CN107353394B

CN107353394B - Coating, polyurethane and preparation method thereof

Info

Publication number: CN107353394B
Application number: CN201710732421.7A
Authority: CN
Inventors: 张威; 朱小勇
Original assignee: Huangshan Liangu New Material Technology Co ltd
Current assignee: Huangshan Liangu New Material Technology Co ltd
Priority date: 2017-08-23
Filing date: 2017-08-23
Publication date: 2022-10-28
Anticipated expiration: 2037-08-23
Also published as: CN107353394A

Abstract

A coating, polyurethane and a preparation method thereof belong to the field of coatings. The polyurethane is mainly prepared by dispersing a prepolymer with hydrophilic groups into emulsion and polymerizing the emulsion in the presence of a polyamine chain extender. The prepolymer with hydrophilic groups is mainly prepared by reacting isocyanate, sulfonate type polyol, polymer polyol and hydroxyl-containing epoxy resin. The polyurethane comprises the following raw materials in parts by weight: 7.00 to 13.00 parts of isocyanate, 8.00 to 12.00 parts of sulfonate polyol, 12.00 to 15.00 parts of polymer polyol, 1.00 to 4.00 parts of hydroxyl-containing epoxy resin, 0.10 to 0.50 part of hydrophilic chain extender, 0.10 to 0.50 part of micromolecule chain extender, 0.20 to 0.70 part of cross-linking agent, 0.01 to 0.05 part of catalyst, 0.10 to 1.00 part of neutralizer, 1.00 to 3.00 parts of polyamine chain extender and 54.00 to 90.00 parts of water.

Description

Coating, polyurethane and preparation method thereof

Technical Field

The invention relates to the field of coatings, and particularly relates to a coating, polyurethane and a preparation method thereof.

Background

The polyurethane is a polymer containing urethane groups on a high molecular main chain, has good wear resistance, scratch resistance, good physical and mechanical properties, adjustable hardness and excellent low-temperature deflection resistance, and has the characteristic of adjustable size of water dispersible particles. Currently, polyurethanes are widely used in the fields of coatings, elastomers, and the like. In recent years, with the increase of environmental protection requirements, research and development of environmental protection polyurethane products have gradually become the subject of polyurethane researchers to explore, and particularly, solvent-free polyurethane and waterborne polyurethane are prominent. The waterborne polyurethane refers to a polyurethane resin material which takes water as a dispersion medium in polyurethane. The environment-friendly flame-retardant polyurethane coating material has the excellent characteristics of non-inflammability, low VOCs (volatile organic chemicals), safety, environmental protection and the like, and is widely applied to the fields of fabric treatment, leather finishing, adhesives, coatings, printing ink and the like. In recent years, research on the water-based polyurethane makes more breakthroughs in the aspect of physical and chemical properties, improves the solid content and the performance of the water-based polyurethane, and greatly expands the application range of the water-based polyurethane.

Although research on waterborne polyurethane is rapidly developing at present, many waterborne polyurethane materials with excellent physicochemical properties are also emerging, the research on special waterborne polyurethane materials with special properties still has a larger bottleneck, and particularly the research and development on self-extinction waterborne polyurethane are more difficult. For example, the existing aqueous polyurethane materials have the problems of weak extinction performance, poor balance between high extinction effect and emulsion stability, poor balance between high extinction effect and resin emulsion stability and the like.

Disclosure of Invention

The invention aims to provide a coating, polyurethane and a preparation method thereof, so as to obtain the polyurethane with self-extinction property, maintain the extinction effect and stability, improve the tensile strength property and improve the dry and wet rub resistance.

According to a first aspect of the present invention, a polyurethane is provided.

The polyurethane has self-extinction properties.

The polyurethane is mainly prepared by dispersing a prepolymer with hydrophilic groups into emulsion and polymerizing the emulsion in the presence of a polyamine chain extender, wherein the prepolymer with hydrophilic groups is mainly prepared by reacting isocyanate, sulfonate type polyol, polymer polyol and hydroxyl-containing epoxy resin.

The raw materials for preparing the polyurethane comprise the following components in parts by weight: 7.00 to 13.00 parts of isocyanate, 8.00 to 12.00 parts of sulfonate polyol, 12.00 to 15.00 parts of polymer polyol, 1.00 to 4.00 parts of hydroxyl-containing epoxy resin, 0.10 to 0.50 part of hydrophilic chain extender, 0.10 to 0.50 part of micromolecule chain extender, 0.20 to 0.70 part of cross-linking agent, 0.01 to 0.05 part of catalyst, 0.10 to 1.00 part of neutralizer, 1.00 to 3.00 parts of polyamine chain extender and 54.00 to 90.00 parts of water.

According to a second aspect of the present invention, there is provided a process for the preparation of the above polyurethane. The preparation method comprises the following steps: under the condition of heating, enabling isocyanate to contact with sulfonate type polyol, polymer polyol and hydroxyl-containing epoxy resin and carrying out polyaddition reaction to obtain a first polymer;

adding a solvent, a hydrophilic chain extender, a micromolecular chain extender, a cross-linking agent, a catalyst and the solvent to react after the first polymer is cooled, and adding a neutralizer and water to disperse to form a water emulsion;

adding the water solution dissolved with the polyamine chain extender into the water emulsion, continuously reacting in a heating and vacuum environment, and removing the solvent after the reaction is finished.

According to a third aspect of the present invention, a coating is provided. The coating mainly comprises the polyurethane.

The embodiment of the invention has the following beneficial effects:

the polyurethane provided by the embodiment of the invention adopts specific raw materials, formula and process to obtain the self-extinction waterborne polyurethane which has ultralow gloss, no solid extinction component, high tensile strength, excellent hand feeling and excellent dry and wet rub resistance. The polyurethane has excellent miscibility with other resins, and can be widely applied to various matt coatings, such as matt wood paint, matt printing adhesive cement, matt leather finishing, packaging matt coatings and the like.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.

The following is a detailed description of the coating, polyurethane and method of making the same of the embodiments of the present invention:

based on the deficiencies of the prior art, the inventors propose a polyurethane. The polyurethane is self-extinction dry-wet-wiping-resistant high-strength water-based polyurethane. In some examples, the resulting polyurethane has the characteristics of 60 ° gloss of 0, tensile break strength of 27MPa, elongation at break > 400%.

The raw materials for preparing the polyurethane comprise the following components in parts by weight: 7.00 to 13.00 portions of isocyanate, 8.00 to 12.00 portions of sulfonate polyol, 12.00 to 15.00 portions of polymer polyol, 1.00 to 4.00 portions of hydroxyl-containing epoxy resin, 0.10 to 0.50 portion of hydrophilic chain extender, 0.10 to 0.50 portion of micromolecule chain extender, 0.20 to 0.70 portion of cross linker, 0.01 to 0.05 portion of catalyst, 0.10 to 1.00 portion of neutralizer, 1.00 to 3.00 portions of polyamine chain extender and 54.00 to 90.00 portions of water.

Further, the raw materials for preparing the polyurethane comprise the following components in parts by weight: 8.00 to 12.00 parts of isocyanate, 9.00 to 11.00 parts of sulfonate polyol, 13.00 to 14.00 parts of polymer polyol, 2.00 to 3.00 parts of hydroxyl-containing epoxy resin, 0.20 to 0.30 part of hydrophilic chain extender, 0.30 to 0.40 part of micromolecule chain extender, 0.40 to 0.60 part of cross-linking agent, 0.02 to 0.04 part of catalyst, 0.40 to 0.80 part of neutralizer, 1.60 to 2.80 parts of polyamine chain extender and 60.00 to 80.00 parts of water.

Wherein the isocyanate may be a mono-isocyanate or a polyisocyanate. As an alternative example, the isocyanate includes any one of isophorone diisocyanate, cyclohexylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, tetramethyl diisocyanate, xylylene diisocyanate, and p-phenylene diisocyanate.

Wherein the sulfonate polyol has a number average molecular weight of 400, or 1000, or 1500, or 2000.

Wherein the polymer polyol has an alcohol hydroxyl value of 50 to 120mg KOH/g. In some examples, the polymer polyol has an alcohol hydroxyl number of 65 to 75KOH/g, or 80 to 90KOH/g, or 100 to 110KOH/g. The alcoholic hydroxyl value is the content (or concentration) of hydroxyl groups, and means the amount of hydroxyl groups contained in a sample per unit weight, and the unit is mgKOH/g. The hydroxyl value was determined by acid-base titration. The proper alcohol hydroxyl value can improve the reaction activity and simultaneously keep the proper viscosity of a reaction system, thereby improving the physical and chemical properties of the polyurethane, such as hardness and temperature resistance. The hydroxyl value of the polymer polyol is high, so that the reactivity of the isocyanate and the polymer polyol is enhanced, and the main reaction is enhanced; if the hydroxyl value of the polymer polyol is low, the reaction between isocyanate and water is enhanced, so that the main reaction speed cannot follow the foaming reaction speed, and the foam collapse phenomenon is easily caused. When the content of the hydroxyl value is increased, the amount of the isocyanate needs to be increased, and the amount of the isocyanate is not adjusted, namely, the isocyanate is added too little, so that the problems of foam crack, poor rebound resilience, poor strength, increased compression set and the like are caused. On the other hand, the decrease in hydroxyl number corresponds to the addition of too much isocyanate, which leads to the formation of large and closed cells in the foam, an increase in hardness, a long curing time and the like, leading to the occurrence of burning.

The polymer polyol may be either one of a polyester polyol, a polyether polyamine, or a mixture of both. When the polymer polyol is a mixture of a polyester polyol, a polyether polyol, the polymer polyol includes a polyester polyol and a polyether polyol. In some examples, the polymer polyol can be any one or more of polybutylene adipate diol, polyethylene adipate diol, polybutylene adipate diol, polyethylene glycol adipate diol, neopentyl glycol adipate diol, polybutylene adipate diethylene glycol diol, polypropylene adipate diol, polyepsilon-caprolactone diol, polyoxypropylene ether diol, polycarbonate diol, polytetrahydrofuran ether diol, and polyoxyethylene ether diol, such as a combination of two (e.g., polybutylene adipate diol and polyethylene glycol adipate at a weight ratio of 1.

Preferably, the polyester polyol is a condensation product of adipic acid and a polyol, wherein the polyol comprises a mixture of any one or more of butanediol, ethylene glycol, neopentyl glycol or propylene glycol. The polyether polyol is one or more of polypropylene glycol, polyethylene glycol and polytetrahydrofuran ether glycol.

Wherein, the hydrophilic chain extender comprises any one or more of sulfamate, dimethylolpropionic acid, dimethylolbutyric acid, dimethylolpropionic acid and hydroxyl sulfonate.

Wherein the small molecular chain extender comprises any one or more of butanediol, 1, 2-propanediol, 1, 3-propanediol, ethylene glycol, diethylene glycol, triethylene glycol, 1, 4-cyclohexanedimethanol, 1, 6-hexanediol and neopentyl glycol.

Wherein the polyamine chain extender comprises any one of ethylenediamine, hexamethylenediamine, hydrazine hydrate, diethylenetriamine and triethylene tetramine.

Wherein the cross-linking agent comprises any one or more of triethanolamine, trimethylolpropane, trifunctional polyether polyol and castor oil.

Wherein the catalyst is an organometallic catalyst. As an alternative example, the organometallic includes organic antimony and/or organic bismuth. The organic bismuth can be any one of bismuth isooctanoate, bismuth laurate 334095 and bismuth neodecanoate.

Wherein the neutralizing agent comprises one or more of triethylamine, dimethylacetamide, N-dimethylethanolamine, N-diethylethanolamine and ammonia water.

Based on the polyurethane, the invention also provides a coating. The coating comprises the polyurethane, and optional pigment, filler, auxiliary agent and the like. When in use, the coating exists in the form of viscous liquid dissolved in organic solvent or water. The application mode can be knife coating, spraying and the like, and can be selected according to actual needs.

The inventor also provides a preparation method of the polyurethane.

The polyurethane is mainly prepared by dispersing a prepolymer with hydrophilic groups into emulsion and polymerizing the emulsion in the presence of a polyamine chain extender. The prepolymer with hydrophilic groups is mainly prepared by reacting isocyanate, sulfonate type polyol, polymer polyol and hydroxyl-containing epoxy resin.

The following is a detailed description of the preparation method of polyurethane.

The method of making the polyurethane comprises:

step S101, under the condition of heating, enabling isocyanate to contact sulfonate type polyol, polymer polyol and hydroxyl-containing epoxy resin and enabling polyaddition reaction to occur.

The isocyanate, sulfonate-type polyol, polymer polyol, hydroxyl group-containing epoxy resin as a part of the raw materials are preferably subjected to dehydration treatment to reduce interference and adverse effects of the polymerization reaction of the isocyanate and alcohol by moisture.

In some examples of the present invention, the dehydration treatment may be performed by subjecting the isocyanate, the sulfonate-type polyol, the polymer polyol, and the hydroxyl group-containing epoxy resin to heat drying in separate devices or apparatuses. For example, the dehydration is carried out under vacuum at 90 to 130 ℃ for 1 to 2 hours, and the drying temperature may be 100 to 110 ℃ or 106 to 125 ℃.

After drying each raw material separately, it is preferable that the sulfonate type polyol, the polymer polyol, and the hydroxyl group-containing epoxy resin are mixed well to form a mixture, and then mixed with the isocyanate, and the polyaddition reaction is carried out under heating. As an alternative embodiment, the polyaddition is carried out at a temperature of from 70 to 90 ℃ for a time of from 2 to 4 hours. Preferably, the temperature of the addition polymerization reaction is 73 to 82 ℃. More preferably, the temperature of the addition polymerization is from 84 to 89 ℃.

The first polymer in which preliminary polymerization occurs can be obtained by this step.

Step S102, adding a solvent, a hydrophilic chain extender, a micromolecular chain extender, a cross-linking agent, a catalyst and the solvent to react after the first polymer is cooled, and adding a neutralizer and water to disperse to form a water emulsion.

The first polymer is further polymerized based on the need to adjust the degree of crosslinking of the polymer, the ratio of soft and hard segments in the polymer chain, etc., so as to obtain improved structural strength and chemical stability.

Wherein, the first polymer is obtained by reacting at 70-90 ℃ for 2-4 hours, so that when the temperature is reduced to 50-70 ℃, the solvent, the hydrophilic chain extender, the micromolecule chain extender, the cross-linking agent, the catalyst and the solvent are reacted and are reacted at 50-70 ℃ for 5-8 hours.

Preferably, the solvent, the hydrophilic chain extender, the small molecular chain extender, the cross-linking agent, the catalyst and the solvent are contacted and reacted with the first polymer in a multi-addition mode. For example, when the first polymer is cooled to 50 to 70 ℃, the hydrophilic chain extender, the small molecule chain extender and the cross-linking agent, the catalyst and the solvent are added and kept at 50 to 70 ℃ for 5 to 8 hours to perform the reaction to obtain the prepolymer, and the prepolymer contains hydrophilic groups such as hydroxyl groups. Wherein, the solvent can be acetone, and the dosage of the acetone is 30 to 50 percent of the mass of the prepolymer.

Further, a neutralizing agent and water are added to the prepolymer and stirred to achieve uniform dispersion, thereby preparing an aqueous emulsion.

Step S103, adding the aqueous solution dissolved with the polyamine chain extender into the aqueous emulsion, continuously reacting in a heating and vacuum environment, and removing the solvent after the reaction is finished.

It should be noted that the term "self-matting" as used in the polyurethane having self-matting properties provided in the present invention means that no matting material such as wax, diatomaceous earth, kaolin, fumed silica, etc., which are generally used, is added to the polyurethane, in other words, low gloss is an intrinsic property thereof.

The coating, polyurethane and process for making the same of the present invention are described in further detail below with reference to the examples.

Example 1

This example provides a polyurethane prepared as described below, wherein the raw materials are used in the amounts indicated in parts by weight.

80.00 parts of polybutylene adipate diol (Mn = 2000), 80.00 parts of polypropylene oxide diol (Mn = 2000) and 130.00 parts of sulfonate type polyester diol (Mn = 1500) were subjected to vacuum extraction at 120 ℃ and 0.09MPa for 2 hours to remove water. 47.04 parts of hexamethylene diisocyanate and 62.16 parts of isophorone diisocyanate were added, stirred and reacted at 80 ℃ for 2 hours. 50.00 parts of acetone, 1.50 parts of dimethylolpropionic acid, 2.90 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst are added and the temperature is maintained at 60 ℃ for reaction for 5 hours. Adding 1.80 parts of triethylamine neutralizer for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersing; 14.00 parts of ethylenediamine is added into 150 parts of water and stirred uniformly, slowly added into the emulsion, and kept stirring for 30min. Keeping the emulsion stirred for 2h under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

Example 2

80.00 parts of polydiethylene glycol butanediol adipate glycol (Mn = 2000), 80.00 parts of polytetrahydrofuran ether glycol (Mn = 2000) and 130.00 parts of sulfonate type polyester diol (Mn = 1500) are subjected to vacuum pumping at 120 ℃ and 0.09MPa for removing water for 2h. 47.04 parts of hexamethylene diisocyanate and 62.16 parts of isophorone diisocyanate were added, stirred and reacted at 80 ℃ for 2 hours. 50.00 parts of acetone, 1.50 parts of dimethylolpropionic acid, 2.90 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst are added and the temperature is maintained at 60 ℃ for reaction for 5 hours. Adding 1.80 parts of triethylamine neutralizer for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersing; 14.00 parts of ethylenediamine is added into 150 parts of water and stirred uniformly, slowly added into the emulsion, and kept stirring for 30min. Keeping the emulsion stirred for 2h under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

Example 3

80.00 parts of polydiethylene glycol butanediol adipate diol (Mn = 2000), 80.00 parts of polypropylene oxide diol (Mn = 2000) and 130.00 parts of sulfonate type polyester diol (Mn = 1500) were subjected to vacuum water removal at 120 ℃ and 0.09MPa for 2h. 47.04 parts of hexamethylene diisocyanate and 73.36 parts of dicyclohexylmethane diisocyanate were added, stirred and kept at 80 ℃ for reaction for 2 hours. 50.00 parts of acetone, 2.00 parts of dimethylolpropionic acid, 2.56 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst are added and the temperature is maintained at 60 ℃ for reaction for 5 hours. Adding 2.00 parts of triethylamine neutralizing agent for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersion; 27.00 parts of hexamethylene diamine is added into 150 parts of water and stirred evenly, slowly added into the emulsion and kept stirring for 30min. Keeping the emulsion stirred for 2h under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

Example 4

80.00 parts of polyethylene glycol butanediol adipate glycol (Mn = 2000), 80.00 parts of polypropylene oxide glycol (Mn = 2000) and 130.00 parts of sulfonate type polyester diol (Mn = 1500) are subjected to vacuum extraction at 120 ℃ and 0.09MPa for removing water for 2h. 146.72 parts of dicyclohexylmethane diisocyanate are added, stirred and reacted for 2h while maintaining 80 ℃. 50.00 parts of acetone, 1.00 part of dimethylolpropionic acid, 3.23 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst are added and the temperature is maintained at 60 ℃ for reaction for 5 hours. Adding 1.00 part of triethylamine neutralizer for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersing; 14.00 parts of ethylenediamine is added into 150 parts of water and stirred uniformly, slowly added into the emulsion, and kept stirring for 30min. Keeping the emulsion stirred for 2 hours under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

Example 5

80.00 parts of poly neopentyl glycol adipate glycol (Mn = 2000), 80.00 parts of polytetrahydrofuran ether glycol (Mn = 2000) and 130.00 parts of sulfonate type polyester diol (Mn = 1500) are subjected to vacuum extraction at 120 ℃ and 0.09MPa for removing water for 2h. 124.32 parts of isophorone diisocyanate are added, stirred and kept at 80 ℃ for reaction for 2h. 50.00 parts of acetone, 2.50 parts of dimethylolpropionic acid, 2.22 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst are added and the temperature is maintained at 60 ℃ for reaction for 5 hours. Adding 2.50 parts of triethylamine neutralizing agent for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersion; 27.00 parts of hexamethylene diamine is added into 150 parts of water and stirred evenly, slowly added into the emulsion and kept stirring for 30min. Keeping the emulsion stirred for 2 hours under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

Example 6

80.00 parts of polycarbonate diol (Mn = 2000), 80.00 parts of polytetrahydrofuran ether glycol (Mn = 2000) and 130.00 parts of sulfonate polyester diol (Mn = 1500) were freed from water at 120 ℃ under a vacuum of 0.09MPa for 2h. 124.32 parts of isophorone diisocyanate are added, stirred and reacted for 2h while maintaining 80 ℃. 50.00 parts of acetone, 3.00 parts of dimethylolpropionic acid, 1.88 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst are added and the temperature is maintained at 60 ℃ for reaction for 5 hours. Adding 3.00 parts of triethylamine neutralizing agent for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersion; adding 15.98 parts of diethylenetriamine into 150 parts of water, stirring uniformly, slowly adding into the emulsion, and continuously stirring for 30min. Keeping the emulsion stirred for 2h under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

Example 7

80.00 parts of polydiethylene glycol butanediol adipate diol (Mn = 2000), 80.00 parts of polypropylene oxide diol (Mn = 2000) and 130.00 parts of sulfonate type polyester diol (Mn = 1500) are subjected to vacuum pumping at 120 ℃ and 0.09MPa to remove water for 2h. 47.04 parts of hexamethylene diisocyanate and 73.36 parts of dicyclohexylmethane diisocyanate were added, stirred and kept at 80 ℃ for reaction for 2 hours. 50.00 parts of acetone, 1.00 part of dimethylolpropionic acid, 3.23 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst are added and the temperature is maintained at 60 ℃ for reaction for 5 hours. Adding 1.00 part of triethylamine neutralizer for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersing; adding 17.03 parts of triethylene tetramine into 150 parts of water, uniformly stirring, slowly adding the mixture into the emulsion, and continuously stirring for 30min. Keeping the emulsion stirred for 2 hours under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

Example 8

86.67 parts of polycaprolactone diol (Mn = 2000), 86.67 parts of polytetrahydrofuran ether glycol (Mn = 2000) and 120.00 parts of sulfonate-type polyester diol (Mn = 1500) were evacuated at 120 ℃ and 0.09MPa for 2h to remove water. 47.04 parts of hexamethylene diisocyanate and 62.16 parts of isophorone diisocyanate were added, stirred and reacted at 80 ℃ for 2 hours. 50.00 parts of acetone, 1.50 parts of dimethylolpropionic acid, 2.90 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst are added and the temperature is maintained at 60 ℃ for reaction for 5 hours. Adding 1.50 parts of triethylamine neutralizing agent for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersion; adding 17.67 parts of tetraethylenepentamine into 150 parts of water, stirring uniformly, slowly adding into the emulsion, and continuously stirring for 30min. Keeping the emulsion stirred for 2h under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

Comparative example 1

(1) 20g (20 mmol) of polytetrahydrofuran ether glycol having a molecular weight of 1000 and 19 (7.5 mmol) of dimethylolpropionic acid are dehydrated in a reaction vessel under vacuum at 120 ℃. After the vacuum was stopped, the temperature was reduced to 60 ℃ and a small amount of dibutyltin dilaurate catalyst and 11g of isophorone diisocyanate (50 mmol) were added, and the temperature was raised to 80 ℃ for reaction for 3 hours. (2) The temperature is reduced to 50 ℃, 0.7g (7 mmol) of triethylamine is added into the product of the step (1) for neutralization reaction for 30min. (3) And continuously cooling to below 30 ℃, adding an aqueous solution (the dilution water consumption accounts for 80 percent of the total water demand in the whole reaction) in which 0.5g (2.6 mmol) of 2- (2-aminoethyl) aminoethanesulfonic acid sodium salt is dissolved into the reaction kettle for emulsification and chain extension for 10min. (4) And adding an aqueous solution containing 0.6g of hydrazine hydrate for secondary chain extension for 1 hour, cooling to room temperature, filtering and discharging to obtain the polyurethane resin.

Test example 1

This experiment was used to test the gloss of the polyurethanes provided in examples 1 to 8 and comparative example 1. In particular, the national standards of the republic of China, the determination of 20 °, 60 ° and 85 ° specular gloss of pigmented paint films, both pigmented and clear, without metallic pigments (GB 9754-88). The results are shown in Table 1.

TABLE 1 polyurethane 60 ℃ gloss

Test example 2

This experiment was used to test the rub fastness and stability of the polyurethanes provided in examples 1-8. Specifically, the color fastness to rubbing is tested by the national standard of the republic of China (GB/T3920-2008); national standard of republic of China, paint storage stability test method (GB 6753.3-86). The results are shown in Table 2.

TABLE 2 polyurethane rub fastness and stability

In table 2, the scale scores for crusting, stress, corrosion and rancid flavor were: 10= none, 8= very mild, 6= mild, 4= moderate, 2= more severe, 0= severe.

The grade score of the degree of sedimentation was: 10= full suspension. Compared with the original state of the colored paint, the color paint has no change. 8= clear sedimentation feel and small amount of deposited pigment on the blade. There is no significant resistance to displacement with the face of the blade. 6= distinct settled pigment cake. The dead weight of the knife can pass through the pigment block and fall to the war part of the container. The knife face of the knife is pushed to have certain resistance. The cake of agglomerated portions can be transferred to a knife. 4= the weight of the knife cannot fall into the battle part of the container. The knife is difficult to move by adjusting the blade after passing through the pigment block, and the blade is slightly resistant when moving along the pot edge. But the pigmented paint can be easily remixed to a uniform state. 2= when the knife is forced to penetrate through the pigment deposit, the knife is difficult to move, and the edge of the knife is moved along the edge of the can with obvious resistance. But the paints can be remixed to a homogeneous state. 0= knot into very H hard lumps. These hard lumps can no longer be remixed with liquid into a homogeneous colored paint by manual stirring within 3-5 min.

The grade scores of the particles, the rubber blocks or the sliding blocks on the paint film are as follows: 10= none, 8= very mild, 6= mild, 4= moderate, 2= more severe, 0= severe.

From the results of the above test examples 1 and 2, it can be seen that the polyurethane provided in the examples of the present invention has the stability and the good gloss characteristics, and the gloss is 0 at an angle of 60 °, and the polyurethane in comparative example 1 is obviously limited, that is, the polyurethane provided in the present invention achieves the advantages of both self-extinction and stability.

While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

1. A polyurethane is characterized in that the preparation method is as follows, wherein the usage of each raw material is calculated by weight parts, 80.00 parts of polybutylene adipate diol Mn =2000, 80.00 parts of polypropylene oxide diol Mn =2000 and 130.00 parts of sulfonate type polyester diol Mn =1500 are vacuumized and dehydrated for 2h at 120 ℃ under 0.09 MPa; adding 47.04 parts of hexamethylene diisocyanate and 62.16 parts of isophorone diisocyanate, stirring and reacting for 2 hours at 80 ℃; adding 50.00 parts of acetone, 1.50 parts of dimethylolpropionic acid, 2.90 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst, and keeping the temperature at 60 ℃ for reaction for 5 hours; adding 1.80 parts of triethylamine neutralizing agent for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersion; adding 14.00 parts of ethylenediamine into 150 parts of water, uniformly stirring, slowly adding the mixture into the emulsion, and continuously stirring for 30min; keeping stirring the emulsion for 2h under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

2. A polyurethane is characterized in that the preparation method is as follows, wherein, the usage of each raw material is calculated by weight parts, 80.00 parts of polydiethylene glycol butanediol adipate diol Mn =2000, 80.00 parts of polytetrahydrofuran ether diol Mn =2000 and 130.00 parts of sulfonate type polyester diol Mn =1500 are vacuumized at 120 ℃ and 0.09MPa for removing water for 2h; adding 47.04 parts of hexamethylene diisocyanate and 62.16 parts of isophorone diisocyanate, stirring and reacting for 2 hours at 80 ℃; adding 50.00 parts of acetone, 1.50 parts of dimethylolpropionic acid, 2.90 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst, and keeping the temperature at 60 ℃ for reaction for 5 hours; adding 1.80 parts of triethylamine neutralizer for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersing; adding 14.00 parts of ethylenediamine into 150 parts of water, uniformly stirring, slowly adding the mixture into the emulsion, and continuously stirring for 30min; keeping stirring the emulsion for 2h under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

3. The polyurethane is characterized by being prepared by the following steps of using 80.00 parts by weight of polydiethylene glycol adipate butanediol ester diol Mn =2000, 80.00 parts by weight of polypropylene oxide diol Mn =2000 and 130.00 parts by weight of sulfonate type polyester diol Mn =1500, and vacuumizing at 120 ℃ and 0.09MPa for removing water for 2h; adding 47.04 parts of hexamethylene diisocyanate and 73.36 parts of dicyclohexylmethane diisocyanate, stirring and keeping the temperature at 80 ℃ for reacting for 2 hours; adding 50.00 parts of acetone, 2.00 parts of dimethylolpropionic acid, 2.56 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst, and keeping the temperature at 60 ℃ for reaction for 5 hours; adding 2.00 parts of triethylamine neutralizing agent for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersion; adding 27.00 parts of hexamethylene diamine into 150 parts of water, uniformly stirring, slowly adding the mixture into the emulsion, and continuously stirring for 30min; keeping stirring the emulsion for 2h under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

4. A polyurethane is characterized in that the preparation method is as follows, wherein, the usage of each raw material is calculated by weight portion, 80.00 portions of poly ethylene glycol adipate butanediol Mn =2000, 80.00 portions of poly propylene oxide diol Mn =2000 and 130.00 portions of sulfonate polyester diol Mn =1500 are vacuumized at 120 ℃ and 0.09MPa to remove water for 2h; adding 146.72 parts of dicyclohexylmethane diisocyanate, stirring and reacting for 2 hours at 80 ℃; adding 50.00 parts of acetone, 1.00 part of dimethylolpropionic acid, 3.23 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst, and keeping the temperature at 60 ℃ for reaction for 5 hours; adding 1.00 part of triethylamine neutralizing agent for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersion; adding 14.00 parts of ethylenediamine into 150 parts of water, uniformly stirring, slowly adding the mixture into the emulsion, and continuously stirring for 30min; keeping stirring the emulsion for 2h under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

5. A polyurethane is characterized in that the preparation method is as follows, wherein, the amount of each raw material is calculated by weight portion, 80.00 portions of poly neopentyl glycol adipate diol Mn =2000, 80.00 portions of polytetrahydrofuran ether diol Mn =2000 and 130.00 portions of sulfonate type polyester diol Mn =1500 are vacuumized at 120 ℃ and 0.09MPa to remove water for 2h; adding 124.32 parts of isophorone diisocyanate, stirring and reacting for 2 hours at 80 ℃; adding 50.00 parts of acetone, 2.50 parts of dimethylolpropionic acid, 2.22 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst, and keeping the temperature at 60 ℃ for reaction for 5 hours; adding 2.50 parts of triethylamine neutralizing agent for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersion; adding 27.00 parts of hexamethylene diamine into 150 parts of water, stirring uniformly, slowly adding into the emulsion, and continuously stirring for 30min; keeping stirring the emulsion for 2h under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

6. A polyurethane is characterized in that the preparation method is as follows, wherein, the amount of each raw material is calculated by weight portion, 80.00 portions of polycarbonate diol Mn =2000, 80.00 portions of polytetrahydrofuran ether diol Mn =2000 and 130.00 portions of sulfonate polyester diol Mn =1500 are vacuumized and dehydrated for 2h at 120 ℃ and 0.09 MPa; adding 124.32 parts of isophorone diisocyanate, stirring and keeping the temperature of 80 ℃ for reaction for 2 hours, adding 50.00 parts of acetone, 3.00 parts of dimethylolpropionic acid, 1.88 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst, and keeping the temperature of 60 ℃ for reaction for 5 hours; adding 3.00 parts of triethylamine neutralizing agent for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersion; adding 15.98 parts of diethylenetriamine into 150 parts of water, stirring uniformly, slowly adding into the emulsion, and continuously stirring for 30min; keeping stirring the emulsion for 2h under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

7. The polyurethane is characterized by being prepared by the following steps of using 80.00 parts by weight of polydiethylene glycol adipate butanediol ester diol Mn =2000, 80.00 parts by weight of polypropylene oxide diol Mn =2000 and 130.00 parts by weight of sulfonate type polyester diol Mn =1500, and vacuumizing at 120 ℃ and 0.09MPa for removing water for 2h; adding 47.04 parts of hexamethylene diisocyanate and 73.36 parts of dicyclohexylmethane diisocyanate, stirring and reacting for 2 hours at 80 ℃; adding 50.00 parts of acetone, 1.00 part of dimethylolpropionic acid, 3.23 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst, keeping the temperature at 60 ℃ for reaction for 5 hours, adding 1.00 part of triethylamine neutralizer for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of a dispersing agent is 1100r/min, and keeping the rotation speed for dispersion; adding 17.03 parts of triethylene tetramine into 150 parts of water, uniformly stirring, slowly adding the triethylene tetramine into the emulsion, and continuously stirring for 30min; keeping stirring the emulsion for 2h under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

8. The polyurethane is characterized by being prepared by the following steps of (1) vacuumizing 86.67 parts of polycaprolactone diol Mn =2000, 86.67 parts of polytetrahydrofuran ether diol Mn =2000 and 120.00 parts of sulfonate polyester diol Mn =1500 at 120 ℃ and 0.09MPa for removing water for 2 hours, wherein the use amounts of the raw materials are calculated by weight parts; adding 47.04 parts of hexamethylene diisocyanate and 62.16 parts of isophorone diisocyanate, stirring and keeping the temperature of 80 ℃ for reaction for 2 hours, adding 50.00 parts of acetone, 1.50 parts of dimethylolpropionic acid, 2.90 parts of butanediol, 6.25 parts of trimethylolpropane and 0.36 part of catalyst, keeping the temperature of 60 ℃ for reaction for 5 hours; adding 1.50 parts of triethylamine neutralizing agent for neutralization, adding 600 parts of water for emulsification after 1min under the condition that the rotation speed of the dispersing agent is 1100r/min, and keeping the rotation speed for dispersion; adding 17.67 parts of tetraethylenepentamine into 150 parts of water, stirring uniformly, slowly adding into the emulsion, and continuously stirring for 30min; keeping stirring the emulsion for 2h under the vacuum condition of 60 ℃ and 0.09MPa, and removing the solvent acetone to obtain the self-extinction aqueous polyurethane emulsion.

9. A paint comprising the polyurethane according to any one of claims 1 to 8.