CN110343413B - Nitrogen-phosphorus intumescent flame retardant and preparation method thereof in application of waterborne polyurethane coating - Google Patents
Nitrogen-phosphorus intumescent flame retardant and preparation method thereof in application of waterborne polyurethane coating Download PDFInfo
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- CN110343413B CN110343413B CN201910643179.5A CN201910643179A CN110343413B CN 110343413 B CN110343413 B CN 110343413B CN 201910643179 A CN201910643179 A CN 201910643179A CN 110343413 B CN110343413 B CN 110343413B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/48—Phosphonous acids R—P(OH)2; Thiophosphonous acids including RHP(=O)(OH); Derivatives thereof
- C07F9/4883—Amides or esteramides thereof, e.g. RP(NR'2)2 or RP(XR')(NR''2) (X = O, S)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
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- C07K1/30—Extraction; Separation; Purification by precipitation
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
- C09D5/185—Intumescent paints
Abstract
The invention relates to a preparation method of a nitrogen-phosphorus intumescent flame retardant and a method for applying the nitrogen-phosphorus intumescent flame retardant to the preparation of waterborne polyurethane paint, wherein dimethyl phosphite, basic catalyst sodium methoxide and acrylamide are mixed and then react to obtain an intermediate, a char forming agent and a substance A are added, the pH value of a solution is stabilized at 6.5-7.0 in the stirring process, a substance B and a substance C are added, the stirring reaction is continued, and the nitrogen-phosphorus intumescent flame retardant is obtained by concentration; the water-based polyurethane coating is prepared by using a nitrogen-phosphorus intumescent flame retardant. The flame retardant prepared by the invention can quickly suffocate flame, and improve the flame retardance of the nitrogen-phosphorus intumescent flame retardant from the aspects of releasing smoke, controlling the flaming combustion time and controlling the carbon layer compactness. In addition, the invention grafts the nitrogen-phosphorus intumescent flame retardant on the polyurethane, thereby further improving the flame retardance of the polyurethane.
Description
Technical Field
The invention relates to a preparation method of a flame retardant and a waterborne polyurethane coating, in particular to a preparation method of a nitrogen-phosphorus intumescent flame retardant and a method for preparing a waterborne polyurethane coating by using the nitrogen-phosphorus intumescent flame retardant.
Background
The flame retardant is mainly used in the fields of plastics, rubber, textiles, coatings and the like. The flame retardant mainly comprises hundreds of halogen flame retardants, phosphorus flame retardants, inorganic flame retardants and the like. The halogen flame retardant has the advantage of high cost performance, but releases a large amount of toxic or highly corrosive gas such as HX in the combustion process, and meanwhile, part of the halogen flame retardant has carcinogenic effect on human bodies, such as pentabromodiphenyl ether and octabromodiphenyl ether.
Common inorganic flame retardants are magnesium oxide and aluminum oxide, which need to absorb heat in the combustion process, so that the heat in the combustion process is reduced, meanwhile, water molecules are released in the combustion process, so that the oxygen concentration in a combustion area is diluted, and simultaneously, the magnesium oxide and the aluminum oxide generated in the combustion process are both refractory materials and cover the surface of a combustion object, so that the continuation of combustion can be slowed down. However, the inorganic flame retardant has the defects of large addition amount and poor compatibility with organic materials, and is easy to cause the reduction of the mechanical properties of the materials.
The Intumescent Flame Retardant (IFR) is an environment-friendly green flame retardant, does not contain halogen, does not adopt antimony oxide as a synergist, and has a synergistic effect. The plastic containing the intumescent flame retardant can generate a carbon foam layer on the surface during combustion, has the effects of heat insulation, oxygen isolation, smoke suppression, drip prevention and the like, has excellent flame retardant property, generates low smoke, low toxicity and no corrosive gas, accords with the research and development direction of future flame retardants, and is one of the most active flame retardant research fields at home and abroad.
Intumescent flame retardants have three basic elements. Namely an acid source, a carbon source and a gas source. The acid source is also called dehydrating agent or charring accelerant, which is inorganic acid or compound that can generate acid in situ during burning, such as phosphoric acid, boric acid, sulfuric acid and phosphate; the carbon source is also called as a carbon forming agent, which is the basis for forming a foam carbonized layer and mainly comprises polyhydroxy compounds with high carbon content, such as starch, cane sugar, dextrin, pentaerythritol, glycol, phenolic resin and the like; the gas source, also called a blowing source, is a nitrogen-containing compound such as urea, melamine, polyamide, and the like. In the three components, the acid source is the most main, the proportion is the largest, and the flame retardant element is contained in the acid source, so the acid source is a flame retardant in the true sense, and the carbon source and the foaming agent are synergistic agents.
The flame retardant effect of IFR relies primarily on the formation of a porous foam coke layer on the surface of the material, which is a heterogeneous system containing solid, liquid and gaseous products. The flame retardant property of the carbon layer is mainly reflected in that: the heat is difficult to penetrate the condensed phase, oxygen is prevented from entering a combustion area, and gaseous or liquid products generated by degradation are prevented from overflowing the surface of the material. The coke layer formation process is: at about 150 ℃, the acid source generates acid which can esterify the polyhydric alcohol and can be used as a dehydrating agent; at a slightly higher temperature, acid and a carbon source are subjected to esterification reaction, and amino in the system is used as a catalyst of the esterification reaction to accelerate the reaction; the system is melted before and during the esterification reaction, the system in a molten state is expanded and foamed by the incombustible gas generated in the reaction process, and meanwhile, the polyhydric alcohol and the ester are dehydrated and carbonized to form inorganic matters and carbon residues, so that the system is further foamed; when the reaction is nearly completed, the system is gelled and solidified, and finally a porous foam carbon layer is formed.
The aqueous polyurethane coating is a coating which takes aqueous polyurethane resin as a base material and water as a dispersion medium. The waterborne polyurethane coating modified by crosslinking has good storage stability, mechanical properties of a coating film, water resistance, solvent resistance and aging resistance, and the performance of the waterborne polyurethane coating is similar to that of the traditional solvent type polyurethane coating, so that the waterborne polyurethane coating is an important development direction of the waterborne polyurethane coating. The variety mainly comprises thermosetting polyurethane coating, water-based polyurethane coating containing blocked isocyanate and the like.
The film-forming raw material of the water-based polyurethane coating containing the blocked isocyanate consists of a polyisocyanate component and a hydroxyl-containing component. The polyisocyanates are blocked by phenol or other monofunctional reactive hydrogen atom-containing compounds, so that the two parts can be combined without reaction to give a one-component coating and have good storage stability. The polyisocyanate component reacts with the blocking agents such as phenol, malonate and caprolactam to generate urethane bonds, and the urethane bonds are cracked under the condition of heating to generate isocyanate, and then react with the hydroxyl component to generate polyurethane. Therefore, the film formation of the closed polyurethane water-based paint is to replace a weaker urethane bond with a more stable urethane bond by utilizing the difference of the thermal stability of the urethane bonds with different structures. There are many types of blocking agents, but aromatic isocyanate aqueous polyurethane coatings are mainly made of phenol or cresol. The aliphatic water-based polyurethane paint does not use phenols to avoid color change, and ethyl lactate, caprolactam, diethyl malonate, acetylacetone, ethyl acetoacetate and the like can be adopted.
Compared with the organic solvent type PU, the water-based PU has the advantages of low application cost, no pollution, easy treatment and good bonding effect, and has good development prospect in the adhesive and coating industries. The PU ionomer has good adhesion to both natural and synthetic rubber surfaces and can be used in the manufacture of footwear. The water-based PU is mainly used as furniture paint, electrophoretic paint, electrodeposition paint, building paint, paper processing paint, glass fiber paint and the like, and has special purposes besides the water-based paint, such as being used as an intermediate coating film of safety glass to prepare non-fragmenting safety glass which is widely used for automobiles, airplanes, ships or aerospace instruments. Aqueous dispersions are widely used as metal coatings, such as cationic electrodeposition coatings, in automotive primers to improve the corrosion resistance of vehicle bodies.
Chinese patent 201811556512.0 discloses an intumescent boron-nitrogen-phosphorus compound flame retardant and a preparation method thereof, and the preparation method comprises the following steps: (1) fully mixing the polypropylene material and the intumescent flame retardant; (2) and extruding and granulating by using a double-screw extruder to form mixed solid particles to obtain the intumescent boron-nitrogen-phosphorus compound flame retardant. According to the invention, by a compounding method, ammonium polyphosphate, pentaerythritol, boric acid and melamine are used as raw materials to obtain the intumescent nitrogen-phosphorus compound flame retardant, which has the characteristics of small addition amount, high flame retardant efficiency, good material compatibility, molten drop generation prevention, low toxicity, environmental protection and the like. The main disadvantages are that: the mechanical property of the flame retardant is reduced because the flame retardant is compounded, namely, the flame retardant is easily poor in compatibility because the inorganic material containing ammonium polyphosphate is mixed with the organic material polyacrylic acid, and meanwhile, the flame retardant is compounded, is suitable for melt mixing of polypropylene and is not suitable for water-based reaction.
Chinese patent 201710275245.9 relates to a halogen-free nitrogen-phosphorus compounded intumescent flame retardant and a preparation method thereof, which is a composite flame retardant taking nitrogen and phosphorus as main components. The product is produced by a special formula and a special process, has obvious flame retardant effect, is white (crystalline or amorphous) powder in appearance, is a mixture, can retard flame of PP through the synergistic effect of P-N, has good flame retardant property, high thermal stability, decomposition temperature of more than 280 ℃, high carbon residue rate, small moisture absorption, excellent dispersibility and good chemical stability, and can be mixed with other substances without chemical change. The main disadvantage is that the mechanical property of the material is easily reduced due to the compound flame retardant.
Chinese patent 201410325853.2 discloses a preparation method of a flame-retardant waterborne polyurethane coating, which comprises the steps of mixing 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with hexamethylene diisocyanate under the action of dibutyltin dilaurate catalyst, reacting for 1-4 h at 90-110 ℃, adding a nitrogen-phosphorus compound into a reaction system, reacting at 70-110 ℃ for 30-60 min, and obtaining a polyurethane prepolymer; adding a chain extender and a butanone solvent into a polyurethane prepolymer, reacting for 2-5 hours at the temperature of 60-85 ℃, adding triethylamine to perform a neutralization reaction for 20-40 min, and adding water to perform emulsification to form waterborne polyurethane; adding the manganese salt dispersion liquid, 5-hydroxytryptophan, hexachlorocyclotriphosphazene and gamma-diethylenetriamine propyl methyldimethoxysilane into polyurethane, and shearing and stirring for 30-80 min under the condition that the pH value is 7 to obtain the flame-retardant waterborne polyurethane coating. The flame retardance and the mechanical property of the obtained polyurethane are both greatly improved. The main disadvantage is that the obtained polyurethane has longer flame combustion time and higher smoke density, which is easy to cause safety hazard.
In summary, the existing water-based polyurethane coating has poor flame retardance, flame combustion time and smoke density are relatively long in the existing research, and polyurethane as a plastic body is easy to generate molten drops in the combustion process to cause secondary harm.
Disclosure of Invention
The invention aims to provide a preparation method of a nitrogen-phosphorus intumescent flame retardant and a method for applying the nitrogen-phosphorus intumescent flame retardant to the preparation of a waterborne polyurethane coating, and aims to solve the technical problem of synthesizing a waterborne nitrogen-phosphorus intumescent flame retardant for replacing the traditional compound or non-hydrophilic intumescent flame retardant and further improving or increasing the flame retardant index (the core index is oxygen index, smoke density, flame combustion time and flameless combustion time) of the waterborne polyurethane coating; meanwhile, the generation and the dripping of burning molten drops are more effectively controlled, and the water-based polyurethane coating with fire resistance and reduced molten drops is obtained.
The technical scheme of the invention is as follows:
the preparation method of the nitrogen-phosphorus intumescent flame retardant is characterized by comprising the following steps: mixing dimethyl phosphite, a basic catalyst sodium methoxide and acrylamide, reacting at 70-90 ℃ for 3-5 hours to obtain 3-dimethoxyphosphoryl propionamide as an intermediate, cooling the intermediate, adding a char forming agent and a substance A, stirring at 60-80 ℃ for 2-5 hours to react, stabilizing the pH of the solution at 6.5-7.0 in the stirring process, adding a substance B and a substance C, stirring at 60-80 ℃ for 2-5 hours to react, and concentrating to obtain a nitrogen-phosphorus intumescent flame retardant;
the char-forming agent is any one of trimethylchlorosilane, cyanuric chloride and trimethylolpropane;
the substance A is any one of potassium sodium tartrate, sodium ammonia triacetate and p-nitrobenzoic acid;
the substance B is any one of 2, 4-dihydroxy benzophenone, itaconic anhydride and citraconic acid;
the substance C is any one of 1,3, 5-triazine, indole-3-acetamide and 1, 4-cyclohexane dimethyl dicarboxylate.
The preparation steps are as follows: adding a basic catalyst sodium methoxide with the mass of 10% of dimethyl phosphite into 1mol of dimethyl phosphite, adding 0.9-1.2 mol of acrylamide, reacting for 3-5 h at 70-90 ℃ to obtain 3-dimethoxyphosphoryl propionamide as an intermediate A, cooling the temperature of the intermediate product to 50-55 ℃, adding 0.9-1.3 mol of a char forming agent and 0.1mol of a substance A0, stirring and reacting for 2-5 h at 60-80 ℃, adjusting the pH of the solution to 6.5-7.0 during stirring, adding 3.1-8.7 g of a substance B and 0.2g-0.4 g of a substance C0, stirring and reacting for 2-5 h at 60-80 ℃, and concentrating until the solid content reaches more than 90% to obtain the nitrogen-phosphorus intumescent flame retardant.
The method for preparing the waterborne polyurethane coating by using the nitrogen-phosphorus intumescent flame retardant is characterized by comprising the following steps of: reacting dihydric alcohol, isocyanate and dibutyltin dilaurate to obtain a polyurethane prepolymer; adding a hydrophilic chain extender, the nitrogen-phosphorus intumescent flame retardant and an acetone solvent into the polyurethane prepolymer for reaction; and adding triethylamine for neutralization, and finally adding water for emulsification to obtain the hydrophilic polyurethane coating.
The preparation steps are as follows: adding 45g of dihydric alcohol, 21.6-24.8 g of isocyanate and 0.12-0.15 g of dibutyltin dilaurate into a container provided with a stirring device, a temperature control display device and a condenser tube, reacting for 2-4 h at 60-80 ℃, adding 0.5-0.7 g of polypeptide and 0.2-0.4 g of 2-tert-butyl-p-cresol, and stirring and reacting for 1-2 h at 50-70 ℃ to obtain a polyurethane prepolymer; adding 2.2-3.4 g of hydrophilic chain extender, 1.3-1.7 g of nitrogen-phosphorus intumescent flame retardant and 6.1-8.2 g of acetone solvent into the polyurethane prepolymer, and reacting for 1-2 h at the temperature of 60-80 ℃; and then adding 0.6-1.2 g of polypeptide and 0.2-0.4 g of dimethylaminopropyl methacrylamide, stirring and reacting for 1-2 hours at 50-60 ℃, adding 2.0-4.5 g of triethylamine for neutralization, and finally adding 150-160 g of water for emulsification for 20-40 minutes to obtain the hydrophilic polyurethane coating.
Preferably, the diol is a polycarbonate diol or hexanediol.
Preferably, the polycarbonate diol has a weight average molecular weight of 2000.
Preferably, the isocyanate is isophorone diisocyanate or hexamethylene diisocyanate.
Preferably, the hydrophilic chain extender is dimethylolpropionic acid.
Preferably, the preparation method of the polypeptide comprises the following steps: mixing 10g of chrome-containing leather scraps, 200-240 g of water, 6-8 g of calcium oxide and 0.6-0.7 g of sodium dodecyl benzene sulfonate, stirring for 6-8 h as pretreatment, adding 5-6 g of calcium oxide, heating to 70-90 ℃, stirring for 5-6 h to obtain a hydrolysate, performing first suction filtration, adding oxalic acid into the filtered hydrolysate to adjust the pH value of the hydrolysate to 6.5-7.5, performing suction filtration, standing, stabilizing the suction filtration liquid, filtering, precipitating, and drying the suction filtration liquid to obtain the polypeptide.
The invention has the positive effects that:
(1) the invention synthesizes the water-based nitrogen-phosphorus intumescent flame retardant by integrating the advantages of the existing intumescent flame retardant, and improves the flame retardance of the water-based polyurethane coating by utilizing the good flame retardant efficiency of the nitrogen-phosphorus intumescent flame retardant. The existing flame retardant has two flame retardant modes, firstly, the flame retardant purpose is achieved by releasing a large amount of smoke and reducing the oxygen concentration in a combustion area, but the main reason for death caused by asphyxiation of human body in fire is the release of a large amount of smoke; the second flame-retardant mode is that the smoke released is small enough to achieve the flame-retardant effect by shortening the flaming combustion time, which is the most ideal treatment mode for flame retardance and is also the main aim of the invention.
(2) The invention utilizes dimethyl phosphite and acrylamide to react under the action of an alkaline catalyst to generate an intermediate 3-dimethoxyphosphoryl propionamide, and obtains a nitrogen-phosphorus intumescent flame retardant under the action of a charring agent (trimethylchlorosilane, cyanuric chloride and trimethylolpropane).
(3) The compactness of a carbonized layer expanded by the nitrogen-phosphorus intumescent flame retardant is one of key factors of flame retardance, the compactness (lateral reaction of residual carbon rate) of the carbonized layer is improved by adopting sodium potassium tartrate, sodium aminotriacetate and p-nitrobenzoic acid, the contact chance of external heat and a burnt object is prevented, meanwhile, the time of flame combustion in the combustion process is reduced by adopting 2, 4-dihydroxybenzophenone, itaconic anhydride and citraconic acid, so that the flame of the burnt object can be quickly choked, the smoke released by combustion is reduced by adopting 1,3, 5-triazine, indole-3-acetamide and 1, 4-dimethyl cyclohexanedicarboxylate, and the flame retardance of the nitrogen-phosphorus intumescent flame retardant is improved from the aspects of smoke release, flame combustion time control and carbon layer compactness.
(4) According to the invention, the nitrogen-phosphorus intumescent flame retardant is grafted to the polyurethane, so that the flame retardance of the polyurethane is further improved, the effect of integrating the flame retardant and the polyurethane is achieved, and the flame retardant effect is brought into play on the basis of keeping the original property of the polyurethane.
(5) The biggest defect of polyurethane combustion is the generation of molten drops, which can cause secondary damage. According to the invention, the polyurethane is modified by adopting the polypeptide obtained by hydrolyzing chrome-containing leather scraps, and 2-tert-butyl-p-cresol and dimethylaminopropyl methacrylamide are adopted to promote the polypeptide to be combined with the polyurethane, so that the polypeptide is uniformly dispersed on a branched chain of a resin chain, the molten drop amount generated by the combustion of the prepared polyurethane resin is further reduced, wherein the 2-tert-butyl-p-cresol reacts with the polypeptide in a prepolymer of the polyurethane to cause the molten drop of the prepolymer to be reduced, the 2-tert-butyl-p-cresol promotes the molten drop of the polyurethane to not drop, the dimethylaminopropyl methacrylamide and the polypeptide act synergistically to reduce the molten drop generated by the polyurethane, and the dimethylaminopropyl methacrylamide plays a role in promoting the reduction of the molten drop.
(6) The flame retardant has the advantages of high water-based, carbon residue rate and expansion height, environmental protection and no toxicity.
Detailed Description
The invention is further illustrated below with reference to specific examples, comparative examples and technical effect data.
Example one
(1) And preparing the nitrogen-phosphorus intumescent flame retardant: adding 1mol of dimethyl phosphite into 1/10 wt% of basic catalyst sodium methoxide, adding 0.9mol of acrylamide, reacting at 70 ℃ for 3h to obtain 3-dimethoxyphosphoryl propionamide, namely an intermediate A, reducing the temperature of the intermediate product to 50 ℃, adding 0.9mol of trimethylchlorosilane and 0.1mol of potassium sodium tartrate, stirring at 60 ℃ for 2h, adjusting the pH of the solution by using sodium hydroxide during stirring to stabilize the pH of the solution at 6.5-7.0, adding 3.1g of 2, 4-dihydroxybenzophenone and 0.2g of 1,3, 5-triazine, stirring at 60 ℃ for 2h, and concentrating until the solid content reaches 90% (not more than 92%) to obtain the nitrogen-phosphorus intumescent flame retardant.
(2) Adding 45g of polycarbonate diol with the molecular weight of 2000, 21.6g of isophorone diisocyanate and 0.12g of dibutyltin dilaurate into a 500ml three-neck flask provided with a stirring paddle, a thermometer and a condenser tube, reacting for 2 hours at 60 ℃, adding 0.5g of polypeptide and 0.2g of 2-tert-butyl-p-cresol, and reacting for 1 hour at 50 ℃ by stirring to obtain a polyurethane prepolymer; adding 2.2g of hydrophilic chain extender dimethylolpropionic acid, 1.3g of the nitrogen-phosphorus intumescent flame retardant in the step (1) and 6.1g of acetone solvent into the polyurethane prepolymer, and reacting for 1h at 60 ℃; then 0.6g of polypeptide and 0.2g of dimethylaminopropyl methacrylamide are added, stirred and reacted for 1 hour at the temperature of 50 ℃, neutralized by 2.0g of triethylamine and emulsified for 20 minutes by adding 150g of water, thus obtaining the waterborne polyurethane coating.
The polycarbonate diol had a weight average molecular weight of 2000.
The preparation method of the polypeptide comprises the following steps: mixing 10g of chrome-containing leather scraps (less than 4% of chromium trioxide and the same below) with 200g of water, 6g of calcium oxide and 0.6g of sodium dodecyl benzene sulfonate, stirring for 6 hours as pretreatment, adding 5g of calcium oxide, heating to 70 ℃, stirring for 5 hours to obtain a hydrolysate, performing first suction filtration, adding oxalic acid into the hydrolysate subjected to suction filtration to adjust the pH value of the hydrolysate to 6.5-7.5, performing suction filtration again, standing, filtering and precipitating after the filtrate is stable, and drying the suction filtration liquid to obtain the polypeptide.
Example two
(1) And preparing the nitrogen-phosphorus intumescent flame retardant: adding 1mol of dimethyl phosphite into sodium methoxide which is an alkaline catalyst, wherein the weight of the sodium methoxide is 1/10% of that of the dimethyl phosphite, then adding 1.2mol of acrylamide, reacting at the reaction temperature of 90 ℃ for 5h to obtain 3-dimethoxyphosphoryl propionamide, namely an intermediate A, reducing the temperature of the intermediate product to 55 ℃, adding 1.3mol of cyanuric chloride and 0.1mol of sodium nitrilotriacetate, stirring at the temperature of 80 ℃ for 5h, adjusting the pH of the solution by using sodium hydroxide during stirring to stabilize the pH of the solution at 6.5-7.0, then adding 8.7g of itaconic anhydride and 0.4g of indole-3-acetamide, stirring at the temperature of 80 ℃ for 5h, and concentrating until the solid content reaches 90% (not more than 92%) to obtain the nitrogen-phosphorus intumescent flame retardant.
(2) Adding 45g of hexanediol, 24.8g of hexamethylene diisocyanate and 0.15g of dibutyltin dilaurate into a 500ml three-neck flask provided with a stirring paddle, a thermometer and a condenser, reacting for 4 hours at 80 ℃, adding 0.7g of polypeptide and 0.4g of 2-tert-butyl-p-cresol, and stirring for reacting for 2 hours at 70 ℃ to obtain a polyurethane prepolymer; adding 3.4g of hydrophilic chain extender dimethylolpropionic acid, 1.7g of the nitrogen-phosphorus intumescent flame retardant in the step (1) and 8.2g of acetone solvent into the polyurethane prepolymer, and reacting for 2 hours at 80 ℃; then adding 1.2g of polypeptide and 0.4g of dimethylaminopropyl methacrylamide, stirring and reacting for 2 hours at the temperature of 60 ℃, then neutralizing with 4.5g of triethylamine, and adding 160g of water for emulsification for 40 minutes to obtain the hydrophilic polyurethane coating.
The preparation method of the polypeptide comprises the following steps: mixing 10g of chrome-containing leather scraps, 240g of water, 8g of calcium oxide and 0.7g of sodium dodecyl benzene sulfonate, stirring for 8 hours as pretreatment, adding 6g of calcium oxide, heating to 90 ℃, stirring for 6 hours to obtain a hydrolysate, performing first suction filtration, adding oxalic acid into the filtered hydrolysate to adjust the pH value of the hydrolysate to 6.5-7.5, performing suction filtration again, standing, filtering and precipitating after the filtrate is stable, and drying the suction filtration liquid to obtain the polypeptide.
Example three
(1) And preparing the nitrogen-phosphorus intumescent flame retardant: adding 1mol of dimethyl phosphite into a basic catalyst sodium methoxide which is 1/10 weight percent of the dimethyl phosphite, adding 1.05mol of acrylamide, reacting at the reaction temperature of 80 ℃ for 4 hours to obtain 3-dimethoxyphosphoryl propionamide, namely an intermediate A, reducing the temperature of the intermediate product to 50 ℃, adding 1.1mol of trimethylolpropane and 0.1mol of p-nitrobenzoic acid, stirring and reacting at the temperature of 70 ℃ for 3.5 hours, adjusting the pH of the solution by using sodium hydroxide during stirring to stabilize the pH of the solution at 6.5-7.0, adding 5.9g of citraconic acid and 0.3g of 1, 4-dimethyl cyclohexanedicarboxylate, stirring and reacting at the temperature of 70 ℃ for 3.5 hours, and concentrating until the solid content reaches 90 percent (not more than 92 percent) to obtain the nitrogen-phosphorus intumescent flame retardant.
(2) Adding 45g of polycarbonate diol, 23.2g of isophorone diisocyanate and 0.13g of dibutyltin dilaurate into a 500ml three-neck flask provided with a stirring paddle, a thermometer and a condenser, reacting for 3 hours at 70 ℃, adding 0.6g of polypeptide and 0.3g of 2-tert-butyl-p-cresol, and reacting for 1.5 hours at 60 ℃ by stirring to obtain a polyurethane prepolymer; adding 2.8g of hydrophilic chain extender dimethylolpropionic acid, 1.5g of the nitrogen-phosphorus intumescent flame retardant in the step (1) and 7.1g of acetone solvent into the polyurethane prepolymer, and reacting for 1.5h at 70 ℃; then 0.9g of polypeptide and 0.3g of dimethylaminopropyl methacrylamide were added, stirred and reacted for 1.5h at 55 ℃, neutralized with 3.2g of triethylamine, and emulsified for 30min by adding 155g of water, thus obtaining the hydrophilic polyurethane coating.
The preparation method of the polypeptide comprises the following steps: mixing 10g of chrome-containing leather scraps, 220g of water, 7g of calcium oxide and 0.65g of sodium dodecyl benzene sulfonate, stirring for 7h as pretreatment, adding 5.5g of calcium oxide, heating to 80 ℃, stirring for 5.5h to obtain hydrolysate, performing first suction filtration, adding oxalic acid into the filtered hydrolysate to adjust the pH value of the hydrolysate to 6.5-7.5, performing suction filtration, standing, filtering and precipitating after the filtrate is stable, and drying the suction filtration to obtain the polypeptide.
Determination of the char yield and the swell height: the sample 1g was weighed, the change in mass of the crucible used was recorded, the crucible to which the sample was added was placed in a muffle furnace, the crucible was removed at 450 ℃, and the height in the sample at that time and the mass M1 of the crucible after heating were measured.
ASTM E662 and GB 8323-87 both specify a smoke density determination method developed by the national institute of standards and technology (NBS), now the national institute of technology and standards, NITS, using a smoke density box. A test sample of 7.6cm multiplied by 2.5cm is vertically fixed in a box body of 91cm multiplied by 63cm, and the heat flow generated by a heater is 25kW per square meter. In the test, the sample is burned in the box to generate smoke, the change of the light transmittance of the parallel light beams passing through the smoke is measured, and the specific optical density, namely the smoke density of the smoke generated by the sample per unit area and diffused in the unit optical path length of the smoke box per unit volume is calculated and is represented by Ds.
GB/T5455-1997 (vertical method for testing textile burning performance) determines the flame burning time (afterflame time) of the film formed by the polyurethane coating.
TABLE 1 Properties of the Nitrogen phosphorus intumescent flame retardants
The comparative sample 2 is the flame retardant prepared by the example 2 of the Chinese patent 201710275245.9, most of the traditional nitrogen-phosphorus intumescent flame retardant is insoluble in water and is difficult to be used in the synthesis of polyurethane, the flame retardant of the invention shows better in the aspects of carbon residue rate and expansion height, and the flame retardant obtained by the invention and the comparative sample are compared under the drying condition.
TABLE 2 film Properties of waterborne polyurethane coatings
The comparison sample 1 is the second example of Chinese patent 201410325853.2, and the flame burning time and smoke density index are superior to those of the second example of comparison document 1, and the burning molten drop phenomenon is that the heated change of the film in burning is observed in the flame burning. The smoke density of the invention is graded to characterize the smoke release property of the polyurethane coating film.
TABLE 3 Properties of the Nitrogen phosphorus intumescent flame retardant (without addition of A)
| Example one | Example two | Example three | |
| Carbon content/%) | 41.2 | 53.2 | 54.3 |
| Height of expansion/cm | 3.12 | 3.56 | 4.98 |
As can be seen from Table 3, the carbon content without the addition of substance A decreased, resulting in a partial release of gas and therefore a decrease in the height of expansion.
TABLE 4 film Properties of waterborne polyurethane coatings (without addition of substance B)
| Example one | Example two | Example three | |
| Flame combustion time/s | 15.6 | 14.8 | 12.3 |
| Density of smoke | 14 | 11 | 15 |
As can be seen from Table 4, the flame burn time without the addition of substance B was improved and the smoke density did not vary much.
TABLE 5 film Properties of waterborne polyurethane coatings (without addition of substance C)
| Example one | Example two | Example three | |
| Flame combustion time/s | 4.2 | 1.6 | 3.5 |
| Density of smoke | 31 | 35 | 42 |
As can be seen from Table 5, the smoke density rating was greatly improved without the addition of substance C.
TABLE 6 film formation Properties of waterborne polyurethane coatings (none of the following)
As can be seen from Table 6, since the addition of one of the above substances causes the generation of droplets and the dropping, the synergistic effect of the above polypeptide, 2-t-butyl-p-cresol and dimethylaminopropyl methacrylamide is required, and the effect of generating a slight amount of droplets but not dropping (e.g., the effect of burning Dacron) can be exerted.
Claims (8)
1. A method for preparing water-based polyurethane coating by using nitrogen and phosphorus intumescent flame retardants is characterized in that a polyurethane prepolymer is obtained by using dihydric alcohol, isocyanate and dibutyltin dilaurate for reaction; adding a hydrophilic chain extender, a nitrogen-phosphorus intumescent flame retardant and an acetone solvent into the polyurethane prepolymer for reaction; adding triethylamine for neutralization, and finally adding water for emulsification to obtain the hydrophilic polyurethane coating;
the preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps: mixing dimethyl phosphite, a basic catalyst sodium methoxide and acrylamide, reacting at 70-90 ℃ for 3-5 hours to obtain 3-dimethoxyphosphoryl propionamide as an intermediate, cooling the intermediate, adding a char forming agent and a substance A, stirring at 60-80 ℃ for 2-5 hours to react, stabilizing the pH of the solution at 6.5-7.0 in the stirring process, adding a substance B and a substance C, stirring at 60-80 ℃ for 2-5 hours to react, and concentrating to obtain a nitrogen-phosphorus intumescent flame retardant;
the char-forming agent is any one of trimethylchlorosilane, cyanuric chloride and trimethylolpropane;
the substance A is any one of potassium sodium tartrate, sodium ammonia triacetate and p-nitrobenzoic acid;
the substance B is any one of 2, 4-dihydroxy benzophenone, itaconic anhydride and citraconic acid;
the substance C is any one of 1,3, 5-triazine, indole-3-acetamide and 1, 4-cyclohexane dimethyl dicarboxylate.
2. The method for preparing the waterborne polyurethane coating from the nitrogen-phosphorus intumescent flame retardant of claim 1, wherein the preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps: adding a basic catalyst sodium methoxide with the mass of 10% of dimethyl phosphite into 1mol of dimethyl phosphite, adding 0.9-1.2 mol of acrylamide, reacting for 3-5 h at 70-90 ℃ to obtain 3-dimethoxyphosphoryl propionamide as an intermediate, reducing the temperature of the intermediate to 50-55 ℃, adding 0.9-1.3 mol of a char forming agent and 0.1mol of a substance A0, stirring and reacting for 2-5 h at 60-80 ℃, adjusting the pH of the solution to 6.5-7.0 in the stirring process, adding 3.1-8.7 g of a substance B and 0.2g-0.4 g of a substance C, stirring and reacting for 2-5 h at 60-80 ℃, and concentrating until the solid content reaches more than 90% to obtain the nitrogen-phosphorus intumescent flame retardant.
3. The method for preparing the waterborne polyurethane coating by using the nitrogen-phosphorus intumescent flame retardant as claimed in claim 1, wherein 45g of the dihydric alcohol, 21.6g to 24.8g of the isocyanate and 0.12g to 0.15g of the dibutyltin dilaurate are added into a container provided with a stirring device, a temperature control display device and a condenser tube, and the mixture is reacted at 60 to 80 ℃ for 2 to 4 hours, then 0.5 to 0.7g of the polypeptide and 0.2 to 0.4g of 2-tert-butyl-p-cresol are added, and the mixture is stirred and reacted at 50 to 70 ℃ for 1 to 2 hours to obtain a polyurethane prepolymer; adding 2.2-3.4 g of hydrophilic chain extender, 1.3-1.7 g of nitrogen-phosphorus intumescent flame retardant and 6.1-8.2 g of acetone solvent into the polyurethane prepolymer, and reacting for 1-2 h at the temperature of 60-80 ℃; and then adding 0.6-1.2 g of polypeptide and 0.2-0.4 g of dimethylaminopropyl methacrylamide, stirring and reacting for 1-2 hours at 50-60 ℃, adding 2.0-4.5 g of triethylamine for neutralization, and finally adding 150-160 g of water for emulsification for 20-40 minutes to obtain the hydrophilic polyurethane coating.
4. The method for preparing the waterborne polyurethane coating from the nitrogen-phosphorus intumescent flame retardant of claim 1, wherein the dihydric alcohol is polycarbonate diol or hexanediol.
5. The method for preparing the waterborne polyurethane coating with the nitrogen-phosphorus intumescent flame retardant of claim 4, wherein the weight average molecular weight of the polycarbonate diol is 2000.
6. The method for preparing the waterborne polyurethane coating by using the nitrogen-phosphorus intumescent flame retardant of claim 1, wherein the isocyanate is isophorone diisocyanate or hexamethylene diisocyanate.
7. The method for preparing the waterborne polyurethane coating from the nitrogen-phosphorus intumescent flame retardant as claimed in claim 1, wherein the hydrophilic chain extender is dimethylolpropionic acid.
8. The method for preparing the waterborne polyurethane coating from the nitrogen-phosphorus intumescent flame retardant as claimed in claim 3, wherein the preparation method of the polypeptide comprises the following steps: mixing 10g of chrome-containing leather scraps, 200-240 g of water, 6-8 g of calcium oxide and 0.6-0.7 g of sodium dodecyl benzene sulfonate, stirring for 6-8 h as pretreatment, adding 5-6 g of calcium oxide, heating to 70-90 ℃, stirring for 5-6 h to obtain a hydrolysate, performing first suction filtration, adding oxalic acid into the filtered hydrolysate to adjust the pH value of the hydrolysate to 6.5-7.5, performing suction filtration, standing, stabilizing the suction filtration liquid, filtering, precipitating, and drying the suction filtration liquid to obtain the polypeptide.
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| CN201910643179.5A CN110343413B (en) | 2019-07-17 | 2019-07-17 | Nitrogen-phosphorus intumescent flame retardant and preparation method thereof in application of waterborne polyurethane coating |
| JP2019236699A JP6773351B1 (en) | 2019-07-17 | 2019-12-26 | Application to nitrogen-phosphorus-based expansive flame retardants and methods for adjusting water-based polyurethane paints |
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