46.4 1.075 549 176 59.3 46.6 1.073 571 177 59.5 46.3 1.071 572 15 This polymeric material can be used in agriculture for the construction of greenhouses, greenhouses, heating platforms and other structures in which vegetables, flowers and other crops are grown under natural lighting conditions.

Claims (12)

1. Greenhouse polymeric material covering a light transparent polymer and an additive capable of absorbing the UV component of daylight and luminescent within the orange-red region of the spectrum, characterized in that it contains at least one compound of additive f elements having the general formula: ΜβηχΥη_. · ΐ * where Me is Sm, Tb, Dy or UO2; n is 2 or 3; m is 0 or 1; k is 0-3; 15. and Y represent chlorine ions or nitrate ions; an anion of a monocarboxylic acid, such as benzoyl benzoic acid or anthranilic acid; or an anion of a β-diketone such as acetylacetone, benzoylacetone, dibenzoylmethane, benzoyltrifluoroacetone, tenoyltrifluoroacetone or hexafluoroacetylacetone; R0 \L = R_7P ”°> R--P - O · O · R0 ^R 25 and R är is alkyl or aryl; or where Me is Eu; n is 3; m is 0 or 1; k is 0-3; X and Y represent chlorine ions or nitrate ions; an anion of a monocarboxylic acid, such as benzoylbenzoic acid; 'Or anthranilic acid, and L has been defined above; or 81820 X and Y are anions of a B-diketone, such as acetylacetone, benzoylacetone, dibenzoylacetone, dibenzoyl methane, benzoyltrifluoroacetone, tenoyltrifluoroacetone or hexafluoroacetylacetone; and R = R ° \ R \ L = R - P · O, RO - p V = O, S * O R * RO ^ R ^ 10 (qO. N_- CH = CH2 and R is alkyl or aryl. 2. Material according to claim 1, characterized in that the content of the additive is 0.001 - 5% by weight. 3. A material according to claim 1 or 2, characterized in that it contains as an additive a europium compound Eu (NO3) 3PhEN, where PhEN is 1,10-phenanthroline. 4. A material according to claim 3, characterized in that the content of the additive is 0.05 to 1.0% by weight. 5. A material according to claim 1 or 2, characterized in that it contains as an additive compounds Eu (BTFA) 3.PhEN and Tb (BTFA) 3.PhEN, where BTFA is benzoyltrifluoroacetone and PhEN is 1.10 -fenantro- 30 Iin. 6. A material according to claim 5, characterized in that the content of the additive is from 0.1 to 0.5% by weight. 7. A material according to claim 1 or 2, characterized in that, as an additive, it contains compounds Eu (NO3) 3PhEN and UO2 (HFAA) 2.TPhPh0 where HFAA is hexafluoroacetylacetone, TPhPhO is triphenylphosphine oxide and PhEN are 1,10-phenanthroline. 8. A material according to claim 7, characterized in that the content of the additive is 0.05 - 0.1% by weight. 9. A material according to claim 1 or 2, characterized in that it contains, as an additive, compounds Eu (BBA) 3.2DP, Eu (NO3) 3PhEN, Eu (TTA) 3PhEN, wherein BBA is a benzoylbenzoic acid anion, DP is 2,2-dipyridyl, PhEN is 1,10-phenanthroline and TTA is tenoyltrifluoroacetone. 10. A material according to claim 9, characterized in that the content of the additive is 0.012 - 0.1% by weight. 11. A material according to any one of claims 1-10, characterized in that it contains as a polymer at least one polymer, such as polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polystyrene, polymethylmethacrylate or copolymers thereof. Use of polymeric material according to any of claims 1-11 for covering greenhouses.