WO2016095289A1 - Preparation method for nanometer material capable of improving fire resistance of waterborne polyurethane coating and adhesive - Google Patents

Abstract

A preparation method for a nanometer material capable of improving fire resistance of a waterborne polyurethane coating and an adhesive comprises: mixing polytetramethylene ether glycol with isophorone diisocyanate, reacting in the presence of a Pd/Fe₃O₄-CNT catalyst, so as to obtain a polyurethane prepolymer A; adding dimethylolpropionic acid to the prepolymer A to react, adding triethylamine and carrying out neutral reaction, and adding water for emulsification, so as to form polyurethane B; and adding a nanometer material emulsion C to the polyurethane B, shearing and stirring under the condition that pH is 7, so as to obtain the fire-resistant polyurethane coating and adhesive. The polyurethane material is environmentally-friendly and low in price.

Description

Method for preparing nano material to improve flame retardancy of waterborne polyurethane coating and adhesive Technical field

The invention relates to a method for preparing a polyurethane, in particular to a method for preparing a nano material to improve the flame retardancy of an aqueous polyurethane coating and an adhesive.

Background technique

Waterborne polyurethane is a polyurethane resin containing a hydrophilic group in the molecular chain of polyurethane. It has a strong affinity with water and can be dispersed in water to form a stable system by a specific process. Waterborne polyurethane is mainly used in leather finishing, textile printing and dyeing, papermaking, architectural coatings, adhesives, etc., and almost all of them are flammable materials. If these materials are not used in flame retardant treatment, they will become a safety hazard. . Flame retardant of waterborne polyurethane is one of the important directions for the functionalization of waterborne polyurethane.

Nanomaterials which can improve the flame retardancy of materials include magnesium hydroxide, magnesium oxide, silicon oxide, etc., and have attracted much attention due to their characteristics of non-toxicity, smoke suppression and high decomposition temperature. However, the above inorganic nanomaterials are added in large amounts (see: Yuan Shaoyan, Xu Hong, Gu Hongchen. Research on flame retardant polymer-based nanocomposites[J]. Functional Materials, 2005, 36(6): 817-820 ), and its surface is hydrophilic and oleophobic, has a relatively large polarity, and is easy to agglomerate, making its compatibility and dispersibility in organic materials poor, which directly leads to a decrease in mechanical properties of the material (see: Zhang Ying, Hou Wensheng, Wei Liqiao, et al. Surface modification of nano-SiO ₂ and its application in polyurethane elastomers [J]. Functional Materials, 2006, 37 (8): 1286-1288), greatly limiting the use of inorganic nanomaterials. In order to improve the compatibility and dispersibility of inorganic nanomaterials in organic materials and improve the surface lipophilicity, surface modification is required. Therefore, surface modification methods are needed to improve their compatibility and to improve materials. The effects of mechanics and flame retardancy.

Polyurethane dilaurate is often used as a catalyst for the synthesis of polyurethane. However, since heavy metal tin is harmful to the environment with the degradation of polyurethane, screening for highly efficient and non-toxic catalysts is a major problem in polyurethane synthesis.

The carbon atoms in carbon nanotubes (CNTs) are dominated by sp2 hybridization, and the hexagonal lattice structure has a certain degree of curvature, forming a spatial topology, in which a certain sp3 hybrid bond can be formed, that is, the formed chemical bond has sp2 And sp3 mixed hybrid state, and these p orbits overlap each other to form a highly delocalized large π bond outside the carbon nanotube graphene sheet layer, and the large π bond of the outer surface of the carbon nanotube is a carbon nanotube with some The macromolecules of yoke properties are modified by carbon nanotubes by a chemical basis of non-covalent bonding, as a catalyst, as a catalyst for polyurethane prepolymers.

Summary of the invention

Pd/Fe ₃ O ₄ -CNT catalyst is selected to replace the traditional polyurethane catalyst, and is added to polytetrahydrofuran ether glycol and isophorone diisocyanate for catalysis, and nano materials such as nano-nickel oxide, nano-arsenide, diamond nano-powder are selected. The nano indium tin metal oxide and nano cerium oxide modify the polyurethane to improve the flame retardancy of the polyurethane coating and the adhesive.

The present invention adopts the following technical solutions.

1. A method for preparing a nano material to improve the flame retardancy of a waterborne polyurethane coating and an adhesive, characterized in that:

(1) Add 3.0g of carbon nanotubes and 250g of concentrated nitric acid to a 500ml three-necked flask, stir at room temperature for 24h, then wash with deionized water until the pH of the solution is neutral, dry at 100 °C overnight, and grind to obtain pretreated carbon nano Pipe; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux 0.5 After h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135g of alcohol, 20g of dioctyl ether and 0.12g of dipotassium edetate, heated to 100 ° C, added with 0.5g Fe ₃ O ₄ /CNT carrier, heated to boiling, refluxed for 0.5h, cooled to The protective gas was turned off at room temperature, suction filtered, washed with absolute ethanol until colorless, and dried overnight at 80 ° C to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

(2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 102 g of polytetrahydrofuran ether glycol and 33.6 g of isophorone diisocyanate were mixed, and Pd/Fe ₃ in the above (1) O ₂ -CNT catalyst in the presence of 0.26g, the reaction at 85 ° C for 1.5h, to obtain 134.5g polyurethane prepolymer A;

(3) Add 4.76 g of dimethylolpropionic acid and 15 g of isopropyl acetate to the polyurethane prepolymer A, react at 75 ° C for 1.5 h, add 5.99 g of triethylamine for neutralization for 30 min, add water 20 g. Emulsifying to form 180 g of polyurethane B for use;

(4) Dissolve 10 g of sodium lauryl sulfate in 50 g of water, add 1 g of nano-nickel oxide, 2 g of vinyl triethoxysilane, 1 g of triethanolamine and 0.4 g of sodium triacetate, and cut at a speed of 600 r/min. After emulsification, the emulsification time is 20 min, and the nano material emulsion C is used;

(5) 8 g of nano material emulsion C was added to the polyurethane B, and under a condition of pH 7, a shear stirring speed of 700 rpm and a stirring time of 30 minutes were carried out to obtain 187 g of a flame-retardant aqueous polyurethane coating and an adhesive.

2. A method for preparing a nano material to improve the flame retardancy of a waterborne polyurethane coating and an adhesive, characterized in that:

(1), adding 3.0g of carbon nanotubes to a 500ml three-necked flask, adding 250g of concentrated nitric acid, stirring at room temperature for 24h, then washing with deionized water until the pH of the solution is neutral, drying at 100 °C overnight, grinding to obtain pretreated carbon Nanotubes; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux After 0.5 h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135 g of diol, 20 g of dioctyl ether and 0.78 g of 3-carboxypyridazine, were purged with nitrogen, heated to 100 ° C, 0.5 g of Fe ₃ O ₄ /CNT carrier was added, heating was continued to boiling, refluxing for 0.5 h, cooling to room temperature The protective gas was turned off, suction filtered, washed with absolute ethanol until colorless, and dried overnight at 80 ° C to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

(2) 100 g of polytetrahydrofuran ether glycol and 109.9 g of isophorone diisocyanate were mixed in a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, and Pd/Fe ₃ in the above (1) O ₄ -CNT catalyst in the presence of 0.76g, reacted at 95 ° C for 3.5h, to obtain 209.1g polyurethane prepolymer A;

(3) Add 21.1 g of dimethylol butyric acid and 51.2 g of tetrahydrofuran to the polyurethane prepolymer A, react at 75 ° C for 4.5 h, add 13.1 g of triethylamine for neutralization for 50 min, and add 20 g of water for emulsification. Forming 306g of polyurethane emulsion B for use;

(4) Dissolving 12 g of sodium polyacrylate in 60 g of water, adding 5 g of nano gallium arsenide, 4 g of vinyl trimethoxysilane, 2.8 g of diethylene triamine pentacarboxylate and 2-aminophenol-4-(2' -carboxyl sulfonanilide 0.21g, shear emulsified at 1200r/min, emulsified for 60min, to obtain nanomaterial emulsion C for use;

(5) 30.6 g of the nano material emulsion C added to B was subjected to a shear stirring speed of 1100 rpm and a shear stirring time of 60 min under a pH of 7, and a flame retardant aqueous polyurethane coating and an adhesive 331 g were obtained.

3. A method for preparing a nano material to improve the flame retardancy of a waterborne polyurethane coating and an adhesive, characterized in that:

(1), adding 3.0g of carbon nanotubes to a 500ml three-necked flask, adding 250g of concentrated nitric acid, stirring at room temperature for 24h, then washing with deionized water until the pH of the solution is neutral, drying at 100 °C overnight, grinding to obtain pretreated carbon Nanotubes; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux After 0.5 h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135 g of diol, 20 g of dioctyl ether and 0.34 g of potassium 2-carboxy-5-nitrobenzenesulfonate, were purged with nitrogen, heated to 100 ° C, 0.5 g of Fe ₃ O ₄ /CNT carrier was added, and heating was continued until boiling. After refluxing for 0.5 h, cooling to room temperature, the shielding gas was turned off, suction filtration, washing with absolute ethanol until colorless, and drying at 80 ° C overnight to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

(2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 69.6 g of isophorone diisocyanate were mixed in a Pd/Fe ₃ O ₄ -CNT catalyst. In the presence of 0.68g, the reaction was carried out at 75 ° C for 3.5 h, to obtain 166.2 g of polyurethane prepolymer A;

(3) Add 10.5 g of dimethylolbutanoic acid and 29.3 g of dimethyl sulfoxide to the polyurethane prepolymer A, react at 85 ° C for 1.5 h, and add 9.78 g of triethylamine for neutralization for 60 min. 20 g of water was added for emulsification to form 231 g of polyurethane B for use;

(4) Dissolving 10 g of polyvinyl alcohol in 50 g of water, adding 3 g of diamond nanopowder, 3 g of γ-methacryloxypropyltrimethoxysilane, 1.9 g of tartaric acid and 0.56 g of p-carboxybenzenesulfonamide at 700 r Shear emulsification at /min and emulsification for 30 min to obtain nanomaterial emulsion C for use;

(5) 17.6 g of nano material emulsion C was added to the polyurethane B, and under a condition of pH 8, a shear stirring speed of 900 rpm and a stirring time of 35 minutes were carried out to obtain 251 g of a flame-retardant aqueous polyurethane coating and an adhesive.

4. A method for preparing a nano material to improve the flame retardancy of a waterborne polyurethane coating and an adhesive, characterized in that:

(1), adding 3.0g of carbon nanotubes to a 500ml three-necked flask, adding 250g of concentrated nitric acid, stirring at room temperature for 24h, then washing with deionized water until the pH of the solution is neutral, drying at 100 °C overnight, grinding to obtain pretreated carbon Nanotubes; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux After 0.5 h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135g of diol, 20g of dioctyl ether and 0.31g of 4-carboxybenzeneboronic acid, heated to 100 ° C, added with 0.5g of F _e3 O ₄ /CNT carrier, heated to boiling, refluxed for 0.5h, cooled to room temperature The protective gas was turned off, suction filtered, washed with absolute ethanol until colorless, and dried overnight at 80 ° C to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

(2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 33.3 g of isophorone diisocyanate were mixed in a Pd/Fe ₃ O ₄ -CNT catalyst. In the presence of 0.66g, the reaction was carried out at 75 ° C for 3.5 h, to obtain 133 g of polyurethane prepolymer A;

(3) Adding 4.75 g of dimethylolpropionic acid and 16 g of acetone solvent to the polyurethane prepolymer A, reacting at 85 ° C for 1.5 h, adding 5.97 g of triethylamine for neutralization for 30 min, and adding 20 g of water for emulsification. Forming 178g of polyurethane B for use;

(4) Dissolving 10 g of sodium polyphosphate in 50 g of water, adding 1 g of nano-indium tin metal oxide, 2 g of γ-aminopropyltriethoxysilane, 1 g of sodium ethylenediamine tetramethylene phosphate, and disalicylic acid The ester was 0.12g, and was emulsified by shear emulsification at 300r/min for 20min to obtain a nano material emulsion C. The chemical composition of the nano indium tin metal oxide was In ₂ O _{3 :} SnO ₂ =90.0wt%:10.0wt%. ;

(5) A 9 g nanomaterial emulsion C was added to A, and under a condition of pH 7, a shear stirring speed of 600 rpm and a stirring time of 50 min were carried out to obtain 187 g of a flame-retardant aqueous polyurethane coating and an adhesive.

5. A method for preparing a nano material to improve the flame retardancy of a waterborne polyurethane coating and an adhesive, characterized in that:

(1), adding 3.0g of carbon nanotubes to a 500ml three-necked flask, adding 250ml of concentrated nitric acid, stirring at room temperature for 24h, then washing with deionized water until the pH of the solution is neutral, drying at 100 ° C overnight, grinding to obtain pretreated carbon Nanotubes; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux After 0.5 h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135 g of diol, 0.1 g of dioctyl ether and 0.17 g of sodium 3-carboxybenzenesulfonate, passed through nitrogen, heated to 100 ° C, added 0.5 g of F _e3 O ₄ /CNT carrier, continued heating to boiling, reflux for 0.5 h, cooling At room temperature, the protective gas was turned off, suction filtered, washed with absolute ethanol until colorless, and dried overnight at 80 ° C to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

(2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 99.9 g of isophorone diisocyanate were mixed in a Pd/Fe ₃ O ₄ -CNT catalyst. In the presence of 0.6g, the reaction at 95 ° C for 1.5h, to obtain 200.9g polyurethane prepolymer A;

(3) Add 21.1 g of dimethylol butyric acid and 50.2 g of acetone solvent to A, react at 85 ° C for 1.5 h, add 12.1 g of triethylamine for neutralization for 50 min, and add 20 g of water to emulsify to form 304 g. Polyurethane emulsion B spare;

(4) Dissolving 10 g of sodium dodecylbenzene sulfonate in 50 g of water, adding 5 g of nano cerium oxide, 4 g of γ-glycidoxypropyl trimethoxysilane, 1 g of sodium alginate, and bis(4-carboxybenzene) Base phenylphosphine oxide 0.12g, shear emulsified at 1100r/min, emulsified for 40min, to obtain nanomaterial emulsion for use;

(5), adding 30.4 g of the above nanomaterial emulsion C to B, under the condition of pH 7, the shear stirring speed was 1100 rpm, and the shear stirring time was 40 min, and 331 g of a flame retardant waterborne polyurethane coating and an adhesive were obtained.

The invention has the following characteristics:

(1) Nanomaterials such as nano-nickel oxide, nano-GaAs, diamond nano-powder, nano-indium-tin oxide and nano-cerium oxide modify polyurethane, improve the defects of traditional inorganic nano-materials, improve polyurethane coatings and Flame retardant of adhesive;

(2) Select dipotassium ethylenediaminetetraacetate, potassium 2-carboxy-5-nitrobenzenesulfonate, potassium 2-carboxy-5-nitrobenzenesulfonate, 4-carboxybenzeneboronic acid and 3-carboxybenzenesulfonic acid Sodium changes carbon nanoparticle to improve catalytic efficiency;

(3) selecting isopropyl acetate, tetrahydrofuran, dimethyl sulfoxide or the like as a solvent for chain extension;

(4) selecting triethanolamine, sodium ammoniatriacetate, diethylenetriamine pentacarboxylate, tartaric acid, sodium alginate 1g and bis(4-carboxyphenyl)phenylphosphine oxide as synergists for nanomaterials, and Certain flame retardancy;

(5) Pd(acac) ₂ is palladium acetylacetonate, and Fe(acac) ₃ is a trivalent iron complex of acetylacetone, both of which modify the carbon nanotubes.

The present invention will be further described below with reference to examples.

Example one

(1) Add 3.0g of carbon nanotubes and 250g of concentrated nitric acid to a 500ml three-necked flask, stir at room temperature for 24h, then wash with deionized water until the pH of the solution is neutral, dry at 100 °C overnight, and grind to obtain pretreated carbon nano Pipe; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux 0.5 After h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135g of alcohol, 20g of dioctyl ether and 0.12g of dipotassium edetate, heated to 100 ° C, added with 0.5g Fe ₃ O ₄ /CNT carrier, heated to boiling, refluxed for 0.5h, cooled to The protective gas was turned off at room temperature, suction filtered, washed with absolute ethanol until colorless, and dried overnight at 80 ° C to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

(2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 102 g of polytetrahydrofuran ether glycol and 33.6 g of isophorone diisocyanate were mixed, and Pd/Fe ₃ in the above (1) O ₂ -CNT catalyst in the presence of 0.26g, the reaction at 85 ° C for 1.5h, to obtain 134.5g polyurethane prepolymer A;

(3) Add 4.76 g of dimethylolpropionic acid and 15 g of isopropyl acetate to the polyurethane prepolymer A, react at 75 ° C for 1.5 h, add 5.99 g of triethylamine for neutralization for 30 min, add water 20 g. Emulsifying to form 180 g of polyurethane B for use;

(4) Dissolve 10 g of sodium lauryl sulfate in 50 g of water, add 1 g of nano-nickel oxide, 2 g of vinyl triethoxysilane, 1 g of triethanolamine and 0.4 g of sodium triacetate, and cut at a speed of 600 r/min. After emulsification, the emulsification time is 20 min, and the nano material emulsion C is used;

(5), adding 8 g of nano material emulsion C to the polyurethane B, under the condition of pH 7, shearing stirring speed 700 rpm, stirring time At 30 min, 187 g of a flame retardant waterborne polyurethane coating and an adhesive were obtained.

Example two

(1), adding 3.0g of carbon nanotubes to a 500ml three-necked flask, adding 250g of concentrated nitric acid, stirring at room temperature for 24h, then washing with deionized water until the pH of the solution is neutral, drying at 100 °C overnight, grinding to obtain pretreated carbon Nanotubes; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux After 0.5 h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135 g of diol, 20 g of dioctyl ether and 0.78 g of 3-carboxypyridazine, were purged with nitrogen, heated to 100 ° C, 0.5 g of Fe ₃ O ₄ /CNT carrier was added, heating was continued to boiling, refluxing for 0.5 h, cooling to room temperature The protective gas was turned off, suction filtered, washed with absolute ethanol until colorless, and dried overnight at 80 ° C to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

(2) 100 g of polytetrahydrofuran ether glycol and 109.9 g of isophorone diisocyanate were mixed in a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, and Pd/Fe ₃ in the above (1) O ₄ -CNT catalyst in the presence of 0.76g, reacted at 95 ° C for 3.5h, to obtain 209.1g polyurethane prepolymer A;

(3) Add 21.1 g of dimethylol butyric acid and 51.2 g of tetrahydrofuran to the polyurethane prepolymer A, react at 75 ° C for 4.5 h, add 13.1 g of triethylamine for neutralization for 50 min, and add 20 g of water for emulsification. Forming 306g of polyurethane emulsion B for use;

(4) Dissolving 12 g of sodium polyacrylate in 60 g of water, adding 5 g of nano gallium arsenide, 4 g of vinyl trimethoxysilane, 2.8 g of diethylene triamine pentacarboxylate and 2-aminophenol-4-(2' -carboxyl sulfonanilide 0.21g, shear emulsified at 1200r/min, emulsified for 60min, to obtain nanomaterial emulsion C for use;

(5) 30.6 g of the nano material emulsion C added to B was subjected to a shear stirring speed of 1100 rpm and a shear stirring time of 60 min under a pH of 7, and a flame retardant aqueous polyurethane coating and an adhesive 331 g were obtained.

Example three

(1), adding 3.0g of carbon nanotubes to a 500ml three-necked flask, adding 250g of concentrated nitric acid, stirring at room temperature for 24h, then washing with deionized water until the pH of the solution is neutral, drying at 100 °C overnight, grinding to obtain pretreated carbon Nanotubes; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux After 0.5 h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135 g of diol, 20 g of dioctyl ether and 0.34 g of potassium 2-carboxy-5-nitrobenzenesulfonate, were purged with nitrogen, heated to 100 ° C, 0.5 g of Fe ₃ O ₄ /CNT carrier was added, and heating was continued until boiling. After refluxing for 0.5 h, cooling to room temperature, the shielding gas was turned off, suction filtration, washing with absolute ethanol until colorless, and drying at 80 ° C overnight to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

(2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 69.6 g of isophorone diisocyanate were mixed in a Pd/Fe ₃ O ₄ -CNT catalyst. In the presence of 0.68g, the reaction was carried out at 75 ° C for 3.5 h, to obtain 166.2 g of polyurethane prepolymer A;

(3) Add 10.5 g of dimethylolbutanoic acid and 29.3 g of dimethyl sulfoxide to the polyurethane prepolymer A, react at 85 ° C for 1.5 h, and add 9.78 g of triethylamine for neutralization for 60 min. 20 g of water was added for emulsification to form 231 g of polyurethane B for use;

(4) Dissolving 10 g of polyvinyl alcohol in 50 g of water, adding 3 g of diamond nanopowder, 3 g of γ-methacryloxypropyltrimethoxysilane, 1.9 g of tartaric acid and 0.56 g of p-carboxybenzenesulfonamide at 700 r Shear emulsification at /min and emulsification for 30 min to obtain nanomaterial emulsion C for use;

(5) 17.6 g of nano material emulsion C was added to the polyurethane B, and under a condition of pH 8, a shear stirring speed of 900 rpm and a stirring time of 35 minutes were carried out to obtain 251 g of a flame-retardant aqueous polyurethane coating and an adhesive.

Example four

(1), adding 3.0g of carbon nanotubes to a 500ml three-necked flask, adding 250g of concentrated nitric acid, stirring at room temperature for 24h, then washing with deionized water until the pH of the solution is neutral, drying at 100 °C overnight, grinding to obtain pretreated carbon Nanotubes; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux After 0.5 h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135g of diol, 20g of dioctyl ether and 0.31g of 4-carboxybenzeneboronic acid, heated to 100 ° C, added with 0.5g of F _e3 O ₄ /CNT carrier, heated to boiling, refluxed for 0.5h, cooled to room temperature The protective gas was turned off, suction filtered, washed with absolute ethanol until colorless, and dried overnight at 80 ° C to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

(2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 33.3 g of isophorone diisocyanate were mixed in a Pd/Fe ₃ O ₄ -CNT catalyst. In the presence of 0.66g, the reaction was carried out at 75 ° C for 3.5 h, to obtain 133 g of polyurethane prepolymer A;

(3) Adding 4.75 g of dimethylolpropionic acid and 16 g of acetone solvent to the polyurethane prepolymer A, reacting at 85 ° C for 1.5 h, adding 5.97 g of triethylamine for neutralization for 30 min, and adding 20 g of water for emulsification. Forming 178g of polyurethane B for use;

(4) Dissolving 10 g of sodium polyphosphate in 50 g of water, adding 1 g of nano-indium tin metal oxide, 2 g of γ-aminopropyltriethoxysilane, 1 g of sodium ethylenediamine tetramethylene phosphate, and disalicylic acid The ester was 0.12g, and was emulsified by shear emulsification at 300r/min for 20min to obtain a nano material emulsion C. The chemical composition of the nano indium tin metal oxide was In ₂ O _{3 :} SnO ₂ =90.0wt%:10.0wt%. ;

(5) A 9 g nanomaterial emulsion C was added to A, and under a condition of pH 7, a shear stirring speed of 600 rpm and a stirring time of 50 min were carried out to obtain 187 g of a flame-retardant aqueous polyurethane coating and an adhesive.

Example five

(1), adding 3.0g of carbon nanotubes to a 500ml three-necked flask, adding 250ml of concentrated nitric acid, stirring at room temperature for 24h, then washing with deionized water until the pH of the solution is neutral, drying at 100 ° C overnight, grinding to obtain pretreated carbon Nanotubes; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux After 0.5 h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135 g of diol, 0.1 g of dioctyl ether and 0.17 g of sodium 3-carboxybenzenesulfonate, passed through nitrogen, heated to 100 ° C, added 0.5 g of F _e3 O ₄ /CNT carrier, continued heating to boiling, reflux for 0.5 h, cooling At room temperature, the protective gas was turned off, suction filtered, washed with absolute ethanol until colorless, and dried overnight at 80 ° C to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

(2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 99.9 g of isophorone diisocyanate were mixed in a Pd/Fe ₃ O ₄ -CNT catalyst. In the presence of 0.6g, the reaction at 95 ° C for 1.5h, to obtain 200.9g polyurethane prepolymer A;

(3) Add 21.1 g of dimethylol butyric acid and 50.2 g of acetone solvent to A, react at 85 ° C for 1.5 h, add 12.1 g of triethylamine for neutralization for 50 min, and add 20 g of water to emulsify to form 304 g. Polyurethane emulsion B spare;

(4) Dissolving 10 g of sodium dodecylbenzene sulfonate in 50 g of water, adding 5 g of nano cerium oxide, 4 g of γ-glycidoxypropyl trimethoxysilane, 1 g of sodium alginate, and bis(4-carboxybenzene) Base phenylphosphine oxide 0.12g, shear emulsified at 1100r/min, emulsified for 40min, to obtain nanomaterial emulsion for use;

(5), adding 30.4 g of the above nanomaterial emulsion C to B, under the condition of pH 7, the shear stirring speed was 1100 rpm, and the shear stirring time was 40 min, and 331 g of a flame retardant waterborne polyurethane coating and an adhesive were obtained.

The beneficial effects of the present invention are further illustrated by relevant experimental data below:

Table 1 Film-forming properties of flame retardant polyurethane coatings and adhesive coatings and adhesives

test group	Example one	Example two	Example three	Example four	Example five
						Film appearance (water resistance 48h)	Transparent	Transparent	Transparent	Transparent	Transparent
hardness	B	B	B	B	B
						Adhesion / level	3	2	3	3	3
Flexibility / mm	2	2	3	2	3

It can be found from Table 1 that the performance is good in terms of film appearance, hardness, adhesion, and flexibility.

Table 2 Mechanical properties of the film obtained from flame retardant polyurethane coatings and adhesives

test group	Example one	Example two	Example three	Example four	Example five
						Elongation at break /%	143	158	129	165	172
Tensile strength / MPa	6.7	6.7	6.7	5.7	5.1
						Anti-wear/grade	3.5	4	3.5	3.5	3.5

The reference method for the detection of the indicators in Table 2 (Jiang Weizhen. Physical and chemical testing of leather products [M]. China Light Industry Press, 1999), the film obtained by the coating of the invention has good elongation at break, tensile strength and antiwear.

The flame retardancy is measured by the smoke density method (maximum smoke density, maximum smoke density time), oxygen index, vertical combustion index (flame burning time, flameless burning time), and the elongation at break is characterized by its mechanical properties.

Table 3 Flame retardancy of films obtained from flame retardant polyurethane coatings and adhesives

	Example one	Example two	Example three	Example four	Example five	Market PU-2
							Maximum smoke density	27	28	30	14	9	34
Maximum smoke density time / s	166	168	182	222	215	245
							Oxygen Index	25.5	25.8	25.8	25.8	26.7	21.1
Flaming burning time / s	21.4	21.4	12.3	11.8	11.1	56.1
							Flameless burning time / s	0	0	0	0	0	0

The indicators of Table 3 are based on the following criteria: smoke density is determined according to GB8323-2008, oxygen index is determined by GB/T5454-1997 "Textile burning performance test - oxygen index method"; flaming burning time and flameless burning time It is determined by GB/T5455-1997 "Textile Burning Energy Test - Vertical Method" meter.

It can be seen from Table 3 that when the film obtained by the flame-retardant polyurethane coating and the adhesive of the present invention is burned, the maximum smoke density is remarkably lowered, the time to reach the maximum smoke density is significantly prolonged, the oxygen index is obviously improved, and the burning time is obviously shortened.

Claims (5)

1. A method for preparing a nano material to improve the flame retardancy of a waterborne polyurethane coating and an adhesive, characterized in that:

   (1) Add 3.0g of carbon nanotubes and 250g of concentrated nitric acid to a 500ml three-necked flask, stir at room temperature for 24h, then wash with deionized water until the pH of the solution is neutral, dry at 100 °C overnight, and grind to obtain pretreated carbon nano Pipe; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux 0.5 After h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135g of alcohol, 20g of dioctyl ether and 0.12g of dipotassium edetate, heated to 100 ° C, added with 0.5g Fe ₃ O ₄ /CNT carrier, heated to boiling, refluxed for 0.5h, cooled to The protective gas was turned off at room temperature, suction filtered, washed with absolute ethanol until colorless, and dried overnight at 80 ° C to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

   (2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 102 g of polytetrahydrofuran ether glycol and 33.6 g of isophorone diisocyanate were mixed, and Pd/Fe ₃ in the above (1) O ₂ -CNT catalyst in the presence of 0.26g, the reaction at 85 ° C for 1.5h, to obtain 134.5g polyurethane prepolymer A;

   (3) Add 4.76 g of dimethylolpropionic acid and 15 g of isopropyl acetate to the polyurethane prepolymer A, react at 75 ° C for 1.5 h, add 5.99 g of triethylamine for neutralization for 30 min, add water 20 g. Emulsifying to form 180 g of polyurethane B for use;

   (4) Dissolve 10 g of sodium lauryl sulfate in 50 g of water, add 1 g of nano-nickel oxide, 2 g of vinyl triethoxysilane, 1 g of triethanolamine and 0.4 g of sodium triacetate, and cut at a speed of 600 r/min. After emulsification, the emulsification time is 20 min, and the nano material emulsion C is used;

   (5) 8 g of nano material emulsion C was added to the polyurethane B, and under a condition of pH 7, a shear stirring speed of 700 rpm and a stirring time of 30 minutes were carried out to obtain 187 g of a flame-retardant aqueous polyurethane coating and an adhesive.
2. A method for preparing a nano material to improve the flame retardancy of a waterborne polyurethane coating and an adhesive, characterized in that:

   (1), adding 3.0g of carbon nanotubes to a 500ml three-necked flask, adding 250g of concentrated nitric acid, stirring at room temperature for 24h, then washing with deionized water until the pH of the solution is neutral, drying at 100 °C overnight, grinding to obtain pretreated carbon Nanotubes; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux After 0.5 h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135 g of diol, 20 g of dioctyl ether and 0.78 g of 3-carboxypyridazine, were purged with nitrogen, heated to 100 ° C, 0.5 g of Fe ₃ O ₄ /CNT carrier was added, heating was continued to boiling, refluxing for 0.5 h, cooling to room temperature The protective gas was turned off, suction filtered, washed with absolute ethanol until colorless, and dried overnight at 80 ° C to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

   (2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 109.9 g of isophorone diisocyanate were mixed, and the Pd/Fe _{3 of the} above (1) was mixed. O ₄ -CNT catalyst in the presence of 0.76g, reacted at 95 ° C for 3.5h, to obtain 209.1g polyurethane prepolymer A;

   (3) Add 21.1 g of dimethylol butyric acid and 51.2 g of tetrahydrofuran to the polyurethane prepolymer A, react at 75 ° C for 4.5 h, add 13.1 g of triethylamine for neutralization for 50 min, and add 20 g of water for emulsification. Forming 306g of polyurethane emulsion B for use;

   (4) Dissolving 12 g of sodium polyacrylate in 60 g of water, adding 5 g of nano gallium arsenide, 4 g of vinyl trimethoxysilane, 2.8 g of diethylene triamine pentacarboxylate and 2-aminophenol-4-(2' -carboxyl sulfonanilide 0.21g, shear emulsified at 1200r/min, emulsified for 60min, to obtain nanomaterial emulsion C for use;

   (5) 30.6 g of the nano material emulsion C added to B was subjected to a shear stirring speed of 1100 rpm and a shear stirring time of 60 min under a pH of 7, and a flame retardant aqueous polyurethane coating and an adhesive 331 g were obtained.
3. A method for preparing a nano material to improve the flame retardancy of a waterborne polyurethane coating and an adhesive, characterized in that:

   (1), adding 3.0g of carbon nanotubes to a 500ml three-necked flask, adding 250g of concentrated nitric acid, stirring at room temperature for 24h, then washing with deionized water until the pH of the solution is neutral, drying at 100 °C overnight, grinding to obtain pretreated carbon Nanotubes; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux After 0.5 h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135 g of diol, 20 g of dioctyl ether and 0.34 g of potassium 2-carboxy-5-nitrobenzenesulfonate, were purged with nitrogen, heated to 100 ° C, 0.5 g of Fe ₃ O ₄ /CNT carrier was added, and heating was continued until boiling. After refluxing for 0.5 h, cooling to room temperature, the shielding gas was turned off, suction filtration, washing with absolute ethanol until colorless, and drying at 80 ° C overnight to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

   (2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 69.6 g of isophorone diisocyanate were mixed in a Pd/Fe ₃ O ₄ -CNT catalyst. In the presence of 0.68g, the reaction was carried out at 75 ° C for 3.5 h, to obtain 166.2 g of polyurethane prepolymer A;

   (3) Add 10.5 g of dimethylolbutanoic acid and 29.3 g of dimethyl sulfoxide to the polyurethane prepolymer A, react at 85 ° C for 1.5 h, and add 9.78 g of triethylamine for neutralization for 60 min. 20 g of water was added for emulsification to form 231 g of polyurethane B for use;

   (4) Dissolving 10 g of polyvinyl alcohol in 50 g of water, adding 3 g of diamond nanopowder, 3 g of γ-methacryloxypropyltrimethoxysilane, 1.9 g of tartaric acid and 0.56 g of p-carboxybenzenesulfonamide at 700 r Shear emulsification at /min and emulsification for 30 min to obtain nanomaterial emulsion C for use;

   (5) 17.6 g of nano material emulsion C was added to the polyurethane B, and under a condition of pH 8, a shear stirring speed of 900 rpm and a stirring time of 35 minutes were carried out to obtain 251 g of a flame-retardant aqueous polyurethane coating and an adhesive.
4. A method for preparing a nano material to improve the flame retardancy of a waterborne polyurethane coating and an adhesive, characterized in that:

   (1), adding 3.0g of carbon nanotubes to a 500ml three-necked flask, adding 250g of concentrated nitric acid, stirring at room temperature for 24h, then washing with deionized water until the pH of the solution is neutral, drying at 100 °C overnight, grinding to obtain pretreated carbon Nanotubes; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux After 0.5 h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135g of diol, 20g of dioctyl ether and 0.31g of 4-carboxybenzeneboronic acid, heated to 100 ° C, added with 0.5g of F _e3 O ₄ /CNT carrier, heated to boiling, refluxed for 0.5h, cooled to room temperature The protective gas was turned off, suction filtered, washed with absolute ethanol until colorless, and dried overnight at 80 ° C to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

   (2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 33.3 g of isophorone diisocyanate were mixed in a Pd/Fe ₃ O ₄ -CNT catalyst. In the presence of 0.66g, the reaction was carried out at 75 ° C for 3.5 h, to obtain 133 g of polyurethane prepolymer A;

   (3) Adding 4.75 g of dimethylolpropionic acid and 16 g of acetone solvent to the polyurethane prepolymer A, reacting at 85 ° C for 1.5 h, adding 5.97 g of triethylamine for neutralization for 30 min, and adding 20 g of water for emulsification. Forming 178g of polyurethane B for use;

   (4) Dissolving 10 g of sodium polyphosphate in 50 g of water, adding 1 g of nano-indium tin metal oxide, 2 g of γ-aminopropyltriethoxysilane, 1 g of sodium ethylenediamine tetramethylene phosphate, and disalicylic acid The ester was 0.12g, and was emulsified by shear emulsification at 300r/min for 20min to obtain a nano material emulsion C. The chemical composition of the nano indium tin metal oxide was In ₂ O _{3 :} SnO ₂ =90.0wt%:10.0wt%. ;

   (5) A 9 g nanomaterial emulsion C was added to A, and under a condition of pH 7, a shear stirring speed of 600 rpm and a stirring time of 50 min were carried out to obtain 187 g of a flame-retardant aqueous polyurethane coating and an adhesive.
5. A method for preparing a nano material to improve the flame retardancy of a waterborne polyurethane coating and an adhesive, characterized in that:

   (1), adding 3.0g of carbon nanotubes to a 500ml three-necked flask, adding 250ml of concentrated nitric acid, stirring at room temperature for 24h, then washing with deionized water until the pH of the solution is neutral, drying at 100 ° C overnight, grinding to obtain pretreated carbon Nanotubes; weigh 1.0g of pretreated carbon nanotubes, add 60g of triethylene glycol, after ultrasonic for 5min, then add Fe(acac) ₃ 1.5g, continue to ultrasonic for 10min, pass nitrogen, heat until the solution boils, reflux After 0.5 h, it was cooled to room temperature, washed with ethanol until it was colorless, and then air-dried at 80 ° C overnight to obtain a Fe ₃ O ₄ /CNT carrier; Pd(acac) ₂ 0.0446 g, 1,2-hexadecane was weighed. 0.1135 g of diol, 0.1 g of dioctyl ether and 0.17 g of sodium 3-carboxybenzenesulfonate, passed through nitrogen, heated to 100 ° C, added 0.5 g of F _e3 O ₄ /CNT carrier, continued heating to boiling, reflux for 0.5 h, cooling At room temperature, the protective gas was turned off, suction filtered, washed with absolute ethanol until colorless, and dried overnight at 80 ° C to obtain a Pd/Fe ₃ O ₄ -CNT catalyst;

   (2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 99.9 g of isophorone diisocyanate were mixed in a Pd/Fe ₃ O ₄ -CNT catalyst. In the presence of 0.6g, the reaction at 95 ° C for 1.5h, to obtain 200.9g polyurethane prepolymer A;

   (3) Add 21.1 g of dimethylol butyric acid and 50.2 g of acetone solvent to A, react at 85 ° C for 1.5 h, add 12.1 g of triethylamine for neutralization for 50 min, and add 20 g of water to emulsify to form 304 g. Polyurethane emulsion B spare;

   (4) Dissolving 10 g of sodium dodecylbenzene sulfonate in 50 g of water, adding 5 g of nano cerium oxide, 4 g of γ-glycidoxypropyl trimethoxysilane, 1 g of sodium alginate, and bis(4-carboxybenzene) Base phenylphosphine oxide 0.12g, shear emulsified at 1100r/min, emulsified for 40min, to obtain nanomaterial emulsion for use;

   (5), adding 30.4 g of the above nanomaterial emulsion C to B, under the condition of pH 7, the shear stirring speed was 1100 rpm, and the shear stirring time was 40 min, and 331 g of a flame retardant waterborne polyurethane coating and an adhesive were obtained.