Background and overview[1][2]
The English name of 10-(2,5-Dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide is: 10-(2,5-Dihydroxyphenyl)- 10-H-9-oxa-10-phospha-phenantbrene-10-oxide, its name in the commercial field uses its English abbreviation ODOPB or DOPO-HQ. 10-(2,5-Dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide is a new generation of halogen-free, environmentally friendly and green new flame retardant. Its market and application needs and application fields are gradually expanding. Mainly used in high-end epoxy resins and curing agents for circuit boards, packaging of semiconductor materials, LED light-emitting diodes, etc. 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide can be incorporated into polyester, polyether, and polyamide chains through copolymerization to improve flame retardancy. While maintaining thermal stability, it does not affect the physical and other properties of polyester, and avoids the shortcomings of general flame retardants being incompatible with polyester, easy to precipitate, and having a great impact on mechanical properties. It is in line with the current development trend of flame retardants for smoke suppression and low toxicity, and is an environmentally friendly flame retardant. DOPO-HQ is white or slightly yellow in appearance, partially soluble in hot methanol, ethanol, toluene and other organic solvents, and almost insoluble in water. Molecular formula C18H13O4P, molecular weight 324, melting point 247~253°C, high thermal stability, used in products that must comply with ROHS requirements, intermediates for the synthesis of reactive flame retardants, etc.
Preparation[1]
In the article “Synthesis of DOPO Derivatives”, a master’s thesis of Nanjing University of Science and Technology, it is mentioned that DOPO and p-benzoquinone are used as reaction raw materials, and the process route of using tetrahydrofuran as the reaction solvent, recrystallization of tetrahydrofuran and toluene are used respectively. Solvent, ethanol recrystallization process route, by comparing the above two process routes, toluene was selected as the reaction solvent, and the process parameters were discussed. The paper “Synthesis and Characterization of New Phosphorus-Containing Flame Retardant ODOPB” was published in “Proceedings of the 2010 China Flame Retardant Academic Annual Conference” and was published in “Fine Chemical Intermediates” (Volume 41, Issue 5, 2011) The paper “Research on the Synthesis Process of New Phosphorus-Containing Flame Retardant DOPO-HQ” in the paper “Synthesis of DOPO Derivatives” further studies the production of DOPO-HQ. The main research contents of the two papers are: : The reaction raw materials DOPO and p-benzoquinone remained unchanged. Toluene, tetrahydrofuran, and ethylene glycol monoethyl ether were used as solvents respectively for comparison. Ethylene glycol monoethyl ether was selected as the solvent. The resulting precipitate was cooled to room temperature, filtered, and The solvent is washed several times and then dried to obtain a crude product, which is recrystallized with ethanol and then dried under vacuum to obtain the final product. The above-mentioned processes all have the following problems: process stability is poor, product quality varies from time to time, mainly in product appearance (color is sometimes light and sometimes heavy), and the purity of the crude product is between 50 and 90%, which brings problems to the post-processing process. Big trouble; the product yield is low; the reaction process is carried out under solvent reflux conditions, the solvent loss is large, and it cannot be repeated; toluene, ethylene glycol monoethyl ether and tetrahydrofuran are highly toxic, smelly, flammable and explosive , the environment of the process operation unit is harsh and the risk is high; during the recrystallization operation, because the product cannot be completely dissolved in solvents such as ethanol and tetrahydrofuran, the purity of the product cannot be effectively improved, and the product quality is difficult to meet the standards.
CN201210243915.6 provides a friendly and efficient method for preparing 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide, that is, DOPO-HQ The synthetic route is used to overcome the problems of unstable process, poor product purity and low yield in the existing technology. It includes the following steps: (1) Dissolve p-benzoquinone and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in a solvent in a mass ratio of 1:0.90~1 , the two are fully reacted in the solvent at a temperature of 60 to 120°C. After the reaction is completed, the reaction system is cooled until the product is fully precipitated, and the reaction system is filtered to obtain a crude solid product; (2) The crude product prepared in step (1) After the solid product is washed and dried, the powdery product obtained is 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide. Figure 1 is the infrared spectrum of the prepared flame retardant DOPO-HQ product; Figure 2 is the nuclear magnetic spectrum of the prepared flame retardant DOPO-HQ product; Figure 3 is the high-efficiency liquid phase of the prepared flame retardant DOPO-HQ product Chromatogram.
Apply [2]
10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide is used to prepare flame-retardant hydroxypropyl methacrylate water-based polyurethane coatings.
CN201410325853.2 uses 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphinephenanthrene-10-oxide to replace traditional polyester polyol or poly Ether polyol reacts with isocyanate, and a nitrogen-phosphorus compound is selected to be synergistically catalyzed with dibutyltin dilaurate. Organic silicon is used to extend the polyurethane prepolymer. At the same time, manganese salt is added to suppress the amount of smoke produced by the polyurethane. The resulting polyurethane burns to produce dense protection. layer, and the smoke released is small.
The present invention adopts the following technical solutions. A method for preparing a flame-retardant water-based polyurethane coating, which is characterized in that: (1), in the presence of a dibutyltin dilaurate catalyst, 10-(2,5-dihydroxyphenyl)-9,10- Mix dihydro-9-oxa-10-phosphine-10-oxide and hexamethylene diisocyanate in a weight ratio of 2:1, react at 90~110°C for 1~4 hours, and then add nitrogen and phosphorus compounds to the reaction System, reaction temperature 70~110℃,The reaction time is 30 to 60 minutes to obtain a polyurethane prepolymer; the catalyst dosage is 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphinephenanthrene-10-oxidation 0.4~0.7% of the total weight of the compound and hexamethylene diisocyanate, the nitrogen and phosphorus compound is 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphinephenanthrene- 1.2~1.4% of the total weight of 10-oxide and hexamethylene diisocyanate; (2) Add 1.2~2.8% of the weight of the polyurethane prepolymer to the polyurethane prepolymer as a chain extender and 15~15% of the weight of the polyurethane prepolymer. 24% butanone solvent is stirred and reacted at 60-85°C for 2-5 hours. Triethylamine is added for neutralization reaction for 20-40 minutes. Water is added for emulsification to form a water-based polyurethane for later use. The triethylamine is 20~30% of the weight of polyurethane prepolymer;
(3) Add a dispersant of 1.5 to 1.8% of the weight of the manganese salt solution to a manganese salt solution with a mass concentration of 10%, and ultrasonically crush it for 20 minutes at a temperature of 30°C and a pH of 7 to obtain manganese. The salt dispersion is ready for use; (4) Mix the manganese salt dispersion with a water-based polyurethane solid content of 10 to 20%, the 5-hydroxytryptophan with a water-based polyurethane solid content of 3 to 4%, and the water-based polyurethane with a solid content of 10 to 20%. Hexachlorocyclotripolyphosphazene and water-based polyurethane with a solid content of 1 to 2%, diethylene triamine propylene plastic deodorant methyl dimethoxysilane are added to the water-based polyurethane, and sheared at a pH of 7 Stir for 30~80 minutes to obtain flame retardant water-based polyurethane coating. The invention has the following characteristics: (1) The prepared flame-retardant water-based polyurethane coating releases significantly less smoke than traditional flame-retardant polyurethane; (2) The nitrogen-phosphorus compound selected in the prepolymer synthesis not only has good flame retardancy properties, and can improve the surface defects of polyurethane films made from dibutyltin dilaurate, making the surface of the product smooth and smooth with good toughness. (3) Choose organic silicon as the chain extender, which can use nitrogen, phosphorus, and silicon compounds to form a good dense layer. The manganese salt compound has good smoke suppression properties and achieves the best flame retardant effect in fire and smoke prevention.
Main reference materials
[1] CN201210243915.6 Method for preparing 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide
[2] CN201410325853.2 Preparation method of flame-retardant water-based polyurethane coating
