A method of reducing the allocation of phosphine from red phosphorus and fire protective polymer composition
(57) Abstract:Use: in the manufacture of fire-protected polymeric materials and products from them. The inventive fire-protected polymer composition comprises a flame retardant 20-80 wt.% the product of the interaction of red phosphorus with cinnamon transliterator, taken in an amount of 0.1-100% by weight of red phosphorus. The relative content of phosphine 14 days in a sealed flask containing 1 g of red phosphorus and 1 g cinnamon translitered, when the moisture content of 70% to 0.22%. 2C. and 5 C.p. f-crystals, 4 PL. The invention relates to a technology for fire protective polymer materials and products and related method of reducing the allocation of phosphine from red phosphorus and polymer compositions containing as a flame retardant, red phosphorus, either in the form of pre-treated red phosphorus, or in conjunction with uterine mixtures, or by adding a process connection that meets the present invention.Red phosphorus, in itself, is a well-known inhibitor of ignition of polymeric materials. However, even at ambient temperatures it tends to medlen, phosphine is released in greater quantities. At atmospheric oxidation of the red phosphorus tends to allocation of phosphorous acid, hydrogen and phosphine, acting as the decomposition products of which the most dangerous is phosphine.Masterbatches containing red phosphorus and a polymer that is widely used, for example, in the electrical industry, including as a cable cover. It's delivered in large quantities and stored until use. For this reason it is important, both from an economic and environmental point of view, to the selection of phosphine from red phosphorus contained in the fallopian mixtures were minimal.There is a method of reducing the allocation of phosphine from red phosphorus treatment of carbonyl-containing compounds, as well as fire protective polymer composition comprising a thermoplastic thermosetting polymer, 1-20 wt. red phosphorus as a flame retardant and 0.01-3.00 wt. aliphatic or aromatic aldehyde or beta-ketone carbonyl-containing as an inhibitor of the formation of phosphine [1, 2] it is Noted that the aldehyde or ketone interact with formed by the decomposition of the red phosphor is FINA from red phosphorus treatment acyclic aliphatic compounds, containing an unsaturated double carbon-carbon bond and an electron-withdrawing group located in the alpha position relative to the double bond, when the mass ratio of the red phosphor and unsaturated acyclic aliphatic compounds, respectively, 5-95 5-50.For example, red phosphorus treated with oligomers or polymers based on maleic, fumaric, crotonic and methacrylic acids or their anhydrides, including their esters, for example methyl methacrylate.In the application described is also fire-protected polymer composition comprising a thermoplastic or thermosetting polymer and 0.2-20 wt. red phosphorus treated with the above unsaturated acyclic aliphatic compound containing in the alpha position electroencephalo group, taken in the mass ratio of the red phosphor, respectively, 5-50 50-95.According to the formula of the invention, the red phosphor is mixed with a polymer-based unsaturated maleic and fumaric acids. However, the examples include only one specific compound of this type, namely: imido-4,4-diphenyl-methane-bis-maleic acid (BMEM).In addition, given n red phosphorus in the composition should include oxides of metals.Due to the high toxicity of phosphine even a relatively small quantity allocated in examples 1, 2 and 5, are too high. Therefore, in accordance with the data only with the addition of copper oxide can be eliminated selection of phosphine.According to the present invention, a method for reducing the allocation of phosphine in which there is no need to add metal oxides.It was found that acyclic aliphatic compounds containing at least one double carbon-carbon bond, which is in the alpha position relative to at least one group, dilatory electrons are effective in minimizing allocation of phosphine from red phosphorus.Accordingly, the technical problem to be solved by the present invention is directed, is a decrease in the allocation of phosphine from red phosphorus.The mentioned technical problem is solved by a method of reducing the allocation of phosphine from red phosphorus interaction with acyclic aliphatic compound containing ethylene unsaturated bond in the alpha position relative to electroanatomic the secure link in the alpha position relative to the electron-withdrawing group, use cinnamon translegal in the amount of from 0.1 to 100% by weight of red phosphorus, preferably in an amount of 5% by weight of red phosphorus.The mentioned technical problem is solved also fire protective polymer composition containing as a flame retardant product of the interaction of red phosphorus with acyclic aliphatic compound containing ethylene unsaturated bond in the alpha position relative to the electron-withdrawing group, and according to the invention contains as a named product of the interaction of red phosphorus with cinnamon transliterator, taken in an amount from 0.1 to 100% by weight of red phosphorus, the content in the composition of the polymer 20-80 wt. named flame retardant 20-80 wt.Preferably fire-protected polymer composition comprises 50 wt. polymer and 50 wt. these flame retardant.As fire protective polymer polymer composition may contain a thermoplastic polymer selected from the group comprising polyethylene, polypropylene, polystyrene, high impact polystyrene, copolymer of Acrylonitrile-butadiene-styrene copolymer is a styrene-butadiene-styrene and a copolymer of styrene with butadiene.For example, fire is amide, polyester, polyacrylate or a vinyl polymer.The composition according to the invention may contain, in addition, thermosetting polymer is selected from the group comprising polyepoxide resin, polyurethane, phenolic resin, urea resin and polyurea.Preferred implementations of the present invention are illustrated by the following examples.Example 1. A method of reducing the allocation of phosphine from red phosphorus.1 g of red phosphorus powder is mixed with 1 g of the inhibitor. The mixture is placed in a sealed conical flask of 250 ml, equipped with a gasket, which allows the selection of gas. The humidity in the flask is maintained at the level of about 70% for what it is connected to a tube containing saturated mixed salt solution of ammonium chloride and potassium nitrate. The amount of phosphine in the flask was measured after 14 days, which produce gas analysis in the throat space on a gas chromatograph equipped with flame photometric detector. The calibration is performed relative to the cylinder with a known concentration of phosphine in nitrogen (see table.1).Example 2. A decrease in the allocation of phosphine from masterbatches containing red phosphor is Elena low density (LDPE) (melt flow index, equal to 7). The mixture is stirred and ekstragiruyut through 25/25-odnochastny extruder, equipped with a mixer, remove voids. Royal blend tabletirujut, and the content of phosphine control by placing 1 g of masterbatches in the flask, 250 ml, as described in example 1 (see tab.2).Example 3. A decrease in the allocation of phosphine from fire protective polymeric composition.Uterine mixture in an amount of 160 g, prepared as described in example 2, is added to 850 g of low density polyethylene (LDPE) (melt flow index equal to 7) and molded by injection molding, receiving the samples in the form of rods, each of which weighs 8,4, the Rod is cut in half and placed in a flask of 250 ml to control the content of phosphine as described in example 1 (see tab.3).Example 4. A decrease in the allocation of phosphine when using media inhibitor.Cinnamon translegal in the amount of 2.5 g dissolved in 10 g of acetone and impregnated with carbon black, taken in an amount of 5 g Acetone is evaporated. The treated carbon black is then injected into the low-density polyethylene (melt flow index equal to seven) for the preparation of masterbatches containing the inhibitor with the media, and determined the, the manual shrink selection of phosphine from red phosphorus according to the invention and of fire protective polymer composition according to the invention are characterized by greater efficiency of inhibition allocation of phosphine than previously known technical solutions. 1. A method of reducing the allocation of phosphine from red phosphorus interaction with acyclic aliphatic compound containing Ethylenediamine bond in the alpha position relative to electroanatomic group, characterized in that as an acyclic aliphatic compounds containing Ethylenediamine bond in the alpha position relative to the electron-withdrawing group, use cinnamon translegal in an amount of 0.1 to 100.0% by weight of red phosphorus.2. The method according to p. 1, characterized in that the cinnamon translegal used in an amount of 5% by weight of red phosphorus.3. Fire protective polymer composition containing as a flame retardant product of the interaction of red phosphorus with acyclic aliphatic compound containing Ethylenediamine bond in the alpha position relative to the electron-withdrawing group, characterized in that it contains as the named product pogo phosphorus, when the content in the composition of the polymer is 20 to 80 wt. named flame retardant 20 to 80 wt.4. The composition according to p. 3, characterized in that it contains 50 wt. polymer and 50 wt. these flame retardant.5. The composition according to PP.3 and 4, characterized in that it contains a polymer selected from the group comprising polyethylene, polypropylene, polystyrene, high impact polystyrene, copolymer of Acrylonitrile-butadienestyrene, a styrene-butadienestyrene and a copolymer of styrene with butadiene.6. The composition according to PP.3 and 4, characterized in that it contains a polymer selected from the group comprising polyamide, polyester, polyacrylate or a vinyl polymer.7. The composition according to PP.3 and 4, characterized in that it contains a polymer selected from the group comprising polyepoxide resin, polyurethane, phenolic resin, urea resin and polyurea.
FIELD: synthetic fiber production.
SUBSTANCE: preparation of composition, which can be used for molding-mediated manufacture of synthetic threads, fibers, and filaments and therefore manufacture of woven, knitted, nonwoven, or napped colored ware, is characterized by that 0.01-0.04% of phosphorus-containing stabilizing additive, 0.10-0.30% of sterically hindered phenol antioxidant, and 0.15-0.5% of light stabilizer are introduced into polymerization medium before or during polymerization, said phosphorus-containing stabilizing additive being selected from phosphorous and hypophosphorous acids and said hindered phenol containing at least one sterically hindered amino group.
EFFECT: increased light stability of polyamide ware and avoided significant foaming during polymerization process.
15 cl, 1 tbl, 3 ex
FIELD: polymer materials.
SUBSTANCE: expandable polystyrene granules are manufactured by polymerization of styrene (if needed, jointly with comonomers) in water suspension, whereto foaming agent is added before, during, or after polymerization. Method is characterized by that polymerization proceeds in presence of swollen graphite having average particle size 20 to 100 μm in amount 2 to 20 wt % as calculated for monomers and granulated expandable polystyrene.
EFFECT: achieved formation of halogen-free fire-protecting components.
6 cl, 3 ex
FIELD: chemistry of polymers, chemical technology.
SUBSTANCE: invention relates to epoxyurethane resin-base polymeric composition. Composition comprises the following ratio of components, mas. p. p.: epoxyurethane resin, 100; aromatic amine hardening agent, 15-65; ammonium polyphosphate, 10-100, and filling agent, 10-170. Epoxyurethane resin is prepared by stirring at heating of epoxy component and polyisocyanate taken in the ratio from 85:15 to 98:2, at temperature 50-120°C for 50-210 min. As epoxy component invention uses a mixture of 4,4'-dioxydiphenylpropane-base epoxy resin of molecular mass 340-600 Da (A), technical polyepichlorohydrin diglycidyl ester (B) and technical laproxide representing oligomer of propylene oxide with terminal epoxide groups of molecular mass 250-900 Da (C). Components A:B:C are taken in the ratio from 5:70:25 to 90:5:5. As aromatic amine hardening agent the composition contains stabilized liquid mixture of aromatic amines. Invention provides decreasing viscosity and foam formation, enhancing working life and resistance to multiple thermal cycles from -60°C to +80°C and to obtain high strength indices. Proposed polymeric composition is used in making armor covers, enclosed charges of ballistic solid rocket fuel and as pouring compounds used in electronics, electric and radio engineering, building and for other aims.
EFFECT: valuable technical properties of composition.
4 tbl, 8 ex
FIELD: chemistry of organophosphorus compounds.
SUBSTANCE: invention relates to a compound, in particular, to halogen-free antipyrene compound. Invention describes compound of the formula (I): Z1-O-[m(R1PO3),n(R2HPO3)]-Z2 wherein [m(R1PO3),n(R2HPO3)] means co-polyphosphate with m links of (R1PO3) and n links of (R2HPO3) wherein R1 means ammonium structural element; R2 means 1,3,5-triazine structural element; Z1 and Z2 mean ammonium or 1,3,5-triazine structural elements that must be chosen independently of one another; m and n mean whole number equal 1 or above under condition that the sum m and n is above 3. Compound of the formula (I) shows improved thermal stability during processing polymers.
EFFECT: improved and valuable properties of compounds.
4 cl, 8 tbl, 4 ex
FIELD: heat-insulation materials.
SUBSTANCE: invention relates to manufacture of environmentally appropriate antimicrobial nonflammable fibrous filler through wet formation from waste produced during processing of linen raw material, which filler can be used to manufacture nonflammable antimicrobial heat-insulation materials. Desired target is achieved by that nonflammable fibrous filler based on cellulose-containing material with diammonium phosphate fixed thereon is comprised of linen pulp having following characteristics: fiber number: 2, content of chaff: 8-12%, fiber length: 50-80 mm, pulp density; 200-300 kg/m2, and heat conductivity: 0.04-0.06 kcal/m.h. degree, which linen pulp is covered with chitosan in amount 8-32% based on the weight of linen pulp.
EFFECT: enhanced valuable characteristics of filler.
4 dwg, 1 tbl, 17 ex
SUBSTANCE: stabilizing agent composition for foaming plastics of halogen-containing polymers contains at least one halogen-containing hydroxyacid salt, for instance sodium or ammonium perchlorate and at least one pore forming agent, wherein content of two components is 0.1 mass % based on total composition mass, wherein composition contains at least one halogen-containing hydroxyacid salt in amount of 0.01-50 mass % and at least one pore forming agent in amount of 0.5-50 mass % as calculated to total composition mass. Moreover composition contains less than 10 % salt crystallites having size more than 3 mum as calculated to total content of halogen-containing hydroxyacid salt. Stabilizing agent composition is useful in polymer composition for foaming plastics such as foamed mould articles, containing at least halogen-containing polymer.
EFFECT: foaming plastics with improved original color.
18 cl, 4 ex, 4 tbl
SUBSTANCE: claimed composition contains carrying material of general formula CaxAl2(OH)2(x+2)HPO3.mH2O, wherein x = 2-12; m = 0-12 and salt of halogen-containing hydroxyacid salt of mixture of two or more such salts, wherein at least one halogen-containing hydroxyacid salt is present on carrying material in fine dispersed form. Composition is obtained by blending of carrying material with solution of halogen-containing hydroxyacid salt and additives.
EFFECT: new stabilizing agent composition for halogen-containing polymers.
FIELD: polymer materials.
SUBSTANCE: biocyde composition containing polystyrene and biocyde additive is characterized by further including stearic acid amide and in that said biocyde additive contains silver phosphate at following proportions of components: 99.85-99.20% polystyrene, 0.10-0.30% stearic acid amide, and 0.05-0.50% silver phosphate. Composition containing silver thiocyanate and silver stearate as biocyde additive are also described.
EFFECT: enhanced bactericidal activity, expanded functional possibilities when used in various industrial fields in manufacture of materials employing molding and extrusion techniques.
3 cl, 1 dwg, 4 tbl, 4 ex
SUBSTANCE: invention pertains to a mixture, the method of obtaining it, method of obtaining the product made from the mixture, and to products in form of layers of sheet material, hollow or solid pipes, and pipe or reservoir bottles. The mixture contains at least one thermoplastic matrix and particles based on a phosphate of zirconium, titanium, cerium and/or silicon. In that case, at least 50% of the above mentioned particles are in the form of nano-metric layered compounds, with a form factor less than or equal to 100. The mixture can be obtained through different methods. One alternative involves mixing the particles based on a phosphate of zirconium, titanium, cerium and/or silicon in the form of nanometric layered compounds with monomers and/or oligomers of a thermoplastic matrix before or during the polymerisation stage. The thermoplastic matrix is then polymerised. In another alternative, the above mentioned particles in the form of nanometric layered compounds are mixed with the thermoplastic matrix, and when necessary, the obtained mixture is mixed with at least one thermoplastic matrix. The product is made using an extrusion or moulding device.
EFFECT: obtaining of a mixture with good mechanical and barrier properties.
20 cl, 6 tbl, 9 ex
SUBSTANCE: invention relates to fireproof polymeric compositions with lower release of hydrogen chloride and smoke when burning and can be used for manufacturing insulation and protective coats of electric wires and cables, as well as for various products which are in conditions of higher fire risk. Composition contains suspension polyvinylchloride, complex-ether plasticiser, stabiliser and antipyren-smoke suppressor and additionally AlO(OH), Al2O3 amorphous, γAl2O3, Ca phosphate and/or Mg and Al phosphate.
EFFECT: increase of fire resistance of polymeric composition and reduction of release of hydrogen chloride, smoke, vapours of benzol, vinylchloride, and carbon monoxide.
FIELD: inorganic chemistry, aluminum silicates, composition for fireproofing of building and construction materials.
SUBSTANCE: invention relates to water resistant aluminum silicate with softening temperature more than 900°C for fireproofing of wood, polymer, and other building and construction materials. Water resistant aluminum silicate has general formula of Na2O*kSiO2*nAl2O3*pP2O5*rMA*mH2O, 1, wherein k = 3.25-11.5; m = 3.5-12; n = 0.052.7; p = 0-0.1; r = 0.3.5; M is K, Ca2+, Mg2+, Zn2+, 1/2Ti4+; A is Cl-, O2-, SO4 2-, CO3 2-. Aluminum silicate represents hardening product of water dispersion containing 1) sodium silicate of general formula Na2O*xSiO2*yH2O, 2, wherein x = 2.9-3.1; y = 17-22; 2) cross-linking agent based on alkali soluble silicium and/or aluminum compound; 3) at least one a) hardening agent (alkali soluble zinc, titanium, magnesium and/or calcium oxide (hydroxide)); b) opener; c) filler (e.g. kaolin, chipped glass fiber, milled sand, etc.); d) modifier in the next component ratio (mass %): sodium silicate 31-83.8, preferably 58-75; alkali soluble silicium compounds 0.05-39.2, preferably 10-15; alkali soluble aluminum compounds 0.4-26, preferably 5-8; hardening agent 0.74-19.9, preferably 3-8; opener 0.013-9.7; filler 1.9-33, preferably 5-15; modifier 0.01-6.3, preferably 0.35-0.75.
EFFECT: composition for production of non-cracked coating with low thermal conductivity and increased fire resistance.
28 cl, 116 ex, 52 tbl
FIELD: synthesis of phosphorus-containing derivatives of organic compounds.
SUBSTANCE: invention relates to method of preparing polyphosphates of organic compounds, to mixture of polyphosphates of organic nitrogenous bases, and to use of polyphosphates and mixture of polyphosphates as fire retardants for plastics, preferably thermoplastics and, more particularly, polyamides and polyesters. Polyphosphates of organic compounds are prepared via exchangeable decomposition of mixture of phosphorus pentoxide and at least one organic nitrogenous base with a compound releasing water when decomposed under reaction conditions, the latter compound being used in such molar proportion that water would release in amount corresponding to essentially two moles of water per one mole of phosphorus pentoxide. Water-releasing compound can be compound forming, along with water, only volatile decomposition products and this compound can be selected from group including anhydrous oxalic acid, oxalic acid dehydrate, and formic acid. Exchangeable decomposition reaction is conducted at 100 to 250°C. Mixture of polyphosphates of organic nitrogenous bases is characterized by following properties: when heated to 320°C it looses less than 2% of its mass; pH value of its 10% water suspension exceeds 5 at 25°C, preferably from 5.2 to 7.7 and, more preferably, from 5.8 to 7; its solubility in water is less than 0.1 g and preferably less than 0.01 g per 100 mL water.
EFFECT: expanded synthetic possibilities.
6 cl, 5 ex
SUBSTANCE: invention refers to constructional composites based on ultra-high molecular polyethylene (UHMPE), used in industrial production of fire-resistant multipurpose products with compaction method. Fire-resistant material contains powdered ultra-high molecular polyethylene of powder particle size 20-50 microns and molecular weight within 1.0 million to 25.0 million, and ammonium polyphosphate of powder particle size not exceeding 10 microns and degree of polymerisation not less than 1200. Material is made by stirring the mixed powdered UHMPE and ammonium polyphosphate in ratio as follows, wt %: ultra-high molecular polyethylene - 80, ammonium polyphosphate - 20.
EFFECT: produced fire-resistant material is characterised with fire resistance "ПВ"-0 and ensures reduced degree of flammability of constructional composites.
1 tbl, 1 ex
SUBSTANCE: composition for fire-proof treatment of synthetic fibres contains the following in pts. wt: methylphosphite borate 20.0-35.0, water 65.0-100.0, ammonia 15.0-25.0, polyacrylamide 15.0-25.0 and potassium persulphate 0.5-1.5.
EFFECT: high fire-resistance, strength, resistance to thermal-oxidative decomposition and endowing synthetic fibre with high strength of binding with isoprene rubber.
2 tbl, 6 ex