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Water borne polyurethane emulsion flame retardant
2017-11-2 11:12:06
Water borne polyurethane emulsion flame retardant
Waterborne polyurethane emulsion is a very important kind of condensation of aqueous polyurethane emulsion has no toxicity, no environmental pollution, energy saving, easy operation and other advantages, in the industry (including adhesives and coatings etc.) are widely used. Therefore, it is gradually becoming an important direction in the development of polyurethane field.
Because of the hydrophobic polyurethane is very strong, must be prepared PU emulsion using a new synthesis method, synthesis process of waterborne polyurethane is mainly as follows: by oligomer polyol, chain extender, formed in the pre PU diisocyanate high relative molecular mass polymer; the neutralized prepolymer emulsification in water, the formation of dispersion liquid. All methods are different in the process of chain extension.
With the rapid development of waterborne polyurethane emulsion flame retardants, the varieties of waterborne polyurethane emulsion flame retardants increase rapidly. Many phosphate esters can be used as water borne polyurethane emulsion flame retardants. But the phosphate ester has plasticizing effect at the same time, it is plasticizer, when the dosage is too large, it will soften polyurethane, reduce the strength and other physical properties.
There are two kinds of preparation methods of polyurethane emulsion: external emulsion method and Internal Emulsification method.
1. emulsion method. The method is the preparation of waterborne polyurethane with the first, external emulsification method is in high shear emulsifying agent, method of compulsory emulsification existence force, the earliest Pschlack invention, W.yandott PU emulsion was synthesized by this method.
The synthesis process is the first synthesis of PU polyether glycol and organic isocyanate prepolymer, and then with small molecular diols or two amine chain extender, organic solution of PU, and then to the strong stirring, water solution gradually adding emulsifier, forming a coarse emulsion, and finally sent into the homogenizer, the formation of the particle size of the emulsion properly.
However, because of the disadvantages of long reaction time, large amount of emulsifier and coarse particle size of emulsion, the poor storage performance and poor physical and mechanical properties of the adhesive layer, the method is not available at present. A method of preparing PU emulsion by low temperature sealing method was developed, which can reduce the amount of emulsifier and make the emulsion with good stability. The method is to end with pre -NCO oxime, dimer lactam, NaHSO3, acetoacetic ester terminated as capping agent, aqueous solution with polyamine containing emulsifier dispersed in together, forming a stable PU emulsion.
2. self emulsifying method. The preparation of stable PU emulsion is mainly through self emulsifying method, and the key is to introduce hydrophilic groups into the molecular skeleton of polyurethane.
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.
The hydrophilic group enters the PU molecular skeleton through the chain extension of hydrophilic monomer, which is composed of salt forming groups and salt forming reagents. According to the type of hydrophilic group, the waterborne PU emulsion prepared by this method can be divided into 4 types, anionic, cationic, amphoteric and nonionic, in which anionic is dominant.
Self emulsified PU emulsion preparation process has many kinds, preparation method is mainly divided into acetone method, prepolymer dispersion method, melting method, ketimine / azine method, its common characteristic is the first preparation of moderate relative molecular mass, PU terminated pre NCO or closed NCO dimers, difference in the main chain extension process. At present, the most important methods in industrial production are acetone method and prepolymer dispersion method (or prepolymer mixing method). The synthetic process is as follows.
2.1 acetone method. Acetone was successfully studied by Ddieterich in germany. Ddieterich first polyether or polyester diol and isocyanate prepolymer, adding acetone reduced viscosity, N- methyl two ethanol amine chain extender, adding acetone reduced viscosity, then adding ionization reagent, stirring ionization.
The ionized PU dispersed to containing 80% acetone, 20% water medium, finally steaming in addition to acetone, to obtain the particle size of 0.03 to 100 mu m aqueous polyurethane. High viscosity pre acetone method was first prepared with NCO terminated prepolymer, adding acetone to lower the viscosity, and then use the hydrophilic monomer chain extender, adding water in high speed stirring, through strong shear dispersing in water, emulsified after vacuum distillation solvent recovery can be prepared PU water dispersion system.
WSPU was prepared by acetone method at Anhui University. WSPU is a kind of shape polyurethane, a new type of functional material. It has a series of advantages, such as large variable shape, easy processing, adjustable degree of transition, biodegradability and good biocompatibility. The preparation process is as follows: sequentially adding polycaprolactone glycol in the four bottle (PCL) and 2 4- (TDI), toluene diisocyanate, 3h at 80 DEG C under stirring in nitrogen, adding a small amount of acetone solvent, stirring 10min after adding catalyst and dimethylol propionic acid (DMPA) and cross-linking agent three hydroxy Trimethylolpropane (TMP) reaction of 4H and preparation of PU prepolymer.
The polyurethane prepolymer was added with three ethylamine 5min under the rapid agitation, then the amount of water was added into the emulsion, and then the acetone was removed by 10min decompression. The solid content of 30%WSPU emulsion was obtained. WSPU processing and sample testing. Finally, when the molecular weight of PCL was 5000, the emulsion was stable, and its shape memory recovery rate was 95%.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
http://www.yaruichem.com
Waterborne polyurethane emulsion is a very important kind of condensation of aqueous polyurethane emulsion has no toxicity, no environmental pollution, energy saving, easy operation and other advantages, in the industry (including adhesives and coatings etc.) are widely used. Therefore, it is gradually becoming an important direction in the development of polyurethane field.
Because of the hydrophobic polyurethane is very strong, must be prepared PU emulsion using a new synthesis method, synthesis process of waterborne polyurethane is mainly as follows: by oligomer polyol, chain extender, formed in the pre PU diisocyanate high relative molecular mass polymer; the neutralized prepolymer emulsification in water, the formation of dispersion liquid. All methods are different in the process of chain extension.
With the rapid development of waterborne polyurethane emulsion flame retardants, the varieties of waterborne polyurethane emulsion flame retardants increase rapidly. Many phosphate esters can be used as water borne polyurethane emulsion flame retardants. But the phosphate ester has plasticizing effect at the same time, it is plasticizer, when the dosage is too large, it will soften polyurethane, reduce the strength and other physical properties.
There are two kinds of preparation methods of polyurethane emulsion: external emulsion method and Internal Emulsification method.
1. emulsion method. The method is the preparation of waterborne polyurethane with the first, external emulsification method is in high shear emulsifying agent, method of compulsory emulsification existence force, the earliest Pschlack invention, W.yandott PU emulsion was synthesized by this method.
The synthesis process is the first synthesis of PU polyether glycol and organic isocyanate prepolymer, and then with small molecular diols or two amine chain extender, organic solution of PU, and then to the strong stirring, water solution gradually adding emulsifier, forming a coarse emulsion, and finally sent into the homogenizer, the formation of the particle size of the emulsion properly.
However, because of the disadvantages of long reaction time, large amount of emulsifier and coarse particle size of emulsion, the poor storage performance and poor physical and mechanical properties of the adhesive layer, the method is not available at present. A method of preparing PU emulsion by low temperature sealing method was developed, which can reduce the amount of emulsifier and make the emulsion with good stability. The method is to end with pre -NCO oxime, dimer lactam, NaHSO3, acetoacetic ester terminated as capping agent, aqueous solution with polyamine containing emulsifier dispersed in together, forming a stable PU emulsion.
2. self emulsifying method. The preparation of stable PU emulsion is mainly through self emulsifying method, and the key is to introduce hydrophilic groups into the molecular skeleton of polyurethane.
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.
The hydrophilic group enters the PU molecular skeleton through the chain extension of hydrophilic monomer, which is composed of salt forming groups and salt forming reagents. According to the type of hydrophilic group, the waterborne PU emulsion prepared by this method can be divided into 4 types, anionic, cationic, amphoteric and nonionic, in which anionic is dominant.
Self emulsified PU emulsion preparation process has many kinds, preparation method is mainly divided into acetone method, prepolymer dispersion method, melting method, ketimine / azine method, its common characteristic is the first preparation of moderate relative molecular mass, PU terminated pre NCO or closed NCO dimers, difference in the main chain extension process. At present, the most important methods in industrial production are acetone method and prepolymer dispersion method (or prepolymer mixing method). The synthetic process is as follows.
2.1 acetone method. Acetone was successfully studied by Ddieterich in germany. Ddieterich first polyether or polyester diol and isocyanate prepolymer, adding acetone reduced viscosity, N- methyl two ethanol amine chain extender, adding acetone reduced viscosity, then adding ionization reagent, stirring ionization.
The ionized PU dispersed to containing 80% acetone, 20% water medium, finally steaming in addition to acetone, to obtain the particle size of 0.03 to 100 mu m aqueous polyurethane. High viscosity pre acetone method was first prepared with NCO terminated prepolymer, adding acetone to lower the viscosity, and then use the hydrophilic monomer chain extender, adding water in high speed stirring, through strong shear dispersing in water, emulsified after vacuum distillation solvent recovery can be prepared PU water dispersion system.
WSPU was prepared by acetone method at Anhui University. WSPU is a kind of shape polyurethane, a new type of functional material. It has a series of advantages, such as large variable shape, easy processing, adjustable degree of transition, biodegradability and good biocompatibility. The preparation process is as follows: sequentially adding polycaprolactone glycol in the four bottle (PCL) and 2 4- (TDI), toluene diisocyanate, 3h at 80 DEG C under stirring in nitrogen, adding a small amount of acetone solvent, stirring 10min after adding catalyst and dimethylol propionic acid (DMPA) and cross-linking agent three hydroxy Trimethylolpropane (TMP) reaction of 4H and preparation of PU prepolymer.
The polyurethane prepolymer was added with three ethylamine 5min under the rapid agitation, then the amount of water was added into the emulsion, and then the acetone was removed by 10min decompression. The solid content of 30%WSPU emulsion was obtained. WSPU processing and sample testing. Finally, when the molecular weight of PCL was 5000, the emulsion was stable, and its shape memory recovery rate was 95%.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
http://www.yaruichem.com
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