阅读说明：本技术 一种利用点击化学功能化的聚氨酯及其制备方法 (Polyurethane functionalized by click chemistry and preparation method thereof ) 是由 聂琼芳 叶如兰 秦涛 赵锦 李长兴 杨明华 吴锦京 黄达云 张晓青 于 2021-01-18 设计创作，主要内容包括：本发明公开了一种利用点击化学功能化的聚氨酯及其制备方法,包括以下步骤：将甲苯二异氰酸酯和脱水后的聚醚多元醇,先后加入三口烧瓶中反应得到预聚体；称取适量的亲水性单体二羟甲基丙酸和中间体,与N-甲基吡咯烷酮混合均匀后,缓慢倒入上述三口烧瓶中与预聚体反应,后将扩链剂缓慢加入反应；后加入丙酮降低粘度,加入三乙胺中和；最后在搅拌机内搅拌均匀,缓慢添加去离子水,即得聚氨酯乳液。该反应条件简单、产率高、无毒害副产物、产物稳定易净化。并且本发明所制备的聚氨酯涂料具有抗菌抗静电的功能,不仅可以防止微生物滋生致使聚氨酯材料产生霉变,还可以防止聚氨酯涂料在应用过程中,由于电阻率过大所导致的短路、火灾等问题。(The invention discloses polyurethane functionalized by click chemistry and a preparation method thereof, wherein the preparation method comprises the following steps: sequentially adding toluene diisocyanate and dehydrated polyether polyol into a three-neck flask to react to obtain a prepolymer; weighing a proper amount of hydrophilic monomer dimethylolpropionic acid and an intermediate, uniformly mixing with N-methyl pyrrolidone, slowly pouring into the three-neck flask to react with the prepolymer, and slowly adding the chain extender to react; adding acetone to reduce viscosity, and adding triethylamine to neutralize; and finally, uniformly stirring in a stirrer, and slowly adding deionized water to obtain the polyurethane emulsion. The reaction condition is simple, the yield is high, no toxic and side products are generated, and the product is stable and easy to purify. The polyurethane coating prepared by the invention has the antibacterial and antistatic functions, so that not only can the mildew of a polyurethane material caused by the breeding of microorganisms be prevented, but also the problems of short circuit, fire and the like caused by overlarge resistivity in the application process of the polyurethane coating can be prevented.)

1. A preparation method of polyurethane functionalized by click chemistry is characterized by comprising the following steps:

1) weighing 10-50 parts of toluene diisocyanate and 300 parts of dehydrated polyether polyol 150-150, sequentially adding the two into a three-neck flask provided with a thermometer, a stirrer and a condenser, reacting for 0.5-3h, controlling the temperature at 50-70 ℃, then heating to 80-100 ℃, and continuing to react for 1-3 h to obtain a prepolymer;

2) weighing 3-10 parts of hydrophilic monomer dimethylolpropionic acid and 5-20 parts of intermediate, uniformly mixing the hydrophilic monomer dimethylolpropionic acid and the intermediate with N-methylpyrrolidone, slowly pouring the mixture into the three-neck flask to react with the prepolymer, preserving heat for 2-3h, slowly adding 5-10 parts of chain extender, and reacting for 1-2 h; adding a certain amount of acetone to reduce viscosity, and then adding 1-10 parts of triethylamine to neutralize for 10-30 min; pouring the mixture into a stirrer, stirring uniformly, slowly adding deionized water, and stirring for 10-30min to obtain the polyurethane emulsion.

2. The method of claim 1, wherein: the preparation method of the intermediate comprises the following steps:

1) dissolving 0.01-1g of p-formyl benzene compound in 10-100mL of ethanol under the protection of nitrogen, adding 0.1-1g of benzenesulfonyl hydrazide, stirring for 10-60 min, precipitating with secondary water, and drying to obtain solid phenylhydrazone; dissolving 0.05-1 ml aniline in the prepared mixed solution, and dissolving 0.01-1g NaNO in ice water₂Dissolving the solid, dropwise adding the mixed solution after dissolving, and stirring for 10-30min to obtain a diazobenzene solution; dissolving 0.1-1g phenylhydrazone in 5-20ml pyridine, dropwise adding into the diazobenzene solution, controlling the reaction temperature at-5-5 deg.C with ice water bath, reacting for 4-8 hr, extracting with extractant, collecting upper organic layer, filtering, and vacuum drying to obtain tetrazole micromolecule；

2) Weighing 1-10g of tetrazole micromolecules and 5-20g of methacrylic acid sulfonate, dissolving the tetrazole micromolecules and the methacrylic acid sulfonate in phosphate buffer solution, and irradiating for 1-5 min by using 200-400nm ultraviolet rays under the conditions of pH =7.5 and room temperature to obtain the required intermediate.

3. The method of claim 1, wherein: the chain extender is one of ethylene glycol, propylene glycol or diethylene glycol.

4. The method of claim 1, wherein: in the step 2), the temperature of the polyurethane emulsion is kept between 10 and 30 ℃ in the preparation process.

5. The method of claim 2, wherein: the mixed solution of the tetrazole micromolecules is prepared from 1-5ml of water, 1-5ml of ethanol and 0.1-1ml of concentrated HCl.

6. The method of claim 2, wherein: the p-formyl benzene compound is one of p-formyl phenol, p-formyl aniline or p-formyl benzoic acid.

7. The method of claim 2, wherein: the extractant is ethyl acetate, and the extraction times are 3-5 times, and 5-20ml each time.

8. Polyurethane functionalized with click chemistry, obtained by the preparation process according to any one of claims 1 to 7.

Technical Field

The invention relates to the technical field of high polymer coatings, in particular to polyurethane functionalized by click chemistry and a preparation method thereof.

Background

In recent years, with the enhancement of environmental awareness, people advocate the production of green products, wherein the coating is used as an important matching material of national economy and is widely applied to industries such as buildings, industry, daily necessities, rubber and plastics. Among a plurality of coating materials, the polyurethane material has excellent performances, such as wear resistance, high temperature resistance, low temperature resistance, chemical resistance, oil resistance and the like, so that the polyurethane material is widely applied to various fields, but in the actual application and storage process of the polyurethane material, bacteria are very easy to grow and propagate under the conditions of proper temperature and humidity, the health of human beings is seriously threatened, and meanwhile, medical accidents and huge economic losses are brought. Thus, scientists have been working on the selection of polyurethane antimicrobial agents and antimicrobial processing methods for many years. The traditional antibacterial agents at present mainly comprise two major types of inorganic antibacterial agents and organic antibacterial agents, wherein the inorganic antibacterial agent is mainly Ag⁺、Cu²⁺、Zn²⁺The antibacterial material can be prepared by dispersing the antibacterial material in the material. But the migration of the antibacterial agent can be caused after a long time, which not only causes environmental pollution, but also has antibacterial effectThe effect cannot be sustained. Organic antibacterial agents are mainly small molecules containing acids, esters, alcohols, quaternary ammonium salts and the like, and although the small molecules can achieve good antibacterial effects when added to materials, the organic antibacterial agents have high toxicity and can also migrate, so that the application range is limited to a large extent.

Polyurethane coating is a high molecular material, and monomers are bonded together through chemical bonds, electrons are bound around atoms and cannot move, so that the resistivity of the high molecular material is very high (generally 10)¹³-10¹⁵Ω · cm), static electricity is easily generated by friction during use, and accumulation of static electricity easily causes short circuit and fire, and explosion occurs in a serious case. Therefore, it is necessary to develop a polyurethane coating with antistatic and antibacterial properties.

Disclosure of Invention

In order to solve the problems in the prior art, the invention aims to provide polyurethane functionalized by click chemistry and a preparation method thereof, the polyurethane coating obtained by the preparation method has good antibacterial and antistatic effects, and tetrazole small molecules and SBMA are chemically synthesized by light click, so that the polyurethane coating is modified, the performance of the polyurethane coating is improved, and meanwhile, the synthesis process is simpler.

In order to achieve the purpose, the invention adopts the following technical scheme:

a method for preparing polyurethane functionalized by click chemistry comprises the following steps:

1) weighing 10-50 parts of toluene diisocyanate and 300 parts of dehydrated polyether polyol 150-150, sequentially adding the two into a three-neck flask provided with a thermometer, a stirrer and a condenser, reacting for 0.5-3h, controlling the temperature at 50-70 ℃, and continuing to react for 1-3 h when the temperature is raised to 50-100 ℃ to obtain a prepolymer;

2) weighing 3-10 parts of hydrophilic monomer dimethylolpropionic acid and 5-20 parts of intermediate, uniformly mixing the hydrophilic monomer dimethylolpropionic acid and the intermediate with N-methylpyrrolidone, slowly pouring the mixture into the three-neck flask to react with the prepolymer, preserving heat for 2-3h, slowly adding 5-10 parts of chain extender, and reacting for 1-2 h; adding a certain amount of acetone to reduce viscosity, and then adding 1-10 parts of triethylamine to neutralize for 10-30 min; pouring the mixture into a stirrer, stirring uniformly, slowly adding deionized water, and stirring for 10-30min to obtain the polyurethane emulsion.

Preferably, the preparation method of the intermediate comprises the following steps:

1) dissolving 0.01-1g of p-formyl benzene compound in 10-100mL of ethanol under the protection of nitrogen, adding 0.1-1g of benzenesulfonyl hydrazide, stirring for 10-60 min, precipitating with secondary water, and drying to obtain solid phenylhydrazone; dissolving 0.05-1 ml aniline in the prepared mixed solution, and dissolving 0.01-1g NaNO in ice water₂Dissolving the solid, dropwise adding the mixed solution after dissolving, and stirring for 10-30min to obtain a diazobenzene solution; dissolving 0.1-1g of phenylhydrazone in 5-20ml of pyridine, dropwise adding the solution into the diazobenzene solution, controlling the reaction temperature to be-5-5 ℃ by using an ice water bath, reacting for 4-8 h, then extracting by using an extractant, taking an upper organic layer, filtering, and drying in vacuum to obtain tetrazole micromolecules;

2) weighing 1-10g of tetrazole micromolecules and 5-20g of methacrylic acid sulfonate, dissolving the tetrazole micromolecules and the methacrylic acid sulfonate in phosphate buffer solution, and irradiating for 1-5 min by using 200-400nm ultraviolet rays under the conditions of pH =7.5 and room temperature to obtain the required intermediate.

Preferably, the chain extender is one of ethylene glycol, propylene glycol or diethylene glycol.

Preferably, the polyurethane emulsion in step 2) is kept at a temperature of 10-30 ℃ during the preparation.

Preferably, the mixed solution of the tetrazole small molecules is prepared by 1-5ml of water, 1-5ml of ethanol and 0.1-1ml of concentrated HCl.

Preferably, the p-formylbenzene compound is one of p-formylphenol, p-formylaniline or p-formylbenzoic acid.

Preferably, the extractant is ethyl acetate, and the extraction times are 3-5 times, and 5-20ml each time.

A polyurethane functionalized by click chemistry prepared according to the above preparation method.

Compared with the prior art, the invention has the beneficial effects that:

1. the polyurethane coating prepared by the invention has an antibacterial effect, and the methacrylate sulfonate added in the preparation process is easily adsorbed on the surface of bacteria with negative charges to interfere the metabolism of the bacteria, so that the antibacterial effect is achieved;

2. in the process of preparing the polyurethane coating, methacrylic acid Sulfonate (SBMA) is added, the SBMA simultaneously has positive charges and negative charges and has hydrophilic performance, a water film layer with a moisture absorption effect can be formed on the surface of a polymer, so that the polymer has an antistatic effect, and meanwhile, hydrogen bonds can be formed between water molecules and oxygen atoms with stronger electronegativity on the SBMA under a certain condition to form a bound water state, so that the antistatic lasting effect is achieved;

3. the intermediate prepared by the invention is synthesized by the light click chemical reaction between tetrazole micromolecules and methacrylate sulfonate, tetrazole can generate active 1, 3-dipole and rapidly react with olefin, and the reaction condition is simple, the yield is high, toxic and side products are not generated, and the product is stable and easy to purify.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The preparation method of polyurethane functionalized by click chemistry comprises the following steps:

firstly, preparing an intermediate:

1) dissolving 0.05g of p-formylphenol in 10mL of ethanol under the protection of nitrogen, adding 0.1g of benzenesulfonyl hydrazide, stirring for 10min, precipitating with secondary water, and drying to obtain solid phenylhydrazone; preparing a mixed solution by using 1ml of water, 2ml of ethanol and 0.1ml of concentrated HCl; dissolving aniline 0.05 ml in the prepared mixed solution, and adding 0.02g NaNO under ice water condition₂Dissolution of the solidAfter dissolving, dropwise adding the mixed solution, and stirring for 10min to obtain a diazobenzene solution; 0.1g of phenylhydrazone is dissolved in 5ml of pyridine, the solution is dropwise added into the diazobenzene solution, the reaction temperature is controlled at minus 3 ℃ by using ice water bath, extraction is carried out by using an extractant after 4 hours of reaction, the extractant is ethyl acetate, and the extraction frequency is 3 times, and 10ml of the extractant is used each time. Taking the upper organic layer, filtering and vacuum drying to obtain tetrazole micromolecules;

2) weighing 3g of tetrazole micromolecules and 5g of methacrylate sulfonate, dissolving the tetrazole micromolecules and the methacrylate sulfonate in a phosphate buffer solution, and irradiating for 1 min by using 200nm ultraviolet rays under the conditions of pH =7.5 and room temperature to obtain the required intermediate.

Preparation of polyurethane emulsion

1) Weighing 10 parts of toluene diisocyanate and 150 parts of dehydrated polyether polyol, sequentially adding the toluene diisocyanate and the dehydrated polyether polyol into a three-neck flask provided with a thermometer, a stirrer and a condenser, reacting for 0.5h, controlling the temperature at 50 ℃, heating to 80 ℃, and continuing to react for 1 h to obtain a prepolymer;

2) weighing 3 parts of hydrophilic monomer dimethylolpropionic acid and 5 parts of intermediate, uniformly mixing the two with N-methylpyrrolidone, slowly pouring the mixture into the three-neck flask to react with the prepolymer, keeping the temperature for 2 hours at 10 ℃, slowly adding 5 parts of glycol, and reacting for 1 hour; adding a certain amount of acetone to reduce the viscosity, and then adding 1 part of triethylamine to neutralize for 10 min; pouring the mixture into a stirrer, stirring uniformly, slowly adding deionized water, and stirring for 10min to obtain the polyurethane emulsion.

Example 2

The preparation method of polyurethane functionalized by click chemistry comprises the following steps:

firstly, preparing an intermediate:

1) dissolving 0.5g of p-formanilide in 50mL of ethanol under the protection of nitrogen, adding 0.5g of benzenesulfonyl hydrazide, stirring for 30min, precipitating with secondary water, and drying to obtain solid phenylhydrazone; preparing a mixed solution by using 3ml of water, 3ml of ethanol and 0.5ml of concentrated HCl; dissolving 0.5ml aniline in the mixed solution, and adding 0.5g NaNO in ice water₂Dissolving the solid, adding the mixed solution dropwise after dissolving, stirring for 20min,obtaining a diazobenzene solution; 0.5g of phenylhydrazone is dissolved in 10ml of pyridine, the solution is dropwise added into the diazobenzene solution, the reaction temperature is controlled at 0 ℃ by using an ice water bath, an extractant is used for extraction after 6 hours of reaction, the extractant is ethyl acetate, and the extraction times are 4 times, and 15ml of the extractant is used each time. Taking the upper organic layer, filtering and vacuum drying to obtain tetrazole micromolecules;

2) weighing 7g of tetrazole micromolecules and 13g of methacrylate sulfonate, dissolving the tetrazole micromolecules and the methacrylate sulfonate in a phosphate buffer solution, and irradiating for 4 min by using 300nm ultraviolet rays under the conditions of pH =7.5 and room temperature to obtain the required intermediate.

Preparation of polyurethane emulsion

1) Weighing 30 parts of toluene diisocyanate and 220 parts of dehydrated polyether polyol, sequentially adding the toluene diisocyanate and the dehydrated polyether polyol into a three-neck flask provided with a thermometer, a stirrer and a condenser, reacting for 2 hours, controlling the temperature at 60 ℃, and continuing to react for 2 hours when the temperature is raised to 70 ℃ to obtain a prepolymer;

2) weighing 7 parts of hydrophilic monomer dimethylolpropionic acid and 11 parts of intermediate, uniformly mixing the two with N-methylpyrrolidone, slowly pouring the mixture into the three-neck flask to react with the prepolymer, keeping the temperature for 3 hours at 20 ℃, slowly adding 7 parts of propylene glycol, and reacting for 2 hours; adding a certain amount of acetone to reduce the viscosity, and then adding 7 parts of triethylamine to neutralize for 20 min; pouring the mixture into a stirrer, stirring uniformly, slowly adding deionized water, and stirring for 20min to obtain the polyurethane emulsion.

Example 3

The preparation method of polyurethane functionalized by click chemistry comprises the following steps:

firstly, preparing an intermediate:

1) dissolving 1g of p-formylbenzoic acid in 100mL of ethanol under the protection of nitrogen, adding 1g of benzenesulfonyl hydrazide, stirring for 60 min, precipitating with secondary water, and drying to obtain solid phenylhydrazone; preparing a mixed solution by using 5ml of water, 5ml of ethanol and 1ml of concentrated HCl; dissolving aniline 1ml in the mixed solution, and dissolving 1g NaNO in ice water₂Dissolving the solid, dropwise adding the mixed solution after dissolving, and stirring for 30min to obtain a diazobenzene solution; 1g of phenylhydrazone was dissolved in 20ml of pyridine and the solution was added dropwiseDropwise adding into the diazobenzene solution, controlling the reaction temperature at 5 ℃ by using an ice water bath, reacting for 8 h, and extracting by using an extracting agent, wherein the extracting agent is ethyl acetate, and the extraction times are 5 times and 20ml each time. Taking the upper organic layer, filtering and vacuum drying to obtain tetrazole micromolecules;

2) weighing 10g of tetrazole micromolecules and 20g of methacrylate sulfonate, dissolving the tetrazole micromolecules and the methacrylate sulfonate in a phosphate buffer solution, and irradiating for 5 min by using 400nm ultraviolet rays under the conditions of pH =7.5 and room temperature to obtain the required intermediate.

Preparation of polyurethane emulsion

1) Weighing 50 parts of toluene diisocyanate and 300 parts of dehydrated polyether polyol, sequentially adding the toluene diisocyanate and the dehydrated polyether polyol into a three-neck flask provided with a thermometer, a stirrer and a condenser, reacting for 3 hours, controlling the temperature at 70 ℃, and continuing to react for 3 hours when the temperature is raised to 100 ℃ to obtain a prepolymer;

2) weighing 10 parts of hydrophilic monomer dimethylolpropionic acid and 20 parts of intermediate, uniformly mixing the two with N-methylpyrrolidone, slowly pouring the mixture into the three-neck flask to react with the prepolymer, keeping the temperature for 3 hours at 30 ℃, slowly adding 5-10 parts of diethylene glycol, and reacting for 2 hours; adding a certain amount of acetone to reduce the viscosity, and then adding 10 parts of triethylamine to neutralize for 30 min; pouring the mixture into a stirrer, stirring uniformly, slowly adding deionized water, and stirring for 30min to obtain the polyurethane emulsion.

Comparative example

The preparation method of polyurethane functionalized by click chemistry comprises the following steps:

1) weighing 30 parts of toluene diisocyanate and 200 parts of dehydrated polyether polyol, sequentially adding the toluene diisocyanate and the dehydrated polyether polyol into a three-neck flask provided with a thermometer, a stirrer and a condenser, reacting for 2 hours, controlling the temperature at 60 ℃, and then heating to 70 ℃, and continuing to react for 2 hours to obtain a prepolymer;

2) weighing 7 parts of hydrophilic monomer dimethylolpropionic acid and 12 parts of intermediate, uniformly mixing the two with N-methylpyrrolidone, slowly pouring the mixture into the three-neck flask to react with the prepolymer, keeping the temperature for 3 hours, slowly adding 10 parts of diethylene glycol, and reacting for 2 hours; adding a certain amount of acetone to reduce the viscosity, and then adding 7 parts of triethylamine to neutralize for 20 min; pouring the mixture into a stirrer, stirring uniformly, slowly adding deionized water, and stirring for 20min to obtain the polyurethane emulsion.

The polyurethane emulsions obtained in examples 1, 2, 3 and comparative examples were subjected to the performance test, and the data are as follows:

(1) test of antibacterial Property

TABLE 1 antibacterial Property test results

	Example 1	Example 2	Example 3	Comparative example
					Antibacterial ratio (%)	99.1%	99.5%	99.8%	0%

(2) Antistatic test

And measuring the surface resistivity and the volume resistivity of the material according to GB/T-1410-2006, and representing the antistatic property of the polyurethane.

TABLE 2 antistatic test results for polyurethanes

	Example 1	Example 2	Example 3	Comparative example
					Surface resistivity/omega	2.1×107	1.8×107	1.6×107	5.3×1014
Volume resistivity/omega.cm	1.7×106	1.5×106	1.3×106	1.4×1013

From the above table, it can be seen that the surface resistivity and the volume resistivity of the modified polyurethane show a decreasing trend compared with those of the comparative examples, and the modified polyurethane has a better antistatic function.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.