CN112279995A - Intrinsic flame-retardant waterborne polyurethane and preparation method thereof - Google Patents
Intrinsic flame-retardant waterborne polyurethane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an intrinsic flame-retardant waterborne polyurethane which is polymerized by isocyanate, polyalcohol, a dihydroxyl high phosphorus nitrogen content flame-retardant functional monomer and a hydrophilic chain extender; the dihydroxyl high phosphorus-nitrogen content flame-retardant functional monomer is prepared by further reacting a phosphorus-nitrogen integrated functional compound prepared by taking glycine, paraformaldehyde and dimethyl phosphite as raw materials with a diepoxy compound. The intrinsic flame-retardant waterborne polyurethane can be used as a flame-retardant additive by adjusting and improving the proportion of the flame-retardant section, has high flame-retardant efficiency and lasting effect, and does not have the problems of volatility, migration, precipitation and the like.
Description
Technical Field
The invention relates to an intrinsic flame-retardant waterborne polyurethane and a preparation method thereof.
Background
Waterborne Polyurethanes (WPU) are polyurethanes that use water as the dispersing medium and contain no or very little organic solvents in the dispersion. The polyurethane coating film has a series of excellent characteristics, such as abrasion resistance, chemical resistance, good toughness, elasticity and adhesion to a substrate, can be cured at room temperature or low temperature, and is widely applied to the fields of leather processing, building coatings, adhesives and the like. However, under normal conditions, most of the waterborne polyurethane is flammable polyurethane materials without flame retardant treatment, which is easy to become a fire hazard, and the flame retardant property of the waterborne polyurethane is one of important directions for the functionalization. The flame-retardant water-based flame-retardant coating adhesive is applied to the surface of a combustible substrate, has the effects of insulating heat and substances, delaying ignition time, delaying combustion development and the like, ensures safety and has wide application prospect.
The intrinsic flame-retardant waterborne polyurethane is also called as reactive flame-retardant waterborne polyurethane, and refers to that a flame-retardant unit is directly introduced into a polyurethane matrix to form a part of the structure of the polyurethane matrix through the synthetic reaction of the waterborne polyurethane, so that the flame-retardant effect is achieved under the condition of not adding foreign matters, the utilization rate of a flame retardant and a flame-retardant modifier is reduced, the intrinsic flame-retardant efficiency is higher, the effect is more durable under the condition of the same flame-retardant element content, and the problems of volatilization, migration, precipitation and the like do not exist. The intrinsic flame retardance is modified from a molecular level, and the problem of a related interface is fundamentally overcome.
The intrinsic flame-retardant waterborne polyurethane can be classified into halogen flame retardant and halogen-free flame retardant. Although halogen flame-retardant waterborne polyurethane has better flame-retardant effect under normal conditions, substances such as hydrogen halide and the like are easily generated during thermal decomposition, and a large amount of smoke, corrosive and toxic gas can be generated in the cracking process, so that the halogen flame-retardant waterborne polyurethane is increasingly stressed in the aspects of environmental protection and the like; the halogen-free flame retardant polyurethane solves the defects to a certain extent, does not volatilize during combustion, does not generate corrosive gas, and has higher char forming rate and lower combustibility, thereby having better application value. The aqueous polyurethane disclosed by the invention is halogen-free and flame-retardant, is safe and environment-friendly, can change the structure of the intrinsic flame-retardant polyurethane by adjusting the proportion of the flame-retardant section, improves the dispersion and flame-retardant properties, has small particle size of a target product, low viscosity and good emulsion stability and flame-retardant property, and has application value in the fields of fabric coatings, leather finishing, aqueous adhesives and the like.
Disclosure of Invention
The invention aims to provide an intrinsic flame-retardant waterborne polyurethane; the technical scheme is as follows:
the intrinsic flame-retardant waterborne polyurethane is prepared by polymerizing isocyanate, polyalcohol, a dihydroxy high-phosphorus-nitrogen-content flame-retardant functional monomer and a hydrophilic chain extender; the dihydroxyl high phosphorus-nitrogen content flame-retardant functional monomer is prepared by further reacting a phosphorus-nitrogen integrated functional compound prepared by taking glycine, paraformaldehyde and dimethyl phosphite as raw materials with a diepoxy compound.
The preparation steps of the dihydroxy high-phosphorus-nitrogen-content flame-retardant functional monomer are as follows:
(1) mixing paraformaldehyde, glycine and tetrahydrofuran, heating to 60-70 ℃, then dropwise adding dimethyl phosphite, and continuing to perform heat preservation reaction until the reaction is sufficient after dropwise adding; after the reaction is finished, removing the solvent tetrahydrofuran to obtain a light yellow viscous liquid which is the phosphorus-nitrogen integrated functional compound;
(2) mixing the phosphorus-nitrogen integrated functional compound with dichloroethane, slowly dropwise adding a diepoxy compound, slowly heating to 45-60 ℃ in the dropwise adding process, carrying out heat preservation reaction at 45-60 ℃ after dropwise adding is finished, heating to 75-90 ℃, and continuing the heat preservation reaction until the reaction is full; after the reaction is finished, removing the dichloroethane as the solvent to obtain yellow viscous liquid, namely the dihydroxyl high phosphorus nitrogen content flame-retardant functional monomer.
In the step (1), the solvent tetrahydrofuran is removed, and then the following treatment is required: firstly adding a small amount of water for washing, then adding anhydrous sodium sulfate for drying, and finally carrying out solid-liquid separation to obtain a light yellow viscous liquid which is the phosphorus-nitrogen integrated functional compound. The amount of water is generally 1/10 to 1/5 volume percent of the amount of tetrahydrofuran.
In the step (2), after dichloroethane is removed, the following treatment is required: firstly adding a small amount of water for washing, then adding anhydrous sodium sulfate for drying, and finally carrying out solid-liquid separation to obtain a faint yellow viscous liquid which is the dihydroxyl high phosphorus-nitrogen content flame-retardant functional monomer. The amount of water is generally 1/10 to 1/5 volume-wise of the amount of dichloroethane.
In the step (1), the dripping speed is 1-2 seconds per drop, and the reaction is finished after the heat preservation reaction is continued for 7-9 hours after the dripping is finished; in the step (2), the dropping speed is 1-2 seconds per drop, the reaction time is 0.5-2 hours at the temperature of 45-60 ℃, and the reaction time is 3-6 hours at the temperature of 75-90 ℃.
The preparation method of the intrinsic flame-retardant waterborne polyurethane comprises the following steps: mixing polyol and a hydrophilic chain extender, heating to 75-90 ℃, starting to dropwise add isocyanate, and continuing to perform heat preservation reaction after dropwise adding is finished until the reaction is complete to prepare a reaction solution; adding a dihydroxy high-phosphorus-nitrogen-content flame-retardant functional monomer into the reaction solution at 75-90 ℃, carrying out heat preservation reaction until the reaction is sufficient, and obtaining the intrinsic flame-retardant waterborne polyurethane after the reaction is finished; the above reaction can be carried out in the presence of a solvent, or a proper amount of a solvent can be added depending on the viscosity change during the reaction to smoothly carry out the stirring, and if the solvent is added, the solvent needs to be removed after the reaction is finished. The dripping time of the isocyanate is generally 1-2 hours, and the time for continuing the heat preservation reaction after the dripping is finished is 1-2 hours; the time of the heat preservation reaction after the dihydroxyl high phosphorus nitrogen content flame retardant functional monomer is added is 3 to 5 hours.
The solvent is butanone, ethyl acetate, dichloroethane or toluene.
After the reaction of the dihydroxyl high phosphorus nitrogen content flame-retardant functional monomer is completed, adding an alkaline neutralizing agent to neutralize the system to weak acidity or neutrality, and after the neutralization is completed, preparing the intrinsic flame-retardant waterborne polyurethane; and if the solvent is added, removing the solvent after the neutralization is finished, and obtaining the intrinsic flame-retardant waterborne polyurethane after the solvent is removed. The neutralization is carried out at a temperature of 40-50 ℃.
The alkaline neutralizing agent is ammonia water, 2-amino-2-methyl-1-propanol, diethanolamine, triethanolamine, diethylamine, triethylamine, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium acetate, sodium pyrophosphate or sodium carbonate.
The molar ratio of the glycine to the paraformaldehyde to the dimethyl phosphite is 1.0-1.2:2.0-4.0:4.0, and the molar ratio of the phosphorus-nitrogen integrated functional compound to the diepoxide is 2.0-2.4: 1.0.
The diepoxide is one or a mixture of more than two of diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether and resorcinol diglycidyl ether.
The isocyanate is selected from one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI) and lysine diisocyanate. Toluene Diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are preferred.
The polyol comprises a polyether polyol or a polyester polyol; the polyether glycol is polyoxypropylene diol, polyoxypropylene triol, polytetrahydrofuran diol or tetrahydrofuran-propylene oxide copolymerization diol; the polyester polyol is one or more of polyethylene glycol adipate diol, 1, 4-butanediol adipate diol, diethylene glycol adipate diol, polycarbonate diol and polycaprolactone diol. Preferably, the polyoxypropylene diol (PPG), more preferably, the polyoxypropylene diol is polyoxypropylene diol-600 (PPG-600).
The hydrophilic chain extender is 2, 2-hydroxymethylpropionic acid (DMPA) or 2, 2-hydroxymethylbutyric acid (DMBA).
The mass ratio of the isocyanate to the polyalcohol is 1:3-3:1, the dosage of the dihydroxy high phosphorus nitrogen content flame-retardant functional monomer is 10-40% of the sum of the isocyanate, the dihydroxy high phosphorus nitrogen content flame-retardant functional monomer and the polyalcohol, and the dosage of the hydrophilic chain extender is 2-10% of the sum of the isocyanate, the dihydroxy high phosphorus nitrogen content flame-retardant functional monomer and the polyalcohol.
On one hand, the preparation reaction process of the dihydroxyl flame-retardant functional monomer is simple, the operation is convenient and safe, the phosphorus content is rich, the halogen-free environment is protected, the char formation rate is high, and the flame-retardant efficiency can be further improved through the synergistic effect of phosphorus and nitrogen; on the other hand, the intrinsic flame-retardant polyurethane polymer can be used as a flame-retardant additive by adjusting and increasing the proportion of the flame-retardant section, has high flame-retardant efficiency and lasting effect, and does not have the problems of volatilization, migration, precipitation and the like; can also be directly used as a flame-retardant modified polyurethane material, and has application value in the fields of fabric coating, leather finishing, water-based adhesives and the like.
Drawings
FIG. 1 is an infrared spectrum of the product obtained in step (1) of example 1;
FIG. 2 is an infrared spectrum of the product obtained in step (2) of example 1;
FIG. 3 is a nuclear magnetic resonance spectrum of the product obtained in step (1) of example 1;
FIG. 4 is a nuclear magnetic resonance spectrum of the product obtained in step (2) of example 1;
FIG. 5 is a graph showing the flame retardant effect of sample 1 produced in example 5;
FIG. 6 is a graph showing the flame retardant effect of sample 2 produced in example 6;
FIG. 7 FTIR spectra of pure PU and FPU prepared in inventive example 9
FIG. 8 TGA profile of pure PU versus FPU prepared in example 9 of the present invention.
Detailed Description
The following examples are provided to illustrate the applicability of the present invention, and should not be construed as limiting the scope of the invention to the specific examples set forth below.
The essential raw materials for preparing the intrinsic flame-retardant waterborne polyurethane comprise isocyanate, polyalcohol, a dihydroxyl high phosphorus nitrogen content flame-retardant functional monomer and a hydrophilic chain extender. The isocyanate may be selected from toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate. The polyol comprises polyether polyol or polyester polyol; the polyether glycol is polyoxypropylene diol, polyoxypropylene triol, polytetrahydrofuran diol or tetrahydrofuran-propylene oxide copolymerization diol; the polyester polyol is polyethylene glycol adipate glycol, 1, 4-butanediol adipate glycol, diethylene glycol adipate glycol, polycarbonate glycol or polycaprolactone glycol. The hydrophilic chain extender is 2, 2-hydroxymethyl propionic acid or 2, 2-hydroxymethyl butyric acid. The isocyanate, the polyol and the hydrophilic chain extender can be purchased in the market, but the dihydroxyl high phosphorus-nitrogen content flame-retardant functional monomer is not sold in the market at present and needs to be prepared.
The feasibility of the preparation of the dihydroxy high phosphorus nitrogen flame retardant functional monomer is illustrated by the following examples.
Example 1
(1) In a 250mL three-necked flask equipped with a stirring device, a thermometer and a reflux condenser, 25.2g of paraformaldehyde, 15.2g of glycine and 40mL of tetrahydrofuran were charged, and the reaction mixture was stirred and heated to 66 ℃ and then 44.0g of dimethyl phosphite was slowly added dropwise over 1 hour in 1 to 2 seconds. Continuously reacting for 8 hours at about 66 ℃ after the dropwise adding is finished, removing the solvent by rotary evaporation after the reaction is finished to obtain a crude product, washing the crude product with 6mL of water, drying the crude product with anhydrous sodium sulfate, and performing suction filtration to obtain 78.2g of light yellow transparent liquid, namely the phosphorus-nitrogen integrated functional compound, wherein the yield is 92.7%;
(2) 76.6g of the phosphorus nitrogen integrated function compound and 100mL of dry dichloroethane were charged into a 250mL three-necked flask equipped with a stirring device, a thermometer and a reflux condenser. And (2) beginning to slowly dropwise add 21.0g of ethylene glycol diglycidyl ether at room temperature, wherein the dropwise adding speed is 1-2 seconds per drop, slowly heating to 50 ℃ in the dropwise adding process, keeping the temperature for reaction for 1 hour at 50 ℃ after the dropwise adding is finished, then heating to 85 ℃ for continuous reaction for 4 hours, stopping the reaction, distilling under reduced pressure to remove the solvent to obtain a crude product, washing the crude product with 15mL of water, drying by anhydrous sodium sulfate, and carrying out suction filtration to obtain 88.9g of yellow viscous liquid, namely the dihydroxy high-phosphorus-nitrogen-content flame-retardant functional monomer. The yield was 91.1%, and the yield of the whole process was 84.4%.
Example 2:
(1) in a 250mL three-necked flask equipped with a stirring device, a thermometer and a reflux condenser, 21.0g of paraformaldehyde, 15.2g of glycine and 40mL of tetrahydrofuran were charged, and the reaction mixture was stirred and heated to 66 ℃ and then 44.0g of dimethyl phosphite was slowly added dropwise over 1 hour in 1 to 2 seconds. Continuously reacting for 8 hours at about 66 ℃ after the dropwise adding is finished, removing the solvent by rotary evaporation after the reaction is finished to obtain a crude product, washing the crude product with 6mL of water, drying the crude product by anhydrous sodium sulfate, and performing suction filtration to obtain 72.7g of light yellow transparent liquid, namely the phosphorus-nitrogen integrated functional compound, wherein the yield is 90.6%;
(2) 70.2g of the phosphorus-nitrogen integrated functional compound and 100mL of dry dichloroethane were charged into a 250mL three-necked flask equipped with a stirring apparatus, a thermometer and a reflux condenser. And (2) slowly dropwise adding 17.4g of ethylene glycol diglycidyl ether at room temperature at a dropwise adding speed of 1-2 seconds per drop, slowly heating to 50 ℃ in the dropwise adding process, keeping the temperature at 50 ℃ for reacting for 1h after the dropwise adding is finished, heating to 85 ℃ for continuously reacting for 4h, stopping the reaction, distilling under reduced pressure to remove the solvent to obtain a crude product, washing the crude product with 15mL of water, drying by anhydrous sodium sulfate, and carrying out suction filtration to obtain 80.2g of yellow viscous liquid, namely the dihydroxy high-phosphorus-nitrogen-content flame-retardant functional monomer. The yield was 91.6%, and the yield of the whole process was 83.0%.
Example 3:
(1) in a 250mL three-necked flask equipped with a stirring device, a thermometer and a reflux condenser, 25.2g of paraformaldehyde, 15.2g of glycine and 40mL of tetrahydrofuran were charged, and the reaction mixture was stirred and heated to 66 ℃ and then 44.0g of dimethyl phosphite was slowly added dropwise over 1 hour in 1 to 2 seconds. Continuously reacting for 8 hours at about 66 ℃ after the dropwise adding is finished, removing the solvent by rotary evaporation after the reaction is finished to obtain a crude product, washing the crude product with 6mL of water, drying the crude product with anhydrous sodium sulfate, and performing suction filtration to obtain 78.2g of light yellow transparent liquid, namely the phosphorus-nitrogen integrated functional compound, wherein the yield is 92.7%;
(2) 76.6g of the phosphorus nitrogen integrated function compound and 100mL of dry dichloroethane were charged into a 250mL three-necked flask equipped with a stirring device, a thermometer and a reflux condenser. And (2) starting to slowly dropwise add 41.0g of bisphenol A diglycidyl ether at room temperature, wherein the dropwise adding speed is 1-2 seconds per drop, slowly heating to 50 ℃ in the dropwise adding process, keeping the temperature for reaction for 1 hour after the dropwise adding is finished, then heating to 85 ℃ for continuous reaction for 4 hours, stopping the reaction, distilling under reduced pressure to remove the solvent to obtain a crude product, washing the crude product with 15mL of water, drying with anhydrous sodium sulfate, and carrying out suction filtration to obtain 108.2g of an orange-yellow viscous liquid, namely the dihydroxy high-phosphorus-nitrogen-content flame-retardant functional monomer. The yield was 92.0%, and the yield of the whole process was 85.3%.
Example 4:
(1) in a 250mL three-necked flask equipped with a stirring device, a thermometer and a reflux condenser, 25.2g of paraformaldehyde, 15.2g of glycine and 40mL of tetrahydrofuran were charged, and the reaction mixture was stirred and heated to 66 ℃ and then 44.0g of dimethyl phosphite was slowly added dropwise over 1 hour in 1 to 2 seconds. Continuously reacting for 8 hours at about 66 ℃ after the dropwise adding is finished, removing the solvent by rotary evaporation after the reaction is finished to obtain a crude product, washing the crude product with 6mL of water, drying the crude product with anhydrous sodium sulfate, and performing suction filtration to obtain 78.2g of light yellow transparent liquid, namely the phosphorus-nitrogen integrated functional compound, wherein the yield is 92.7%;
(2) 76.6g of the phosphorus nitrogen integrated function compound and 100mL of dry dichloroethane were charged into a 250mL three-necked flask equipped with a stirring device, a thermometer and a reflux condenser. Slowly dropwise adding 24.3g of 1, 4-butanediol diglycidyl ether at room temperature at a dropwise speed of 1-2 seconds per drop, slowly heating to 50 ℃ in the dropwise adding process, keeping the temperature at 50 ℃ for reacting for 1 hour after the dropwise adding is finished, then heating to 85 ℃ for continuously reacting for 4 hours, stopping the reaction, distilling under reduced pressure to remove the solvent to obtain a crude product, washing the crude product with 15mL of water, drying with anhydrous sodium sulfate, and carrying out suction filtration to obtain 91.4g of yellow viscous liquid, namely the dihydroxy high-phosphorus-nitrogen-content flame-retardant functional monomer. The yield was 90.6%, and the yield of the whole process was 84.0%.
Example 5:
in another aspect of the invention, an environment-friendly halogen-free fabric flame-retardant coating adhesive is provided, which comprises the dihydroxy high-phosphorus-nitrogen-content flame-retardant functional monomer, and is prepared by compounding the monomer with other flame retardants and acrylate emulsion.
Cyclic phosphate ester (PCU), ammonium polyphosphate type II (APP), the bishydroxy high phosphorus nitrogen content flame retardant functional monomer prepared in inventive example 1, zinc borate, triazine Char Forming Agent (CFA), phenolic resin were blended as follows 1.5: 5.0: 2.0: 2.0: 2.5: 2.0, preparing the material mixture with the total mass of 15.0g, adding the material mixture into a mixing container, adding 26g of acrylate emulsion (the solid content of the emulsion is 50%), 15g of water, 0.5g of emulsifier and 0.5g of defoamer, and uniformly stirring and dispersing to obtain the flame-retardant coating adhesive.
The flame-retardant coating adhesive is blade-coated on the back of the fabric (the fabric is unbleached terylene fabric, the gram weight of which is 200g, namely the weight of each square meter of fabric is 200g), and the fabric is baked (150 ℃ and 180s) to obtain the low-smoke high-efficiency flame-retardant terylene sofa textile fabric (sample 1), and the gram weight of which is 99.6g (namely the coating adhesive with the coating mass of each square meter of fabric is 99.6 g).
Comparative example 6
Cyclic phosphate ester (PCU), ammonium polyphosphate type II (APP), zinc borate, triazine Char Former (CFA), phenolic resin according to 1.5: 7.0: 2.0: 2.5: 2.0, preparing the material mixture with the total mass of 15.0g, adding the material mixture into a mixing container, adding 26g of acrylate emulsion (the solid content of the emulsion is 50%), 15g of water, 0.5g of emulsifier and 0.5g of defoamer, and uniformly stirring and dispersing to obtain the flame-retardant coating adhesive. The flame-retardant coating adhesive was also knife-coated onto the back of the unbleached polyester fabric, with a gram weight gain of 100.1 g.
The flame-retardant coating adhesive is blade-coated on the back of the fabric (the fabric is unbleached terylene fabric, the gram weight of which is 200g, namely the weight of each square meter of fabric is 200g), and the fabric is baked (150 ℃ and 180s) to obtain the low-smoke high-efficiency flame-retardant terylene sofa textile fabric (sample 2), and the gram weight of which is 100.1g (namely the coating adhesive with the coating mass of each square meter of fabric is 100.1 g).
Referring to the BS5852 flame-retardant test standard, respectively covering a sample 1 and a sample 2 on specified polyurethane sponge, placing the polyurethane sponge under a specified burner to ignite, wherein the butane flame height is 35mm, stabilizing the flame for 30s, continuously burning the sample for 20s by using flame, and testing the flame-retardant performance of the sample. Wherein, the specimen 1 containing the dihydroxyl high phosphorus nitrogen content flame-retardant functional monomer is extinguished after being burnt for 20s, passes the BS5852 standard, and the test effect is shown in figure 5; the sample 2 which does not contain the dihydroxy high phosphorus nitrogen content flame-retardant functional monomer is burnt through within 20s, the flame is continuously burnt without self-extinguishing and can not pass the standard, and the test effect is shown in the attached figure 6.
Example 7
The embodiment 5 is repeated by sequentially replacing the dihydroxy high phosphorus nitrogen content flame retardant functional monomer prepared in the embodiment with the dihydroxy high phosphorus nitrogen content flame retardant functional monomer prepared in the embodiment 2, 3 or 4, and the prepared sample is tested, so that the similar flame retardant effect shown in the attached figure 5 can be obtained.
Through the examples 1-7, not only the specific implementation of the dihydroxyl high phosphorus nitrogen content flame retardant functional monomer is elaborated, but also the dihydroxyl high phosphorus nitrogen content flame retardant functional monomer is verified to have good flame retardant effect. On the basis of preparing the dihydroxy high-phosphorus-nitrogen content flame-retardant functional monomer, the concrete implementation mode of the intrinsic flame-retardant waterborne polyurethane is explained in detail by the example below.
The relevant performance indexes of the intrinsic flame-retardant waterborne polyurethane need to be tested, and the test method is as follows.
Average particle size test: diluting the intrinsic flame-retardant waterborne polyurethane to 1 wt% by using deionized water to obtain emulsion, and measuring the particle size of the emulsion by using a Malvern Zetasizer Nano ZS90 type laser particle size tester (Marvin instruments, Co., Ltd., England) at the measurement temperature of 25 ℃ for 120 s.
And (3) viscosity testing: the shear viscosity of the essentially flame-retardant aqueous polyurethane emulsion was measured using a Brookfield programmable DV-II + Viscometer type rotational Viscometer (Bohler fly, USA), using a No. 0 spindle, at room temperature.
LOI test: the test standard of an ISO 4589-2 combustion performance oxygen index method is referred to. And (3) coating the intrinsic flame-retardant waterborne polyurethane emulsion on a polytetrafluoroethylene plate, standing for 4-5 days at room temperature to naturally form a film, slowly volatilizing water, and then putting into a vacuum drying oven to be dried in vacuum for 24 hours at 80 ℃ to obtain the intrinsic flame-retardant waterborne polyurethane film. The film was prepared into 70X 6.5X 3.2mm3 strips of 15 pieces each. The change of the oxygen concentration is 0.5% each time, after a certain oxygen concentration test of the sample passes, the oxygen concentration which is increased by 0.5% cannot pass, and the oxygen concentration is reduced by 0.5% to pass. The low oxygen concentration is taken as the corresponding oxygen index.
Solid content test: with reference to GB/T1725-. Weighing 1g (error is 0.001g) of the intrinsic flame-retardant waterborne polyurethane emulsion as m, weighing the mass of a glass culture dish with the diameter of 60mm, adding the intrinsic flame-retardant polyurethane with high phosphorus and nitrogen content into the culture dish, putting the culture dish into an oven, heating to 80 ℃, vacuum drying for 8 hours, taking out the culture dish and the rest substances, weighing, subtracting the mass of the culture dish, and calculating the mass of the rest substances of the intrinsic flame-retardant waterborne polyurethane as m 1. The calculation formula of the solid content (x) of the intrinsic flame retardant polyurethane is as follows: x is m1/m × 100%.
Example 8
20g of polyoxypropylene glycol 600(PPG-600) and 3.5g of DMPA were charged into a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and nitrogen was introduced thereinto while maintaining the same, and 60g of methyl ethyl ketone was further added. The temperature is raised to 75 ℃, 20g of Toluene Diisocyanate (TDI) is slowly dripped, and the dripping is controlled to be finished for 2 hours. Keeping the temperature for 0.5h, then slowly dripping 10g of the dihydroxyl high-phosphorus-nitrogen-content flame-retardant functional monomer prepared in the example 1, and controlling the dripping for 1 h. And (3) after the dripping is finished, carrying out heat preservation reaction for 5h, then cooling to 45 ℃, adding 3.5g of triethylamine alkaline neutralizing agent for neutralization for 20min, stopping introducing nitrogen, and carrying out rotary evaporation to remove the solvent to obtain the intrinsic flame-retardant waterborne polyurethane (which can be named as FPU).
The prepared intrinsic flame-retardant waterborne polyurethane is added into 70g of deionized water, and emulsified for 20min under the high-speed stirring of 3000rmp/min, so that the intrinsic flame-retardant waterborne polyurethane emulsion can be prepared.
Tests show that the average particle size of the intrinsic flame-retardant waterborne polyurethane is as follows: 138.6 nm; the viscosity of the intrinsically flame-retardant aqueous polyurethane emulsion prepared in the embodiment is 16.9 mPas; the LOI of the essentially flame-retardant aqueous polyurethane emulsion prepared in the embodiment after film formation is 27.5; the solid content of the essentially flame-retardant aqueous polyurethane emulsion prepared in this example was 38.7%.
Example 9
15.0g of polyoxypropylene glycol-600 (PPG-600), 3.5g of DMBA were charged into a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and nitrogen was introduced thereinto while maintaining it, and 60g of methyl ethyl ketone was further added. The temperature is raised to 75 ℃, 20g of Toluene Diisocyanate (TDI) is slowly dripped, and the dripping is controlled to be finished for 2 hours. Keeping the temperature for 0.5h, then slowly dripping 15.0g of the dihydroxyl high phosphorus nitrogen content flame-retardant functional monomer prepared in the example 2, and controlling the dripping for 1 h. And after the dropwise addition, carrying out heat preservation reaction for 5 hours, then cooling to 45 ℃, adding 3.5g of triethylamine basic neutralizing agent for neutralization for 20 minutes, stopping introducing nitrogen, and carrying out rotary evaporation to remove the solvent to obtain the intrinsic flame-retardant waterborne polyurethane (which can be named as FPU).
The prepared intrinsic flame-retardant waterborne polyurethane is added into 70g of deionized water, and emulsified for 20min under the high-speed stirring of 3000rmp/min, so that the intrinsic flame-retardant waterborne polyurethane emulsion can be prepared.
Tests show that the average particle size of the intrinsic flame-retardant waterborne polyurethane is as follows: 147.7 nm; the viscosity of the essentially flame-retardant aqueous polyurethane emulsion prepared in the embodiment is 16.2 mPas; the LOI of the essentially flame-retardant aqueous polyurethane emulsion prepared in the embodiment after film formation is 30.0; the solid content of the essentially flame-retardant aqueous polyurethane emulsion prepared in this example was 38.3%.
Example 10
12.5g of polyethylene glycol adipate and 4.0g of DMPA were put into a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, nitrogen was introduced thereinto and maintained, and 60g of ethyl acetate was further added. The temperature is raised to 75 ℃, 20g of Toluene Diisocyanate (TDI) is slowly dripped, and the dripping is controlled to be finished for 2 hours. Keeping the temperature for 0.5h, then slowly dripping 17.5g of the dihydroxyl high phosphorus nitrogen content flame-retardant functional monomer prepared in the example 1, and controlling the dripping for 1 h. After dripping, the temperature is kept for reaction for 5h, then the temperature is reduced to 45 ℃, 4.0g of triethylamine alkaline neutralizer is added for neutralization for 20min, nitrogen is stopped to be introduced, and the solvent is removed by rotary evaporation to obtain the intrinsic flame-retardant waterborne polyurethane (which can be named as FPU).
The prepared intrinsic flame-retardant waterborne polyurethane is added into 70g of deionized water, and emulsified for 20min under the high-speed stirring of 3000rmp/min, so that the intrinsic flame-retardant waterborne polyurethane emulsion can be prepared.
Tests show that the average particle size of the intrinsic flame-retardant waterborne polyurethane is as follows: 129.2 nm; the viscosity of the essentially flame-retardant aqueous polyurethane emulsion prepared in the embodiment is 17.5 mPas; the LOI of the essentially flame-retardant aqueous polyurethane emulsion prepared in the embodiment after film formation is 32.0; the solid content of the essentially flame-retardant aqueous polyurethane emulsion prepared in this example was 40.2%.
Example 11
12.5g of polyoxypropylene glycol-600 (PPG-600), 4.0g of DMBA were charged into a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, nitrogen was introduced thereinto while maintaining it, and 60g of dichloroethane was further added thereto. The temperature is raised to 80 ℃, 20g of diphenylmethane diisocyanate (MDI) is slowly dripped, and the dripping is controlled to be finished within 2 hours. Keeping the temperature for 0.5h, then slowly dripping 17.5g of the dihydroxyl high phosphorus nitrogen content flame-retardant functional monomer prepared in the example 3, and controlling the dripping for 1 h. After dripping, the temperature is kept for reaction for 5h, then the temperature is reduced to 45 ℃, 4.0g of triethylamine alkaline neutralizer is added for neutralization for 20min, nitrogen is stopped to be introduced, and the solvent is removed by rotary evaporation to obtain the intrinsic flame-retardant waterborne polyurethane (which can be named as FPU).
The prepared intrinsic flame-retardant waterborne polyurethane is added into 70g of deionized water, and emulsified for 20min under the high-speed stirring of 3000rmp/min, so that the intrinsic flame-retardant waterborne polyurethane emulsion can be prepared.
Tests show that the average particle size of the intrinsic flame-retardant waterborne polyurethane is as follows: 134.1 nm; the viscosity of the essentially flame-retardant aqueous polyurethane emulsion prepared in the embodiment is 19.8 mPas; the LOI of the essentially flame-retardant aqueous polyurethane emulsion prepared in the embodiment after film formation is 28.5; the solid content of the essentially flame-retardant aqueous polyurethane emulsion prepared in this example was 39.6%.
Example 12
12.5g of polyethylene glycol adipate and 4.0g of DMBA were charged into a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and nitrogen was introduced thereinto while maintaining it, and 60g of toluene was further added. The temperature is raised to 90 ℃, 20g of diphenylmethane diisocyanate (MDI) is slowly dripped, and the dripping is controlled to be finished within 2 hours. Keeping the temperature for 0.5h, then slowly dripping 17.5g of the dihydroxyl high phosphorus nitrogen content flame-retardant functional monomer prepared in the example 4, and controlling the dripping for 1 h. After dripping, the temperature is kept for reaction for 5h, then the temperature is reduced to 45 ℃, 4.0g of triethylamine alkaline neutralizer is added for neutralization for 20min, nitrogen is stopped to be introduced, and the solvent is removed by rotary evaporation to obtain the intrinsic flame-retardant waterborne polyurethane (which can be named as FPU).
The prepared intrinsic flame-retardant waterborne polyurethane is added into 70g of deionized water, and emulsified for 20min under the high-speed stirring of 3000rmp/min, so that the intrinsic flame-retardant waterborne polyurethane emulsion can be prepared.
Tests show that the average particle size of the intrinsic flame-retardant waterborne polyurethane is as follows: the viscosity of the intrinsic flame-retardant aqueous polyurethane emulsion prepared by the embodiment at 130.7nm is 18.6mPa & s; the LOI of the essentially flame-retardant aqueous polyurethane emulsion prepared in the embodiment after film formation is 28.5; the solid content of the essentially flame-retardant aqueous polyurethane emulsion prepared in this example was 39.3%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical solutions of the present invention in any way. Any equivalent substitutions or partial modifications made under the technical spirit of the present invention will be considered to be within the scope of the present invention.
Claims (15)
1. An intrinsic flame-retardant waterborne polyurethane is characterized in that the intrinsic flame-retardant waterborne polyurethane is polymerized by isocyanate, polyalcohol, a dihydroxyl high phosphorus nitrogen content flame-retardant functional monomer and a hydrophilic chain extender; the dihydroxyl high phosphorus-nitrogen content flame-retardant functional monomer is prepared by further reacting a phosphorus-nitrogen integrated functional compound prepared by taking glycine, paraformaldehyde and dimethyl phosphite as raw materials with a diepoxy compound.
2. The intrinsically flame-retardant waterborne polyurethane of claim 1, wherein the dihydroxy high phosphorus nitrogen content flame-retardant functional monomer is prepared by the following steps:
(1) mixing paraformaldehyde, glycine and tetrahydrofuran, heating to 60-70 ℃, then dropwise adding dimethyl phosphite, and continuing to perform heat preservation reaction until the reaction is sufficient after dropwise adding; after the reaction is finished, removing the solvent tetrahydrofuran to obtain a light yellow viscous liquid which is the phosphorus-nitrogen integrated functional compound;
(2) mixing the phosphorus-nitrogen integrated functional compound with dichloroethane, slowly dropwise adding a diepoxy compound, slowly heating to 45-60 ℃ in the dropwise adding process, carrying out heat preservation reaction at 45-60 ℃ after dropwise adding is finished, heating to 75-90 ℃, and continuing the heat preservation reaction until the reaction is full; after the reaction is finished, removing the dichloroethane as the solvent to obtain yellow viscous liquid, namely the dihydroxyl high phosphorus nitrogen content flame-retardant functional monomer.
3. The intrinsically flame retardant waterborne polyurethane of claim 2, wherein: in the step (1), the solvent tetrahydrofuran is removed, and then the following treatment is required: firstly adding a small amount of water for washing, then adding anhydrous sodium sulfate for drying, and finally carrying out solid-liquid separation to obtain a light yellow viscous liquid which is the phosphorus-nitrogen integrated functional compound.
4. The intrinsically flame retardant waterborne polyurethane of claim 2, wherein: in the step (2), after dichloroethane is removed, the following treatment is required: firstly adding a small amount of water for washing, then adding anhydrous sodium sulfate for drying, and finally carrying out solid-liquid separation to obtain a faint yellow viscous liquid which is the dihydroxyl high phosphorus-nitrogen content flame-retardant functional monomer.
5. The intrinsically flame retardant waterborne polyurethane of claim 2, wherein: in the step (1), the dripping speed is 1-2 seconds per drop, and the reaction is finished after the heat preservation reaction is continued for 7-9 hours after the dripping is finished; in the step (2), the dropping speed is 1-2 seconds per drop, the reaction time is 0.5-2 hours at the temperature of 45-60 ℃, and the reaction time is 3-6 hours at the temperature of 75-90 ℃.
6. The intrinsically flame retardant waterborne polyurethane of claim 1, wherein: the preparation method comprises the following steps: mixing polyol and a hydrophilic chain extender, heating to 75-90 ℃, starting to dropwise add isocyanate, and continuing to perform heat preservation reaction after dropwise adding is finished until the reaction is complete to prepare a reaction solution; adding a dihydroxy high-phosphorus-nitrogen-content flame-retardant functional monomer into the reaction solution at 75-90 ℃, carrying out heat preservation reaction until the reaction is sufficient, and obtaining the intrinsic flame-retardant waterborne polyurethane after the reaction is finished; the above reaction can be carried out in the presence of a solvent, or a proper amount of a solvent can be added depending on the viscosity change during the reaction to smoothly carry out the stirring, and if the solvent is added, the solvent needs to be removed after the reaction is finished.
7. The intrinsically flame retardant waterborne polyurethane of claim 6, wherein: the solvent is butanone, ethyl acetate, dichloroethane or toluene.
8. The intrinsically flame retardant waterborne polyurethane of claim 6, wherein: after the reaction of the dihydroxyl high phosphorus nitrogen content flame-retardant functional monomer is completed, adding an alkaline neutralizing agent to neutralize the system to weak acidity or neutrality, and after the neutralization is completed, preparing the intrinsic flame-retardant waterborne polyurethane; and if the solvent is added, removing the solvent after the neutralization is finished, and obtaining the intrinsic flame-retardant waterborne polyurethane after the solvent is removed.
9. The intrinsically flame retardant waterborne polyurethane of claim 8, wherein: the alkaline neutralizing agent is ammonia water, 2-amino-2-methyl-1-propanol, diethanolamine, triethanolamine, diethylamine, triethylamine, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium acetate, sodium pyrophosphate or sodium carbonate.
10. The intrinsically flame retardant waterborne polyurethane of any one of claims 1 to 9, wherein: the molar ratio of the glycine to the paraformaldehyde to the dimethyl phosphite is 1.0-1.2:2.0-4.0:4.0, and the molar ratio of the phosphorus-nitrogen integrated functional compound to the diepoxide is 2.0-2.4: 1.0.
11. The intrinsically flame retardant waterborne polyurethane of any one of claims 1 to 9, wherein: the diepoxide is one or a mixture of more than two of diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether and resorcinol diglycidyl ether.
12. The intrinsically flame retardant waterborne polyurethane of any one of claims 1 to 9, wherein: the isocyanate is one or more than two of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
13. The intrinsically flame retardant waterborne polyurethane of any one of claims 1 to 9, wherein: the polyol comprises a polyether polyol or a polyester polyol; the polyether glycol is polyoxypropylene diol, polyoxypropylene triol, polytetrahydrofuran diol or tetrahydrofuran-propylene oxide copolymerization diol; the polyester polyol is one or more of polyethylene glycol adipate diol, 1, 4-butanediol adipate diol, diethylene glycol adipate diol, polycarbonate diol and polycaprolactone diol.
14. The intrinsically flame retardant waterborne polyurethane of any one of claims 1 to 9, wherein: the hydrophilic chain extender is 2, 2-hydroxymethyl propionic acid or 2, 2-hydroxymethyl butyric acid.
15. The intrinsically flame retardant waterborne polyurethane of any one of claims 1 to 9, wherein: the mass ratio of the isocyanate to the polyalcohol is 1:3-3:1, the dosage of the dihydroxy high phosphorus nitrogen content flame-retardant functional monomer is 10-40% of the sum of the isocyanate, the dihydroxy high phosphorus nitrogen content flame-retardant functional monomer and the polyalcohol, and the dosage of the hydrophilic chain extender is 2-10% of the sum of the isocyanate, the dihydroxy high phosphorus nitrogen content flame-retardant functional monomer and the polyalcohol.
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