阅读说明：本技术 一种松香基荧光聚氨酯的制备方法 (Preparation method of rosin-based fluorescent polyurethane ) 是由 余彩莉 严成飞 张发爱 刘浩 于 2021-07-17 设计创作，主要内容包括：本发明公开了一种松香基荧光聚氨酯的制备方法。以异佛尔酮二异氰酸酯(IPDI)、松香基多元醇(RAG)、聚己内酯二醇(PCL-1000)为反应单体,1,5-二羟基萘(1,5-DN)及1,4丁二醇(BDO)为扩链剂,制备了松香基荧光聚氨酯(FPU)。本发明以松香改性制备的多元醇等为原料,将有机荧光小分子键合到聚氨酯主链上得到松香基荧光聚氨酯,将松香和荧光聚氨酯的优势结合起来,并为合理开发利用松香资源提供了新的应用途径,拓宽了松香的应用范围,制备的荧光聚氨酯,其优异的光泽度、铅笔硬度、柔韧性、附着力、耐冲击强度等性能,可应用于荧光涂料、荧光检测等领域。(The invention discloses a preparation method of rosin-based fluorescent polyurethane. Isophorone diisocyanate (IPDI), rosin-based polyol (RAG) and polycaprolactone diol (PCL-1000) are used as reaction monomers, 1, 5-dihydroxynaphthalene (1,5-DN) and 1, 4-Butanediol (BDO) are used as chain extenders, and rosin-based Fluorescent Polyurethane (FPU) is prepared. According to the invention, polyol and the like prepared by modifying rosin are used as raw materials, organic fluorescent micromolecules are bonded to a polyurethane main chain to obtain rosin-based fluorescent polyurethane, the advantages of the rosin and the fluorescent polyurethane are combined, a new application approach is provided for reasonably developing and utilizing rosin resources, the application range of the rosin is widened, and the prepared fluorescent polyurethane has excellent performances of glossiness, pencil hardness, flexibility, adhesive force, impact strength and the like, and can be applied to the fields of fluorescent paint, fluorescent detection and the like.)

1. A preparation method of rosin-based fluorescent polyurethane is characterized by comprising the following specific steps:

2.00-4.00 parts by mass of rosin-based polyol namely RAG, 0.02-0.04 part by mass of chemically pure dibutyltin dilaurate and 10.00-20.00 parts by mass of analytically pure toluene are added into a 100mL three-neck flask provided with a stirring rod and a condenser pipe, and the set rotating speed is 400 r.min^-1In N at₂Heating to 55 ℃ under protection, adding 1.50-2.40 parts by mass of isophorone diisocyanate (IPDI) with the mass percentage concentration of 99% to react until the-NCO content is reduced to a theoretical value, adding 0.64-1.64 parts by mass of analytically pure polycaprolactone diol (PCL-1000), heating to 80 ℃ when the-NCO content is reduced to the theoretical value, adding 0.06-0.42 part by mass of 1, 5-dihydroxynaphthalene (1,5-DN) with the mass percentage concentration of 98% and 0.02-0.22 part by mass of analytically pure 1, 4-Butanediol (BDO), finishing the reaction when the-NCO content is reduced to 0, obtaining the rosin-based fluorescent polyurethane, and measuring the mass percentage of solid to be 30%;

the preparation method of the rosin-based polyol namely RAG comprises the following steps:

(1) adding 100.0 parts by mass of rosin into a stirring rod, a reflux condenser tube, a thermometer and a nitrogen protection deviceIn the reaction kettle, heating and melting the mixture at 400 r.min^-1Stirring, heating to 230 ℃, slowly dropwise adding 28.60 parts by mass of chemically pure acrylic acid for 1 hour, continuously reacting at 230 ℃ for 2 hours after dropwise adding, and discharging when the temperature is reduced to 200 ℃ to obtain an acrylic rosin adduct namely RA;

(2) 50.00 parts by mass of the acrylic rosin adduct obtained in the step (1), 88.76 parts by mass of analytically pure toluene and 0.30 part by mass of analytically pure 1, 4-hydroquinone are added into a 250mL three-neck flask provided with a stirring rod, a reflux condenser tube, a thermometer and a nitrogen protection device, and the set rotating speed is 400 r.min^-1Heating to 120 ℃, adding 37.96 parts by mass of 97% glycidyl methacrylate and 0.50 part by mass of analytically pure triethylamine, reacting for 5 hours, and measuring the acid value to be 3.50mgKOH/g to obtain a toluene solution of rosin-based polyol namely RAG, wherein the measured solid mass percentage is 50%.

Technical Field

The invention relates to a preparation method of rosin-based fluorescent polyurethane.

Background

With the development of society and the improvement of living standard of people, people have higher and higher requirements on material performance, a single-performance material is difficult to meet the requirements, and a composite material with functionality becomes a hot spot of research of people. The fluorescent polyurethane is used as a functional composite material, has the advantages of both fluorescence and polyurethane, and is widely applied to the aspects of coating, fluorescence detection and the like. The traditional small molecular fluorescent compound has the problems of poor water solubility, toxic and side effects, easy migration on the surface of a substrate, easy accumulation in the environment and the like, and is limited in use. In recent years, fluorescent polyurethane obtained by introducing functional small-molecule fluorescent compounds into polyurethane molecular chains has received more and more attention and research. The synthesis method of fluorescent polyurethane is divided into a physical synthesis method and a chemical synthesis method, wherein the physical synthesis method is formed by directly mixing a small molecular fluorescent compound and polyurethane, and the physical synthesis method has fatal defects of poor thermal stability, weak mechanical property and low fluorescence intensity. The chemical synthesis method is an important method for solving the problems that a fluorescent compound is linked to a polyurethane molecular chain in a chemical bonding mode, and the fluorescent compound is insoluble in water or the fluorescence is quenched due to overlarge concentration. The fluorescent polyurethane as a coating can be used as an external wall coating, an internal wall coating, a safety mark and the like; as a detection means, the fluorescent polyurethane has the advantages of good selectivity, accurate measurement result and the like, so that the fluorescent polyurethane has great research value and development prospect.

Rosin is the most common one of natural products, has the obvious advantages of abundant resources, simple exploitation, no toxicity and no harm, and unsaturated double bonds and carboxyl groups in the molecular structure of the rosin are utilized to prepare polyol containing a rosin characteristic structure through chemical modification, and the polyol is used for partially or completely replacing petroleum-based polyol raw materials to prepare novel rosin-based polyurethane materials, so that the physical and chemical properties of the polyurethane materials are improved while the consumption of petroleum resources is reduced and the environment is protected.

Disclosure of Invention

The invention aims to provide a preparation method of rosin-based fluorescent polyurethane, which takes rosin as a raw material, obtains rosin-based dihydric alcohol (RAG) through modification, and reacts with diisocyanate in the presence of a fluorescent agent to obtain the rosin-based fluorescent polyurethane.

The method comprises the following specific steps:

in a 100mL three-neck flask equipped with a stirring rod and a condenserAdding 2.00-4.00 parts by mass of rosin-based polyol (RAG), 0.02-0.04 part by mass of chemically pure dibutyltin dilaurate and 10.00-20.00 parts by mass of analytically pure toluene, and setting the rotating speed to 400 r.min^-1In N at₂Heating to 55 ℃ under protection, adding 1.50-2.40 parts by mass of isophorone diisocyanate (IPDI) with the mass percentage concentration of 99% to react until the-NCO content is reduced to the theoretical value, adding 0.64-1.64 parts by mass of analytically pure polycaprolactone diol (PCL-1000), heating to 80 ℃ when the-NCO content is reduced to the theoretical value, adding 0.06-0.42 part by mass of 98% 1, 5-dihydroxynaphthalene (1,5-DN) and 0.02-0.22 part by mass of analytically pure 1, 4-Butanediol (BDO), finishing the reaction when the-NCO content is reduced to 0, obtaining the rosin-based fluorescent polyurethane, and measuring the solid mass percentage to be 30%.

The preparation method of the rosin-based polyol (RAG) comprises the following steps:

(1) adding 100.0 parts by mass of rosin into a reaction kettle provided with a stirring rod, a reflux condenser tube, a thermometer and a nitrogen protection device, heating and melting the rosin, and then heating and melting the rosin at 400 r.min^-1Stirring, heating to 230 ℃, then slowly dripping 28.60 parts by mass of chemically pure acrylic acid for 1 hour, continuously reacting for 2 hours at 230 ℃ after dripping is finished, and discharging when the temperature is reduced to 200 ℃ to obtain an acrylic Rosin Adduct (RA).

(2) 50.00 parts by mass of RA, 88.76 parts by mass of analytically pure toluene and 0.30 part by mass of analytically pure 1, 4-hydroquinone are added into a 250mL three-neck flask provided with a stirring rod, a reflux condenser tube, a thermometer and a nitrogen protection device, and the set rotating speed is 400 r.min^-1Heating to 120 ℃, adding 37.96 parts by mass of 97% glycidyl methacrylate and 0.50 part by mass of analytically pure triethylamine, reacting for 5 hours, and measuring the acid value to be 3.50mgKOH/g to obtain a toluene solution of rosin-based polyol (RAG), wherein the measured solid mass percentage is 50%.

According to the invention, polyol and the like prepared by modifying rosin are used as raw materials, organic fluorescent micromolecules are bonded to a polyurethane main chain to obtain rosin-based fluorescent polyurethane, the advantages of the rosin and the fluorescent polyurethane are combined, a new application approach is provided for reasonably developing and utilizing rosin resources, the application range of the rosin is widened, and the prepared fluorescent polyurethane has excellent performances of glossiness, pencil hardness, flexibility, adhesive force, impact strength and the like, and can be applied to the fields of fluorescent paint, fluorescent detection and the like.

Detailed Description

The preparation method of the rosin-based polyol (RAG) comprises the following steps:

(1) adding 100.0 parts by mass of rosin into a reaction kettle provided with a stirring rod, a reflux condenser tube, a thermometer and a nitrogen protection device, heating and melting the rosin, and then heating and melting the rosin at 400 r.min^-1Stirring, heating to 230 ℃, then slowly dripping 28.60 parts by mass of chemically pure acrylic acid for 1 hour, continuously reacting for 2 hours at 230 ℃ after dripping is finished, and discharging when the temperature is reduced to 200 ℃ to obtain an acrylic Rosin Adduct (RA).

(2) 50.00 parts by mass of RA, 88.76 parts by mass of analytically pure toluene and 0.30 part by mass of analytically pure 1, 4-hydroquinone are added into a 250mL three-neck flask provided with a stirring rod, a reflux condenser tube, a thermometer and a nitrogen protection device, and the set rotating speed is 400 r.min^-1Heating to 120 ℃, adding 37.96 parts by mass of 97% glycidyl methacrylate and 0.50 part by mass of analytically pure triethylamine, reacting for 5 hours, and measuring the acid value to be 3.50mgKOH/g to obtain a toluene solution of rosin-based polyol (RAG), wherein the measured solid mass percentage is 50%.

Example 1:

3.00 parts by mass of rosin-based polyol (RAG), 0.03 part by mass of chemically pure dibutyltin dilaurate and 14.81 parts by mass of analytically pure toluene were placed in a 100mL three-necked flask equipped with a stirring rod and a condenser at a set rotation speed of 400 r.min^-1In N at₂Heating to 55 ℃ under protection, adding 1.90 parts by mass of isophorone diisocyanate (IPDI) with the mass percent concentration of 99% to react until the-NCO content is reduced to the theoretical value, adding 1.14 parts by mass of analytically pure polycaprolactone diol (PCL-1000), heating to 80 ℃ when the-NCO content is reduced to the theoretical value, adding 0.06 part by mass of 98% 1, 5-dihydroxynaphthalene (1,5-DN) and 0.22 part by mass of analytically pure 1, 4-Butanediol (BDO), and when the-NCO content is reduced to 0And (5) finishing the reaction to obtain the rosin-based IPDI type fluorescent polyurethane, wherein the measured solid mass percentage is 30%. Uniformly coating the rosin-based IPDI type fluorescent polyurethane on a glass plate and a tin plate, drying for 48 hours at 25 ℃ to obtain a paint film with the thickness of 15.0um, and measuring that the glossiness of the paint film is 170.6, the pencil hardness is 2H, the flexibility is 1mm, the adhesive force is 1 grade, and the impact strength reaches 50Kg & cm. The fluorescence intensity of the paint film is 2139a.u measured under the test conditions that the excitation wavelength is 365nm, the emission wavelength is 443nm and the slit of a monochromator is 2.5 nm.

Example 2:

3.00 parts by mass of a rosin-based polyol (RAG), 0.03 part by mass of chemically pure dibutyltin dilaurate and 14.94 parts by mass of analytically pure toluene were placed in a 100mL three-necked flask equipped with a stirring rod and a condenser at a set rotation speed of 400 r.min^-1In N at₂Heating to 55 ℃ under protection, adding 1.90 parts by mass of isophorone diisocyanate (IPDI) with the mass percent concentration of 99% to react until the-NCO content is reduced to a theoretical value, adding 1.14 parts by mass of analytically pure polycaprolactone diol (PCL-1000), heating to 80 ℃ when the-NCO content is reduced to the theoretical value, adding 0.18 part by mass of 98% 1, 5-dihydroxynaphthalene (1,5-DN) and 0.15 part by mass of analytically pure 1, 4-Butanediol (BDO), finishing the reaction when the-NCO content is reduced to 0, obtaining rosin-based IPDI type fluorescent polyurethane, and measuring the solid mass percent to be 30%. Uniformly coating the rosin-based IPDI type fluorescent polyurethane on a glass plate and a tin plate, drying for 48 hours at 25 ℃ to obtain a paint film with the thickness of 15.0um, and measuring that the glossiness of the paint film is 167.1, the pencil hardness is 3H, the flexibility is 1mm, the adhesive force is 1 grade, and the impact strength reaches 50Kg & cm. The fluorescence intensity of the paint film is 2624a.u measured under the test conditions of 365nm excitation wavelength, 443nm emission wavelength and 2.5nm monochromator slit.

Example 3:

3.00 parts by mass of rosin-based polyol (RAG), 0.03 part by mass of chemically pure dibutyltin dilaurate and 15.06 parts by mass of analytically pure toluene were placed in a 100mL three-necked flask equipped with a stirring rod and a condenser at a set rotation speed of 400 r.min^-1In N at₂Heating to 55 ℃ under protection, and adding 1.90 parts by massReacting isophorone diisocyanate (IPDI) with the mass percent concentration of 99% until the-NCO content is reduced to a theoretical value, adding 1.14 parts by mass of analytically pure polycaprolactone diol (PCL-1000), heating to 80 ℃ when the-NCO content is reduced to the theoretical value, adding 0.30 part by mass of 98% 1, 5-dihydroxynaphthalene (1,5-DN) and 0.09 part by mass of analytically pure 1, 4-Butanediol (BDO), finishing the reaction when the-NCO content is reduced to 0, obtaining the rosin-based IPDI type fluorescent polyurethane, and measuring the solid mass percent to be 30%. Uniformly coating the rosin-based IPDI type fluorescent polyurethane on a glass plate and a tin plate, drying for 48 hours at 25 ℃ to obtain a paint film with the thickness of 15.0um, measuring the glossiness of the paint film to be 161.0, the pencil hardness to be 3H, the flexibility to be 1mm, the adhesive force to be 1 grade, and the impact strength to be 50Kg & cm. The fluorescence intensity of the paint film is 2155a.u measured under the test conditions that the excitation wavelength is 365nm, the emission wavelength is 443nm and the slit of a monochromator is 2.5 nm.