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Composite boron based flame retardant for Polyurethane
2017-12-3 15:48:15
Composite boron based flame retardant for Polyurethane
Polyurethane is used to produce boric anhydride or boric acid in the combustion process of composite boron flame retardants, forming a glass like melt on thermal insulation, covering the polyurethane and isolating the transmission of oxygen and heat.
In the solidification phase, boric acid react with cellulose hydroxyl to form boric acid ester, thus inhibiting the formation of the left glucose, making cellulose directly oxidized to carbon dioxide, and reducing the formation of carbon monoxide in flammable gas. This is different from that of phosphorus containing flame retardants during the combustion process, because of the formation of carbon monoxide due to the catalysis of phosphoric acid, and its flame retardancy also occurs in the solidification phase, and the resulting vitreous body can prevent the flammable gases from diffusing outward. The above factors can achieve the purpose of flame retardancy and good smoke suppression.
The synergistic effect of boron and phosphorus in the composite boron flame retardants made the organic boron containing flame retardant improve the hydrolytic stability and reduce the toxicity of phosphorus containing flame retardants.
Organophosphorous flame retardants are washable, but they are highly toxic. For example, if organo boron compounds are incorporated into molecules, boron phosphorus flame retardants can be synthesized, and various products can be obtained. Boric acid is used as the basic raw material to react with chloroethanol to get chloroethyl borate and then react with ethylene glycol amine. The reaction of three chlorosoxy phosphine and chloroethanol to obtain ethyl chloride and phosphonate is the same boron compound flame retardant for polyurethane. Because of the three elements containing boron, phosphorus and nitrogen in the molecule, the flame retardancy is very good and the LOI value can reach 37~38.
Such as boric acid and glycerol by reaction of boric acid diglyceride, and ethylene glycol and three phosphorus oxychloride by reaction of diethylene glycol phosphorus chloride, using the former residual hydroxyl phosphate ester flame retardant, introducing boron and phosphorus elements within the same molecule. Because there are many hydroxyl groups in the molecule, the cotton fiber can be covalent bonded with the cotton fiber under the catalysis of Louise acid, so the washability is better. Through water-soluble polyurethane as a crosslinking agent, it can be used for polyester fabric flame retardancy, good flame-retardant effect, LOI value is 38.5 (unfinished polyester fabric LOI value is 29), water washing 5 times to 30.8.
Boron - halogen compound flame retardant is suitable for polyester material. When halogen compounds are used as flame retardants, halogen free radicals are first released during combustion, and the high energy free radicals produced by polyester combustion can inhibit chain growth. At the same time, because of the formation of halogenated hydrogen with combustible gases, halogenated hydrogen also acts as a free radical generated by chain growth and disaggregation when polyester is burning, resulting in the flame retardant effect. In addition, the concentration of flammable gas produced by pyrolysis of polyester fiber is diluted by hydrogen halide gas and delayed combustion.
The effect of halide flame retardants mainly occurs in the gas phase. In the gas phase, boron halogen composite flame retardant produces gaseous three halogenated boron during combustion, then releases halogenated hydrogen, and also prevents the chain reaction between highly active radicals. In solid phase, boron flame retardants melt and seal up the surface of the combustion products, forming a glass covering layer, which also controls the escape of halogenated hydrogen from corrosive toxic gases. In addition, the endothermic effect of boron compounds released from the combined water changes the thermal decomposition pathway of the combustible materials and inhibits the formation of combustible gases.
Tris(2-chloroisopropyl)Phosphate(TCPP)
Tris(2-chloroisopropyl)Phosphate(Flame retardant TCPP) is a colorless or yellowish oily liquid. It is soluble in benzene, alcohol, carbon tetrachloride and other organic solvents, but insoluble in water and aliphatic hydrocarbons. Its relative density is 1.27-1.31, refractive index is 1.4916 ( 21.5 ), viscosity is 58mm2 / S, chlorine content is 32.8%, and phosphorus content is 9.5%. As the molecule contains phosphorus and chlorine element simultaneously, its flame retardant properties is significant, as well as the plasticization, damp-proof, antistatic effects and so on. Tris(2-chloropropyl) phosphate (TCPP) is an additive flame retardant.
The product is used for the soft / hard polyurethane foam, with thermal and hydrolytic stability good, especially suitable for ASTME84 (Level 11) foam, with low viscosity unsaturated polyester resin in low temperature application and phenolic plastics at. This product is also used to grab the foam sealant and sheet production. For polyvinyl chloride, polystyrene, phenolic resin, acrylic resin and rubber, coating, flame retardant, also used for soft and hard polyurethane foam, epoxy resin, polystyrene, cellulose acetate, ethyl cellulose tree and phenolic plastics, polyvinyl acetate and gun type foam sealant production. Particularly recommended for rigid polyurethane foam has excellent thermal and hydrolytic stability is particularly suitable for ASTM84 (II), compound for polyurethane foam and unsaturated resin and phenolic plastics.
Brominated flame retardants are the main varieties of halogen flame retardant, flame retardant polyester and other synthetic fibers are widely used in finishing, but such as decabromodiphenyl oxide, six bromo alkyl ring twelve, polybrominated biphenyls are due to serious harm to human health and the environment, the EU have been banned. Therefore, the development of boron bromide compound flame retardant can be a substitute for brominated flame retardant.
The FR-B currently produced in China is a liquid containing additive containing bromine and boron. It is named as boric acid three (2,3- dibromo) propyl ester, which is obtained from esterification and dehydration of 2,3- dibromo propanol and three oxidation two boron.
The LOI value of the flame retardant is 28.5, and it has the effect of smoke suppression. It has less effect on the physical and mechanical properties of the products and is easy to process. It is mainly used in polyurethane, unsaturated polyester resin and phenolic epoxy resin, and it can also produce good flame retardancy on cotton fabric. But because of the bromine contained in the molecule, the hydrogen bromide gas is formed during the combustion, which has an adverse effect on the environment.
Boron halogen compound flame retardant can be obtained by 2- allyl -1,3- oxo heteropentane. A boron halide composite flame retardant can be obtained from vinyl double chain bromination of allyl, and another boron halide composite flame retardant is obtained from 3- chlorine -1,2- two hydroxypropane. The LOI value is 28.5, which has good flame retardancy.
The application of these boron halogen compound flame retardants to cotton fabric can produce good flame retardancy. The flame retardancy can be greatly improved after the introduction of the halogen atoms in the boron molecule, and the synergistic effect is the same as that of the organophosphorus compounds.
The main raw materials for the synthesis of three kinds of boron and nitrogen, phosphorus and halogen compound flame retardants are basically boric acid and 2- allyl -1,3- oxopentane. The former is boric acid ester. The hydrolysis resistance of the former is not as good as the latter, which affects the washability of the ester. The flame retardancy after washing is reduced by 20%, but it is still a semi permanent flame retardant. The latter because of the existence of B - N molecular internal ligand, its hydrolytic ability is high, 4% flame retardant decreased after washing.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
http://www.yaruichem.com
Polyurethane is used to produce boric anhydride or boric acid in the combustion process of composite boron flame retardants, forming a glass like melt on thermal insulation, covering the polyurethane and isolating the transmission of oxygen and heat.
In the solidification phase, boric acid react with cellulose hydroxyl to form boric acid ester, thus inhibiting the formation of the left glucose, making cellulose directly oxidized to carbon dioxide, and reducing the formation of carbon monoxide in flammable gas. This is different from that of phosphorus containing flame retardants during the combustion process, because of the formation of carbon monoxide due to the catalysis of phosphoric acid, and its flame retardancy also occurs in the solidification phase, and the resulting vitreous body can prevent the flammable gases from diffusing outward. The above factors can achieve the purpose of flame retardancy and good smoke suppression.
The synergistic effect of boron and phosphorus in the composite boron flame retardants made the organic boron containing flame retardant improve the hydrolytic stability and reduce the toxicity of phosphorus containing flame retardants.
Organophosphorous flame retardants are washable, but they are highly toxic. For example, if organo boron compounds are incorporated into molecules, boron phosphorus flame retardants can be synthesized, and various products can be obtained. Boric acid is used as the basic raw material to react with chloroethanol to get chloroethyl borate and then react with ethylene glycol amine. The reaction of three chlorosoxy phosphine and chloroethanol to obtain ethyl chloride and phosphonate is the same boron compound flame retardant for polyurethane. Because of the three elements containing boron, phosphorus and nitrogen in the molecule, the flame retardancy is very good and the LOI value can reach 37~38.
Such as boric acid and glycerol by reaction of boric acid diglyceride, and ethylene glycol and three phosphorus oxychloride by reaction of diethylene glycol phosphorus chloride, using the former residual hydroxyl phosphate ester flame retardant, introducing boron and phosphorus elements within the same molecule. Because there are many hydroxyl groups in the molecule, the cotton fiber can be covalent bonded with the cotton fiber under the catalysis of Louise acid, so the washability is better. Through water-soluble polyurethane as a crosslinking agent, it can be used for polyester fabric flame retardancy, good flame-retardant effect, LOI value is 38.5 (unfinished polyester fabric LOI value is 29), water washing 5 times to 30.8.
Boron - halogen compound flame retardant is suitable for polyester material. When halogen compounds are used as flame retardants, halogen free radicals are first released during combustion, and the high energy free radicals produced by polyester combustion can inhibit chain growth. At the same time, because of the formation of halogenated hydrogen with combustible gases, halogenated hydrogen also acts as a free radical generated by chain growth and disaggregation when polyester is burning, resulting in the flame retardant effect. In addition, the concentration of flammable gas produced by pyrolysis of polyester fiber is diluted by hydrogen halide gas and delayed combustion.
The effect of halide flame retardants mainly occurs in the gas phase. In the gas phase, boron halogen composite flame retardant produces gaseous three halogenated boron during combustion, then releases halogenated hydrogen, and also prevents the chain reaction between highly active radicals. In solid phase, boron flame retardants melt and seal up the surface of the combustion products, forming a glass covering layer, which also controls the escape of halogenated hydrogen from corrosive toxic gases. In addition, the endothermic effect of boron compounds released from the combined water changes the thermal decomposition pathway of the combustible materials and inhibits the formation of combustible gases.
Tris(2-chloroisopropyl)Phosphate(TCPP)
Tris(2-chloroisopropyl)Phosphate(Flame retardant TCPP) is a colorless or yellowish oily liquid. It is soluble in benzene, alcohol, carbon tetrachloride and other organic solvents, but insoluble in water and aliphatic hydrocarbons. Its relative density is 1.27-1.31, refractive index is 1.4916 ( 21.5 ), viscosity is 58mm2 / S, chlorine content is 32.8%, and phosphorus content is 9.5%. As the molecule contains phosphorus and chlorine element simultaneously, its flame retardant properties is significant, as well as the plasticization, damp-proof, antistatic effects and so on. Tris(2-chloropropyl) phosphate (TCPP) is an additive flame retardant.
The product is used for the soft / hard polyurethane foam, with thermal and hydrolytic stability good, especially suitable for ASTME84 (Level 11) foam, with low viscosity unsaturated polyester resin in low temperature application and phenolic plastics at. This product is also used to grab the foam sealant and sheet production. For polyvinyl chloride, polystyrene, phenolic resin, acrylic resin and rubber, coating, flame retardant, also used for soft and hard polyurethane foam, epoxy resin, polystyrene, cellulose acetate, ethyl cellulose tree and phenolic plastics, polyvinyl acetate and gun type foam sealant production. Particularly recommended for rigid polyurethane foam has excellent thermal and hydrolytic stability is particularly suitable for ASTM84 (II), compound for polyurethane foam and unsaturated resin and phenolic plastics.
Brominated flame retardants are the main varieties of halogen flame retardant, flame retardant polyester and other synthetic fibers are widely used in finishing, but such as decabromodiphenyl oxide, six bromo alkyl ring twelve, polybrominated biphenyls are due to serious harm to human health and the environment, the EU have been banned. Therefore, the development of boron bromide compound flame retardant can be a substitute for brominated flame retardant.
The FR-B currently produced in China is a liquid containing additive containing bromine and boron. It is named as boric acid three (2,3- dibromo) propyl ester, which is obtained from esterification and dehydration of 2,3- dibromo propanol and three oxidation two boron.
The LOI value of the flame retardant is 28.5, and it has the effect of smoke suppression. It has less effect on the physical and mechanical properties of the products and is easy to process. It is mainly used in polyurethane, unsaturated polyester resin and phenolic epoxy resin, and it can also produce good flame retardancy on cotton fabric. But because of the bromine contained in the molecule, the hydrogen bromide gas is formed during the combustion, which has an adverse effect on the environment.
Boron halogen compound flame retardant can be obtained by 2- allyl -1,3- oxo heteropentane. A boron halide composite flame retardant can be obtained from vinyl double chain bromination of allyl, and another boron halide composite flame retardant is obtained from 3- chlorine -1,2- two hydroxypropane. The LOI value is 28.5, which has good flame retardancy.
The application of these boron halogen compound flame retardants to cotton fabric can produce good flame retardancy. The flame retardancy can be greatly improved after the introduction of the halogen atoms in the boron molecule, and the synergistic effect is the same as that of the organophosphorus compounds.
The main raw materials for the synthesis of three kinds of boron and nitrogen, phosphorus and halogen compound flame retardants are basically boric acid and 2- allyl -1,3- oxopentane. The former is boric acid ester. The hydrolysis resistance of the former is not as good as the latter, which affects the washability of the ester. The flame retardancy after washing is reduced by 20%, but it is still a semi permanent flame retardant. The latter because of the existence of B - N molecular internal ligand, its hydrolytic ability is high, 4% flame retardant decreased after washing.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
http://www.yaruichem.com
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