阅读说明：本技术 一种紫外光固化聚碳酸酯丙烯酸酯及其制备方法 (Ultraviolet light curing polycarbonate acrylate and preparation method thereof ) 是由 曹敏 兰兴仲 于 2019-12-09 设计创作，主要内容包括：本发明公开了一种紫外光固化聚碳酸酯丙烯酸酯及其制备方法,用于生产UV固化涂料的原料。所述聚碳酸酯丙烯酸酯具有式I所示的分子结构,其中,末端丙烯酸酯化率大于99％,且数均分子量为500-8000。由其制备的紫外光固化涂层,具有杰出抗划伤性、耐溶剂性及耐水解特性,在3C、木器、纺织品、金属等表面具有广泛的应用前景<Image he="77" wi="700" file="DDA0002309002220000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention discloses ultraviolet light curing polycarbonate acrylate and a preparation method thereof, which are used as raw materials for producing UV curing coatings. The polycarbonate acrylate has a molecular structure shown in formula I, wherein the terminal acrylation rate is more than 99%, and the number average molecular weight is 500-8000. The ultraviolet curing coating prepared by the ultraviolet curing coating has the characteristics of excellent scratch resistance, solvent resistance and hydrolysis resistance, and has wide application prospect on the surfaces of 3C, woodware, textiles, metal and the like)

1. A preparation method of ultraviolet light curing polycarbonate acrylate is characterized in that: the method comprises the following steps:

1) 50 to 60 parts of diphenyl carbonate, 20 to 30 parts of a diol compound and 0.1 to 0.3 part of tetraethoxytitanate are charged into a four-neck flask equipped with a thermometer and a rectifying column, and the mixture is subjected to distillation in the presence of N₂Under protection, heating the mixture to 180-190 ℃, reacting for 2-3 hours under normal pressure, controlling the temperature of a rectifying column to 170-180 ℃, evaporating a byproduct phenol in time, then reducing the pressure of a reaction system to 60-80 kPa, reducing the reaction temperature to 150-160 ℃, performing reduced pressure polycondensation for 4-6 hours, and reducing the temperature to room temperature to obtain hydroxyl-terminated polycarbonate;

2) adding 80-100 parts of hydroxyl-terminated polycarbonate, 2-8 parts of carboxyl-containing olefin, 0.1-0.2 polymerization inhibitor, 0.2-0.4 catalyst and 2-3 parts of water-carrying agent into a four-neck flask provided with a spherical condensation reflux pipe, a water separator, a thermometer and a stirrer, carrying out esterification reaction at 70-100 ℃, cooling reaction liquid to room temperature after 4-6 h reaction, washing the reaction liquid to be neutral by using a sodium bicarbonate aqueous solution with the mass fraction of 5% and a sodium hydroxide aqueous solution with the mass fraction of 5%, and finally washing the reaction liquid to be neutral by using a sodium chloride aqueous solution with the mass fraction of 15% and distilled water to obtain the polycarbonate acrylate.

2. The method for preparing an ultraviolet light curing polycarbonate acrylate as claimed in claim 1, wherein the method comprises the following steps: the diol compound comprises one or more of 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol.

3. The method for preparing an ultraviolet light curing polycarbonate acrylate as claimed in claim 2, wherein the method comprises the following steps: the carboxyl-containing olefin comprises one or more of acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid and 10-undecylenic acid.

4. The method for preparing an ultraviolet light curing polycarbonate acrylate as claimed in claim 3, wherein the method comprises the following steps: the polymerization inhibitor comprises one or more of sodium bisulfate, hydroquinone monomethyl ether, phenothiazine, copper acetate, copper dibutyldithiocarbamate and tetramethyl piperidine nitroxide radical phosphite triester.

5. The method for preparing an ultraviolet light curing polycarbonate acrylate as claimed in claim 4, wherein the method comprises the following steps: the catalyst comprises one or more of p-toluenesulfonic acid, sulfuric acid, phosphoric acid, boric acid, ferric trichloride, ferric sulfate, ferrous sulfate, zinc chloride, copper sulfate, zirconium sulfate, acetic titanate, acetic zirconate, tetraethoxysilane titanate, tetraisopropyl titanate, tetrapropyl titanate, tetrabutyl titanate, zinc oxide, tin oxide, stannous oxide, antimony trioxide and zinc acetate.

6. The method for preparing an ultraviolet light curing polycarbonate acrylate as claimed in claim 5, wherein the method comprises the following steps: the water-carrying agent is one or more of benzene, toluene, cyclohexane, isoamylol and ethyl acetate.

7. The polycarbonate acrylate prepared by the method for preparing an ultraviolet light curing polycarbonate acrylate as claimed in claim 1.

8. The UV curable polycarbonate acrylate of claim 7, wherein: the polycarbonate acrylate has the chemical formula:

wherein R represents an alkylene group having 3 to 6 carbon atoms,

m and n represent the average degree of polymerization, m is a number of 0 to 15, and n is a number of 1 to 50.

Technical Field

The invention relates to ultraviolet light curing polycarbonate acrylate and a preparation method thereof.

Background

Compared with the traditional coating, the ultraviolet curing coating has the characteristics of 100% solid content, no pollution, high crosslinking degree and the like, and the coating prepared from the ultraviolet curing coating has high toughness, stain resistance, abrasion resistance, chemical resistance and fingerprint resistance, is an ideal environment-friendly coating with high green performance and good development prospect. Currently, resins for ultraviolet curable coatings include urethane acrylates, acrylic acrylates, epoxy acrylates, silicone acrylates, polyester acrylates, and the like.

The polycarbonate diol is a high-performance polyol with regular molecular structure and strong intermolecular cohesion, is usually used for preparing polyurethane resin, and shows excellent heat resistance, weather resistance, water resistance, oil resistance and wear resistance. Currently, polycarbonate diols are mainly used for uv-curable coatings by synthesizing urethane acrylates. Polycarbonate acrylate directly used for UV light-cured coatings is not reported at present.

Patent document 102858844a discloses a method for producing polycarbonate diol diacrylate by catalyzing polycarbonate diol and a vinyl acrylate compound with a hydrolase, wherein the conversion of terminal acrylic acid is 97% or more. The conversion rate of the terminal acrylic acid is low, and when the polymerization is initiated by light, the residual polycarbonate diol is used as a filler, so that the physical and chemical properties of the coating are greatly weakened, and the application of the coating in high-performance UV coating is limited.

Disclosure of Invention

In view of the above, the invention provides an ultraviolet light curing polycarbonate acrylate and a preparation method thereof, wherein a new catalytic system is adopted, and the conversion rate of the terminal acrylic acid of the prepared polycarbonate acrylate is higher than 99%, so that the polycarbonate acrylate can be used for UV coating.

In order to solve the problems in the prior art, the technical scheme of the invention is as follows: a preparation method of ultraviolet light curing polycarbonate acrylate is characterized in that: the method comprises the following steps:

1) 50 to 60 parts of diphenyl carbonate, 20 to 30 parts of a diol compound and 0.1 to 0.3 part of tetraethoxytitanate are charged into a four-neck flask equipped with a thermometer and a rectifying column, and the mixture is subjected to distillation in the presence of N₂Under protection, heating the mixture to 180-190 ℃, reacting for 2-3 hours under normal pressure, controlling the temperature of a rectifying column to 170-180 ℃, evaporating a byproduct phenol in time, then reducing the pressure of a reaction system to 60-80 kPa, reducing the reaction temperature to 150-160 ℃, performing reduced pressure polycondensation for 4-6 hours, and reducing the temperature to room temperature to obtain hydroxyl-terminated polycarbonate;

2) adding 80-100 parts of hydroxyl-terminated polycarbonate, 2-8 parts of carboxyl-containing olefin, 0.1-0.2 polymerization inhibitor, 0.2-0.4 catalyst and 2-3 parts of water-carrying agent into a four-neck flask provided with a spherical condensation reflux pipe, a water separator, a thermometer and a stirrer, carrying out esterification reaction at 70-100 ℃, cooling reaction liquid to room temperature after 4-6 h reaction, washing the reaction liquid to be neutral by using a sodium bicarbonate aqueous solution with the mass fraction of 5% and a sodium hydroxide aqueous solution with the mass fraction of 5%, and finally washing the reaction liquid to be neutral by using a sodium chloride aqueous solution with the mass fraction of 15% and distilled water to obtain the polycarbonate acrylate.

Further, the diol compound includes one or more of 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, and 1, 6-hexanediol.

Further, the carboxyl-containing olefin comprises one or more of acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid and 10-undecenoic acid.

Further, the polymerization inhibitor comprises one or more of sodium bisulfate, hydroquinone monomethyl ether, phenothiazine, copper acetate, copper dibutyldithiocarbamate and tetramethylpiperidine nitroxide radical phosphite triester.

Further, the catalyst comprises one or more of p-toluenesulfonic acid, sulfuric acid, phosphoric acid, boric acid, ferric chloride, ferric sulfate, ferrous sulfate, zinc chloride, copper sulfate, zirconium sulfate, acetic titanate, acetic zirconate, tetraethoxysilane titanate, tetraisopropyl titanate, tetrapropyl titanate, tetrabutyl titanate, zinc oxide, tin oxide, stannous oxide, antimony trioxide and zinc acetate.

Further, the water-carrying agent is one or more of benzene, toluene, cyclohexane, isoamyl alcohol and ethyl acetate.

The polycarbonate acrylate prepared by the preparation method of the ultraviolet light curing polycarbonate acrylate.

Further, the polycarbonate acrylate has the formula:

wherein R represents an alkylene group having 3 to 6 carbon atoms,

m and n represent the average degree of polymerization, m is a number of 0 to 15, and n is a number of 1 to 50.

Compared with the prior art, the invention has the following advantages:

1) the polycarbonate acrylate prepared by adopting the catalytic system has the conversion rate of the terminal acrylate higher than 99 percent, is white solid or transparent viscous liquid at normal temperature, has 100 percent of solid content, and can be used for ultraviolet curing coating;

2) the ultraviolet curing coating prepared from the polycarbonate acrylate has high crystallinity, high hardness of the coating, and better scratch resistance, solvent resistance and adhesion performance than the prior art.

Detailed Description

An ultraviolet light cured polycarbonate acrylate having the formula:

wherein R represents an alkylene group having 3 to 6 carbon atoms,

m and n represent the average degree of polymerization, m is a number of 0 to 15, and n is a number of 1 to 50.

The preparation method of the ultraviolet light curing polycarbonate acrylate comprises the following steps:

1) 50 to 60 parts of diphenyl carbonate, 20 to 30 parts of a diol compound and 0.1 to 0.3 part of tetraethoxytitanate are charged into a four-neck flask equipped with a thermometer and a rectifying column, and the mixture is subjected to distillation in the presence of N₂Under protection, heating the mixture to 180-190 ℃, reacting for 2-3 hours under normal pressure, controlling the temperature of a rectifying column to 170-180 ℃, evaporating a byproduct phenol in time, then reducing the pressure of a reaction system to 60-80 kPa, reducing the reaction temperature to 150-160 ℃, performing reduced pressure polycondensation for 4-6 hours, and reducing the temperature to room temperature to obtain hydroxyl-terminated polycarbonate;

the diol compound comprises 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol or a combination thereof; the carboxyl-containing olefin comprises acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 10-undecenoic acid or the combination of the acrylic acid, the 3-butenoic acid and the 4-pentenoic acid;

2) adding 80-100 parts of hydroxyl-terminated polycarbonate, 2-8 parts of carboxyl-containing olefin, 0.1-0.2 polymerization inhibitor, 0.2-0.4 catalyst and 2-3 parts of water-carrying agent into a four-neck flask provided with a spherical condensation reflux pipe, a water separator, a thermometer and a stirrer, carrying out esterification reaction at 70-100 ℃, cooling reaction liquid to room temperature after 4-6 h reaction, washing the reaction liquid to be neutral by using a sodium bicarbonate aqueous solution with the mass fraction of 5% and a sodium hydroxide aqueous solution with the mass fraction of 5%, and finally washing the reaction liquid to be neutral by using a sodium chloride aqueous solution with the mass fraction of 15% and distilled water to obtain the polycarbonate acrylate.

The polymerization inhibitor comprises one or more of sodium bisulfate, hydroquinone monomethyl ether, phenothiazine, copper acetate, copper dibutyldithiocarbamate and tetramethyl piperidine nitroxide radical phosphite triester;

the catalyst comprises one or more of p-toluenesulfonic acid, sulfuric acid, phosphoric acid, boric acid, ferric chloride, ferric sulfate, ferrous sulfate, zinc chloride, copper sulfate, zirconium sulfate, acetic titanate, acetic zirconate, tetraethoxysilane titanate, tetraisopropyl titanate, tetrapropyl titanate, tetrabutyl titanate, zinc oxide, tin oxide, stannous oxide, antimony trioxide and zinc acetate;

the water-carrying agent is one or more of benzene, toluene, cyclohexane, isoamylol and ethyl acetate.

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.