WO2020000919A1

WO2020000919A1 - Method for preparing flame-retardant, antibacterial, and waterborne polyurethane coating and adhesive

Info

Publication number: WO2020000919A1
Application number: PCT/CN2018/120907
Authority: WO
Inventors: 段小宁; 何宏昌; 赵玉真
Original assignee: 周连惠
Priority date: 2018-06-26
Filing date: 2018-12-13
Publication date: 2020-01-02
Also published as: CA3028507A1; CN108715729B; CN108715729A

Abstract

A method for preparing a flame-retardant, antibacterial, and waterborne polyurethane coating and adhesive, comprising: adding 0.05 g of dibutyltin dilaurate, 73 g of poly(tetramethylene ether)glycol, and 16 g of isocyanate to a 250 mL three-necked flask equipped with a stirrer, a condenser, and a thermometer, and carrying out a reaction at 70-90°C for 1-3 h to obtain a polyurethane prepolymer A; adding 3.1 g of a flame retardant A, 1.5 g of an antibacterial agent, and 16.7 g of a solvent acetone to the polyurethane prepolymer A, and carrying out a reaction at 60-90°C for 2-4 h, adding 6.7 g of triethylamine and carrying out a neutralization reaction for 90 min, adding 80-90 g of water and performing stirring and emulsification for 0.5 h , so as to obtain a flame-retardant, antibacterial, and waterborne polyurethane coating and adhesive. The material can be used for interior and exterior wall coatings, metal finishing and anti-corrosion coatings, paints for wood, and as a leather finishing agent.

Description

Preparation method of flame-retardant and antibacterial water-based polyurethane coating and adhesive

Technical field

The invention relates to a method for preparing water-based polyurethane coatings and adhesives, in particular to a method for preparing flame-retardant and antibacterial water-based polyurethane coatings and adhesives.

Background technique

Paint is a general term for a class of liquid or solid materials that can form a solid coating film with protection, decoration, or special properties (such as insulation, corrosion resistance, signs, etc.) on the surface of an object, including oil (nature) paint, water-based paint, powder coating. Lacquers are flowable liquid coatings, including oil (based) paints and water-based paints. Paint is an organic solvent-based or high solid, solvent-free oil paint. Water-based paints are paints that can be dissolved or dispersed in water. As one of the main materials for home decoration, paint accounts for a large proportion in decoration and decoration. The qualification of buying paint directly affects the overall decoration effect and the environment of the living room, and sometimes even causes great harm to human health.

The structure of the world's coatings varieties is developing towards reducing VOC, and water-based coatings are one of the development directions. The proportion of traditional solvent-based coatings in China has gradually decreased, and the development rate of water-based coatings is also fast. However, low-grade polyvinyl alcohols still account for a large proportion. Improving the quality of water-based coatings and developing new varieties are important links to consolidate and develop water-based coatings. Focus on research and development should be based on vinyl acetate-acrylic copolymer emulsion, styrene-acrylic copolymer emulsion and pure acrylic series latex coatings as the main material, and strive for durability, film smoothness, fullness, construction, decoration There are some breakthroughs in terms of performance; for more mature epoxy emulsions and water-based polyurethane water-based binders, we should continue to study high-performance water-based coatings to meet some special requirements.

As an ideal performance of coatings, not only to protect and beautify the substrate, but also to give the substrate special functions that cannot be possessed by itself, the use of some new base materials can make coatings achieve amazing performance, high value-added, advanced Effects such as fluororesin coatings with high weather resistance, good results in construction. Because fluororesin coatings have superior weather resistance, durability, and chemical resistance compared to other synthetic resins. However, fluororesins are relatively expensive, and their use in building exterior wall finishes is greatly restricted. Attach importance to the research on the development of fluororesin in water, especially the fluororesin-modified copolymer emulsion based on fluoroethylene, which makes it a high-quality base material with good performance, high grade, and affordable price. Lay the foundation for the development of high-performance, high-grade coatings. In the research of waterborne polyurethane coatings, efforts should be focused on developing products. Polyurethane is one of the high-end materials with excellent performance, making it water-based, which not only meets the requirements of reducing pollution and saving energy, but also maintains the characteristics of polyurethane itself.

201610824849.X provides a flame retardant polyurethane and a preparation method thereof, the flame retardant polyurethane includes a composite flame retardant and polyurethane, and the composite flame retardant includes a bromine-containing flame retardant and a sulfur-containing flame retardant and / or A phosphorus-containing flame retardant, the bromine-containing flame retardant is a bromine-containing phenolic compound and an epoxy resin thereof. The bromine-containing flame retardant and the sulfur-containing flame retardant and / or phosphorus-containing flame retardant have a synergistic effect on the flame retardant effect, can enhance the flame retardant performance of the composite flame retardant, and thus enhance the flame retardant performance of the finally obtained polyurethane, In addition, the flame-retardant polyurethane of the present invention has good mechanical properties and heat resistance, and is a kind of polyurethane with greater economical efficiency and environmental protection, and its oxygen index can reach 28.

201711369135.5 discloses a flame retardant, light resistance and low VOC polyurethane coating and a preparation method thereof. In a 250 ml three-necked bottle with a stirrer, a condenser tube, and a thermometer, 0.22 g of triethylenetetramine, 70 g of polytetrahydrofuran glycol and six 15g of methylene diisocyanate was reacted at 80 ° C for 2h to obtain polyurethane prepolymer A; 0.62g of acetamide and 8.2g of methyl ethyl ketone were added to prepolymer A, and reacted at 75 ° C for 3.5h, and 2g step was added ( 1) 2.5 g of modified manganese hypophosphite, 4 g of 4-carboxyphenylboronic acid and diethylene triamine pentamethylene phosphonic acid, the reaction temperature is 80 ° C., the reaction time is 2 h, and 7.1 g of triethylamine is added for a neutralization reaction for 60 min. Vitamin C 0.9g and water 70g are stirred and emulsified to obtain flame-retardant, light-resistant and low-VOC polyurethane coatings. The prepared flame-retardant, light-resistant and low-VOC polyurethane coatings are environmentally friendly and inexpensive, and are widely used in wall and furniture On the surface of metal appliances, as an adhesive for plastics, glass, papermaking, and textiles, the oxygen index can reach 27.6, the flame burning time can be less than 7.2s, and the flameless burning time can basically be achieved.

201711443934.2 discloses an antibacterial and weather-resistant polyurethane glass glue, the raw materials of which include 45-65 parts of polyurethane prepolymer, 10-16 parts of montmorillonite, 3-8 parts of spherical silica powder, 2-11 parts of nano titanium dioxide, Cordierite 2-9 parts, catalyst 0.02-0.07 parts, plasticizer 12-18 parts, glycidyl ether oxypropyltrimethoxysilane 0.1-0.5 parts, thixotropic agent 0.5-2.3 parts, composite antibacterial agent 3-11 Parts, benzalkonium chloride 0.1-0.35 parts; composite antibacterial agents are allicin, naphthalene polyphenols, nano zinc oxide, silver-loaded activated carbon, citrated chitosan, 8-hydroxyquinoline, dandelion polyphenols, ε-poly Lysine mixture. The antibacterial and weather-resistant polyurethane glass glue provided by the present invention has high bonding strength, good antibacterial property, excellent weather resistance and long service life.

201410346698.2 discloses a method for preparing a flame-retardant and antibacterial waterborne polyurethane coating. In the presence of a dibutyltin dilaurate catalyst, N, N ′, N〃-tri (2,3-dihydroxy-5-sulfonate Acid benzoyl) -1,5,10-triazadecane and isophorone diisocyanate are mixed in a weight ratio of 1: 1.2 to 1: 2.5, and a synergist and sodium cloprostenol are added at 50 Reaction at ~ 70 ° C for 2 ~ 3h to obtain polyurethane prepolymer A; to prepolymer A are added a chain extender of 1.2 to 3.2% by weight of prepolymer A and a solvent of 12-25% by weight of prepolymer A. The reaction is performed at 65-85 ° C for 1.5-3.5 hours, and the prepolymer A is added with 10-15% by weight of triethylamine for neutralization reaction for 30-50 minutes, and water and sodium dodecylsulfonate are emulsified to obtain flame retardancy. With antibacterial polyurethane coating. The prepared flame retardant and antibacterial polyurethane is environmentally friendly and low in price. It is widely used in wall, furniture and metal appliance surfaces as adhesives for plastics, glass, papermaking and textiles. As a result, it was found that Staphylococcus aureus, E. coli and yellow Kojn has a very good effect, its oxygen index can reach 28.4, flame burning time is 9.7s, flameless burning time is 0.

Summary of the invention

The invention relates to a method for preparing flame-retardant and antibacterial waterborne polyurethane coatings and adhesives. The main idea is to synthesize a flame retardant and antibacterial agent, and react the flame retardant and antibacterial agent with a polyurethane prepolymer to Improve the flame retardant performance and water resistance of polyurethane coatings, change the traditional antibacterial agents and flame retardants with polyurethane is simply mixed (that is, additive), for antibacterial agents and flame retardants to react with polyurethane prepolymers (that is, reactive ), The obtained polyurethane has long-lasting antibacterial properties and flame retardancy, and a new catalyst is used in the process of resynthesizing the flame retardant, which changes the traditional reaction of dimethyl phosphite with acrylamide using sodium methoxide, and the resulting system will produce methanol, At the same time, it reacts with tetramethylol phosphate, pentaerythritol, and phosphoric acid, which also reduces the reaction problem between pentaerythritol and phosphoric acid. It makes the acid source phosphoric acid, tetramethylol phosphate sulfate, acrylamide, and carbon source pentaerythritol of the intumescent flame retardant. It is firmly combined with dimethyl phosphite. There are a large number of hydroxyl groups in the system that react with polyurethane and prepolymer. Under the action of substance A, the expansion rate and residual carbon ratio in the system increase. While selecting sulfathiazole, sulfadiazine, meprobamate, oxalyl chloride and chlorobutanol added to the system, so that in effect γ-- butyrolactone, lasting antimicrobial.

The preparation method of flame-retardant and antibacterial water-based polyurethane coating and adhesive is as follows:

(1) In a 250 ml three-necked flask with a stirrer, a condenser, and a thermometer, add 0.05 g of dibutyltin dilaurate, 73 g of polytetrahydrofuran diol, and 16 g of isocyanate, and react at 70 to 90 ° C for 1 to 3 hours to obtain Polyurethane prepolymer A;

(2) The flame retardant A added to the polyurethane prepolymer A is 3.1 g, the antibacterial agent 1.5 g, and the solvent acetone 16.7 g. The reaction is performed at 60 to 90 ° C for 2 to 4 hours, and 6.7 g of triethylamine is added. After reacting for 90 minutes, 80-90 g of water was added and stirred for 0.5 h to obtain a flame-retardant and antibacterial water-based polyurethane coating and an adhesive.

The preparation method of the flame retardant A is: adding 0.6 mol of dimethyl phosphite into a three-necked flask, adding 0.01 mol of catalyst A and 0.66 to 0.9 mol mol of acrylamide, connecting a stirring blade, a condenser tube and a thermometer, and slowly heating up The temperature was maintained at 70 to 90 ° C for 2 to 5 hours, and a pale yellow liquid was obtained as 3-dimethoxyphosphoryl propionamide. To the obtained 3-dimethoxyphosphoryl propionamide was added 0.2 to tetramethylphosphoryl sulfate. 0.6mol, reaction temperature 50 ℃ ～ 110 ℃, reaction time 2 ～ 3h, then add 0.1mol pentaerythritol to fully dissolve pentaerythritol, warm to 70 ～ 90 ℃, reaction time 2 ～ 3h, add substance A0.1mol and phosphoric acid 0.05 mol, reaction temperature 70 ～ 90 ℃, reaction time 2h, cooling and cooling to obtain flame retardant A; catalyst A is 4-acetamido-2-ethoxybenzoic acid methyl ester, N-methylacetamide, dimethyl Either ethylene glycol acrylate or methyl diphenyl glycolate. The substance A is any one of acetyl tributyl citrate, tetraethoxysilane, phenyltriethoxysilane, and p-toluenesulfonamide; the preparation method of the antibacterial agent is 3g of sulfathiazole, 1.6 g of sulfadiazine, 1.3 g of meprobamate, and 15 g of acetone were added to the flask, 0.5 g of oxalyl chloride and 4.4 g of trichloro-tert-butanol were added to the reaction at 60 ° C for 2 to 3 hours, and melamine 0.2 was added. g and γ-butyrolactone 0.003g at 70 ° C for 2 to 3 hours, removing acetone to obtain the antibacterial agent; the molecular weight of polytetrahydrofuran glycol is any one of 650, 1000, 1800, 2000; isocyanate is six Any of methylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

The advantages of the invention are:

(1) The obtained polyurethane has long-lasting antibacterial properties and flame retardancy. A new catalyst was used in the process of resynthesizing the flame retardant, which changed the traditional reaction of dimethyl phosphite and acrylamide using sodium methoxide (using catalyst A). The system will produce methanol and react with tetramethylol phosphate sulfate, pentaerythritol, and phosphoric acid at the same time, which also reduces the problem of reaction between pentaerythritol and phosphoric acid. Acrylamide and carbon source pentaerythritol and dimethyl phosphite are firmly combined. A large number of hydroxyl groups in the system react with polyurethane and prepolymer. Under the action of substance A, the expansion rate and residual carbon rate in the system increase;

(2) Sulfathiazol, sulfadiazine, meprobamate, oxalyl chloride and trichloro-tert-butyl alcohol are added to the system at the same time, so that the antibacterial effect is durable under the action of γ-butyrolactone.

(3) γ-butyrolactone was purchased from Shaanxi Jinxinyi Chemical Technology Co., Ltd., but not limited to the above-mentioned manufacturers.

detailed description

Example 1

(1) In a 250 ml three-necked bottle with a stirrer, a condenser, and a thermometer, add 0.05 g of dibutyltin dilaurate, 73 g of polytetrahydrofuran diol, and 16 g of isocyanate, and react at 70 ° C for 1 hour to obtain a polyurethane prepolymer. A;

(2) The flame retardant A added to the polyurethane prepolymer A is 3.1 g, the antibacterial agent 1.5 g, and the solvent acetone 16.7 g. The reaction is performed at 60 ° C for 2 hours, and 6.7 g of triethylamine is added for a neutralization reaction for 90 min. 80 g of water was added and stirred for 0.5 h to obtain a flame-retardant and antibacterial water-based polyurethane coating and an adhesive.

The preparation method of the flame retardant A is: adding 0.6 mol of dimethyl phosphite to a three-necked flask, adding 0.01 mol of catalyst A and 0.66 mol of acrylamide, connecting a stirring blade, a condenser tube and a thermometer, and slowly raising the temperature to 70. ℃, incubate the reaction for 2h, the light yellow liquid is 3-dimethoxyphosphoryl propionamide; 0.2 mol of tetramethylol phosphate sulfate is added to the obtained 3-dimethoxyphosphoryl propionamide, the reaction temperature is 50 ℃, the reaction After 2 hours, add 0.1 mol of pentaerythritol to fully dissolve the pentaerythritol, heat up to 70 ℃, reaction time 2 h, add substance A 0.1 mol and phosphoric acid 0.05 mol, reaction temperature 70 ℃, reaction time 2 h, cool down to obtain flame retardant A ;

Catalyst A was methyl 4-acetamido-2-ethoxybenzoate.

The substance A is acetyl tributyl citrate;

The preparation method of the antibacterial agent is to add 3g of sulfathiazolyl, 1.6g of sulfadiazine, 1.3g of methionine and 15g of acetone to a flask, and then add 0.5g of oxalyl chloride and 4.4g of trichlorot-butanol to 60. The reaction was performed at 2 ° C for 2 hours, and 0.2 g of cyanuric acid and 0.003 g of γ-butyrolactone were added to the reaction at 70 ° C for 2 hours. The acetone was removed to obtain the antibacterial agent.

Polytetrahydrofuran diol has a molecular weight of 650;

The isocyanate is hexamethylene diisocyanate.

Example 2

(1) In a 250 ml three-necked bottle with a stirrer, a condenser, and a thermometer, add 0.05 g of dibutyltin dilaurate, 73 g of polytetrahydrofuran diol and 16 g of isocyanate, and react at 90 ° C for 3 hours to obtain a polyurethane prepolymer. A;

(2) The flame retardant A added to the polyurethane prepolymer A is 3.1 g, the antibacterial agent 1.5 g, and the solvent acetone 16.7 g. The reaction is carried out at 90 ° C for 4 hours, and 6.7 g of triethylamine is added for a neutralization reaction for 90 minutes. 90 g of water was added and stirred for 0.5 h to obtain a flame-retardant and antibacterial water-based polyurethane coating and an adhesive.

The preparation method of the flame retardant A is: adding 0.6 mol of dimethyl phosphite to a three-necked flask, adding 0.01 mol of catalyst A and 0.9 mol of acrylamide, connecting a stirring blade, a condenser tube and a thermometer, and slowly raising the temperature to 90 ℃, holding the reaction for 5h, the light yellow liquid was 3-dimethoxyphosphoryl propionamide; to the obtained 3-dimethoxyphosphoryl propionamide was added 0.6 mol of tetramethylol phosphate sulfate, and the reaction temperature was 110 ° C. The reaction After 3 hours, 0.1 mol of pentaerythritol was added to fully dissolve pentaerythritol, and the temperature was raised to 90 ° C. The reaction time was 3 hours, and then 0.1 mol of substance A and 0.05 mol of phosphoric acid were added. ;

Catalyst A was N-methylacetamide.

The substance A is tetraethoxysilane; the preparation method of the antibacterial agent is to add 3 g of sulfathiazolyl, 1.6 g of sulfadiazine, 1.3 g of methylalanine, and 15 g of acetone to a flask, and then add oxalyl chloride 0.5g and 4.4g of trichloro-tert-butanol were reacted at 60 ° C for 3h, 0.2g of cyanuric chloride and 0.003g of γ-butyrolactone were reacted at 70 ° C for 3h, acetone was removed to obtain the antibacterial agent;

The molecular weight of polytetrahydrofuran diol is 1000;

The isocyanate is toluene diisocyanate.

Example 3

(1) In a 250 ml three-necked bottle with a stirrer, a condenser, and a thermometer, add 0.05 g of dibutyltin dilaurate, 73 g of polytetrahydrofuran diol, and 16 g of isocyanate, and react at 80 ° C for 2 hours to obtain a polyurethane prepolymer. A;

(2) The flame retardant A added to the polyurethane prepolymer A is 3.1 g, an antibacterial agent 1.5 g, and a solvent acetone 16.7 g. The reaction is performed at 75 ° C for 3 hours, and 6.7 g of triethylamine is added for a neutralization reaction for 90 min. 85 g of water was added and stirred for 0.5 h to obtain a flame-retardant and antibacterial water-based polyurethane coating and an adhesive.

The preparation method of the flame retardant A is: adding 0.6 mol of dimethyl phosphite to a three-necked flask, adding 0.01 mol of catalyst A and 0.78 mol of acrylamide, connecting a stirring blade, a condenser tube and a thermometer, and slowly raising the temperature to 80 ℃, holding the reaction for 3.5h to obtain a pale yellow liquid, which is 3-dimethoxyphosphoryl propionamide; to the obtained 3-dimethoxyphosphoryl propionamide, 0.4 mol of tetramethylol phosphate sulfate was added, and the reaction temperature was 80 ° C , The reaction time is 2.5h, and then add 0.1mol of pentaerythritol to fully dissolve the pentaerythritol, warm up to 80 ℃, the reaction time is 2.5h, then add the substance A0.1mol and phosphoric acid 0.05mol, the reaction temperature is 80 ℃, the reaction time is 2h, cool down Flame retardant A;

Catalyst A was ethylene glycol dimethacrylate.

The substance A is phenyltriethoxysilane;

The preparation method of the antibacterial agent is to add 3g of sulfathiazolyl, 1.6g of sulfadiazine, 1.3g of methionine and 15g of acetone to a flask, and then add 0.5g of oxalyl chloride and 4.4g of trichlorot-butanol to 60. The reaction was carried out at 2.5 ° C for 2.5h, 0.2g of cyanuric acid and 0.003g of γ-butyrolactone were added, and the reaction was performed at 70 ° C for 2.5h, and acetone was removed to obtain the antibacterial agent;

Polytetrahydrofuran diol has a molecular weight of 1800;

Isocyanate is isophorone diisocyanate.

Example 4

(1) In a 250 ml three-necked bottle with a stirrer, a condenser tube and a thermometer, add 0.05 g of dibutyltin dilaurate, 73 g of polytetrahydrofuran diol and 16 g of isocyanate, and react at 70 ° C for 3 hours to obtain a polyurethane prepolymer. A;

(2) The flame retardant A added to the polyurethane prepolymer A is 3.1 g, the antibacterial agent 1.5 g, and the solvent acetone 16.7 g. The reaction is carried out at 90 ° C for 4 hours, and 6.7 g of triethylamine is added for a neutralization reaction for 90 minutes. 80 g of water was added and stirred for 0.5 h to obtain a flame-retardant and antibacterial water-based polyurethane coating and an adhesive.

The preparation method of the flame retardant A is: adding 0.6 mol of dimethyl phosphite to a three-necked flask, adding 0.01 mol of catalyst A and 0.9 mol of acrylamide, connecting a stirring blade, a condenser tube and a thermometer, and slowly raising the temperature to 70. ℃, holding the reaction for 2h to obtain a pale yellow liquid, which is 3-dimethoxyphosphoryl propionamide; To the obtained 3-dimethoxyphosphoryl propionamide, 0.2 mol of tetramethylol phosphate sulfate was added, and the reaction temperature was 110 ° C. After 3 hours reaction time, add 0.1 mol of pentaerythritol to fully dissolve pentaerythritol, raise the temperature to 70 ° C, reaction time 2 h, add substance A0.1 mol and phosphoric acid 0.05 mol, reaction temperature 70 ℃, reaction time 2 h, cool down to obtain flame retardant A;

Catalyst A was methyl diphenylglycolate.

The substance A is p-toluenesulfonamide;

The preparation method of the antibacterial agent is to add 3g of sulfathiazolyl, 1.6g of sulfadiazine, 1.3g of methionine and 15g of acetone to a flask, and then add 0.5g of oxalyl chloride and 4.4g of trichlorot-butanol to 60. The reaction was carried out for 3 hours at ℃, 0.2 g of cyanuric acid and 0.003 g of γ-butyrolactone were added and reacted at 70 ° C. for 2 hours, and acetone was removed to obtain the antibacterial agent;

The molecular weight of polytetrahydrofuran diol is 2000;

The isocyanate is 4,4'-dicyclohexylmethane diisocyanate.

Example 5

(1) In a 250 ml three-necked bottle with a stirrer, a condenser, and a thermometer, add 0.05 g of dibutyltin dilaurate, 73 g of polytetrahydrofuran diol, and 16 g of isocyanate, and react at 80 ° C for 1 hour to obtain a polyurethane prepolymer. A;

The flame retardant A is prepared by adding 0.6 mol of dimethyl phosphite to a three-necked flask, adding 0.01 mol of catalyst A and 0.66 mol of acrylamide, connecting a stirring blade, a condenser tube and a thermometer, and slowly raising the temperature to 80 ℃, holding the reaction for 2h to obtain a pale yellow liquid, which is 3-dimethoxyphosphoryl propionamide; To the obtained 3-dimethoxyphosphoryl propionamide, 0.2 mol of tetramethylol phosphate sulfate was added, and the reaction temperature was 110 ° C. The reaction time is 3 hours, and then add 0.1 mol of pentaerythritol to fully dissolve the pentaerythritol. The temperature is raised to 90 ° C, the reaction time is 3 hrs, and then add 0.1 mol of substance A and 0.05 mol of phosphoric acid. A;

Catalyst A was methyl 4-acetamido-2-ethoxybenzoate.

The substance A is acetyl tributyl citrate; the preparation method of the antibacterial agent is to add 3 g of sulfathiazole, 1.6 g of sulfadiazine, 1.3 g of methylpropionate, and 15 g of acetone to the flask, and then add ethylene glycol 0.5 g of acid chloride and 4.4 g of trichloro-tert-butanol were reacted at 60 ° C for 3 h, 0.2 g of cyanuric chloride and 0.003 g of γ-butyrolactone were reacted at 70 ° C for 2 h, and acetone was removed to obtain the antibacterial agent;

The molecular weight of polytetrahydrofuran diol is 2000;

Isocyanate is isophorone diisocyanate.

The flame retardancy is measured by the oxygen index and the burning time with flame. The swelling property and the residual carbon ratio are measured by the performance and swelling property of the film formed by the polyurethane coating. The muffle furnace is heated to 500 ° C, and 1 g ( The crucible with an error not exceeding 0.1 g) was placed in a muffle furnace and heated for 10 minutes, and the expansion rate and the residual carbon ratio were measured (only the flame retardant was measured).

Table 1 Test performance

It can be seen from Table 1 that the polyurethane coating and the adhesive have a better oxygen index and flame burning time than the comparative patents of the background art, showing a good flame retardant effect.

Table 2 Test performance (without flame retardant A)

It can be seen from Table 2 that the flame retardancy of the polyurethane coating without the flame retardant is reduced, indicating that polyurethane is added in the present invention, and a good effect is achieved.

Table 3 Test performance (with flame retardant A, but without catalyst A)

As can be seen from Table 3, the flame retardancy was better than that of Table 2 with the addition of the flame retardant without the catalyst A.

Table 4 Test performance (with flame retardant, with catalyst A, without substance A)

As can be seen from Table 4, the substance A has an increased residual carbon ratio and an expansion ratio.

Antibacterial properties were measured using E. coli, Staphylococcus aureus and Aspergillus flavus.

Table 5 Antibacterial data (%) of flame-retardant and antibacterial waterborne polyurethane coatings and adhesives

As can be seen from Table 5, the antibacterial agent has a better antibacterial effect.

Table 5 Antibacterial data (%) of flame retardant and antibacterial waterborne polyurethane coatings and adhesives for 360 days

As can be seen from Table 5, the antibacterial agent has good antibacterial durability.

Table 6 Antibacterial data (%) of flame-retardant and antibacterial waterborne polyurethane coatings and adhesives

It can be seen from Table 6 that trichlorot-butanol in this antibacterial agent has an effect of improving antibacterial properties.

Table 7 Antibacterial data (%) of flame-retardant and antibacterial waterborne polyurethane coatings and adhesives on the day without addition of (γ-butyrolactone)

As can be seen from Table 7, γ-butyrolactone improves its antibacterial properties.

Claims

The preparation method of flame-retardant and antibacterial water-based polyurethane coating and adhesive is as follows:

(1) In a 250 ml three-necked flask with a stirrer, a condenser, and a thermometer, add 0.05 g of dibutyltin dilaurate, 73 g of polytetrahydrofuran diol, and 16 g of isocyanate, and react at 70 to 90 ° C for 1 to 3 hours to obtain Polyurethane prepolymer A;

(2) The flame retardant A added to the polyurethane prepolymer A is 3.1 g, the antibacterial agent 1.5 g, and the solvent acetone 16.7 g. The reaction is performed at 60 to 90 ° C for 2 to 4 hours, and 6.7 g of triethylamine is added. After reacting for 90 minutes, 80-90 g of water was added and stirred for 0.5 h to obtain a flame-retardant and antibacterial water-based polyurethane coating and an adhesive.
The method for preparing a flame-retardant and antibacterial water-based polyurethane coating and adhesive according to claim 1, wherein the method for preparing the flame retardant A is: adding 0.6 mol of dimethyl phosphite to a three-necked flask, and adding catalyst A0 .01mol and 0.66 ～ 0.9molmol of acrylamide, connected to a stirring paddle, a condenser tube and a thermometer, slowly warmed to 70-90 ° C, holding the reaction for 2 ~ 5h, the light yellow liquid was 3-dimethoxyphosphoryl propionamide; To the obtained 3-dimethoxyphosphoryl propionamide, 0.2-0.6 mol of tetramethylol phosphate sulfate was added, the reaction temperature was 50 ° C to 110 ° C, the reaction time was 2 to 3 hours, and then 0.1 mol of pentaerythritol was added to fully dissolve the pentaerythritol and raise the temperature To 70 ~ 90 ° C, the reaction time is 2 ~ 3h, and then add 0.1mol of substance A and 0.05mol of phosphoric acid, the reaction temperature is 70 ~ 90 ° C, the reaction time is 2h, and the flame retardant A is obtained by cooling down.
The method for preparing a flame-retardant and antibacterial water-based polyurethane coating and an adhesive according to claim 2, wherein the catalyst A is methyl 4-acetamido-2-ethoxybenzoate and N-methylacetamide , Ethylene glycol dimethacrylate, or methyl diphenyl glycolate.
The method for preparing a flame-retardant and antibacterial aqueous polyurethane coating and an adhesive according to claim 2, wherein the substance A is acetyl tributyl citrate, tetraethoxysilane, phenyltriethoxysilane, Any of tosylamide.
The method for preparing a flame-retardant and antibacterial aqueous polyurethane coating and an adhesive according to claim 1, wherein the method for preparing the antibacterial agent is to use 3 g of sulfathiazole, 1.6 g of sulfadiazine, 1.3 g of meprobamate, and 15 g of acetone. Add to the flask, add 0.5g of glyoxyl chloride and 4.4g of trichloro-tert-butanol at 60 ° C for 2 to 3 hours, add 0.2g of cyanuric chloride and 0.003g of γ-butyrolactone at 70 ° C After 2 to 3 hours of reaction, acetone was removed to obtain the antibacterial agent.
The method for preparing a flame-retardant and antibacterial aqueous polyurethane coating and an adhesive according to claim 1, wherein the molecular weight of the polytetrahydrofuran ether glycol is any one of 650, 1000, 1800, and 2000.
The method for preparing a flame-retardant, waterproof, light-resistant water-based polyurethane coating and an adhesive according to claim 1, wherein the isocyanate is hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, 4,4 ' -Any of dicyclohexylmethane diisocyanates.