阅读说明：本技术 一种可光聚合单组分硫杂蒽酮类光引发剂 (Photopolymerisable single-component thioxanthone photoinitiator ) 是由 管和平 于 2021-08-12 设计创作，主要内容包括：本发明属于光固化材料领域。本发明涉及一种可光聚合单组分硫杂蒽酮类光引发剂,以羟基硫杂蒽酮、溴乙醇、含氟酸酐、4-羟甲基-1,3-二氧-2-硫酮、环氧氯丙烷以及丙烯酰氯作为原料,经过偶联、酯化、环氧开环、环氧化等多步骤反应得到了一种可光聚合单组分硫杂蒽酮类光引发剂材料。该新型光引发剂不仅有效解决现有技术中双组分光引发剂引发效率低且需要添加助引发剂而导致黄变等问题,同时还可具有难迁移、应用广泛、环保等优势,该新型材料尤其适用3C产品、3D打印等领域。(The invention belongs to the field of light-cured materials. The invention relates to a photopolymerisable single-component thioxanthone photoinitiator, which is prepared from hydroxythioxanthone, bromoethanol, fluorine-containing anhydride, 4-hydroxymethyl-1, 3-dioxo-2-thione, epichlorohydrin and acryloyl chloride through multi-step reactions such as coupling, esterification, epoxy ring opening, epoxidation and the like. The novel photoinitiator not only effectively solves the problems that in the prior art, a double-component photoinitiator has low initiation efficiency and needs to be added with an auxiliary initiator to cause yellowing and the like, but also has the advantages of difficult migration, wide application, environmental protection and the like, and the novel material is particularly suitable for the fields of 3C products, 3D printing and the like.)

1. A photopolymerisable single-component thioxanthone photoinitiator is characterized in that the structural formula is as follows:

wherein-R-is-CF₂-or-C₂F₄-。

2. A preparation method of a photopolymerisable single-component thioxanthone photoinitiator is characterized by comprising the following steps: comprises the following steps:

(1) adding 1mol of hydroxy thioxanthone, 1-1.2mol of bromoethanol and 1-1.2mol of potassium carbonate into 50mol of DMF, heating to 110-; slowly adding 60mol of water, stirring for 30min, adding 50mol of DMSO, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product I;

(2) adding 1mol of I, 1.1-1.4mol of fluorine-containing acid anhydride and 0.5-4 wt% of catalyst into 50mol of DMSO, introducing nitrogen, heating to 80-110 ℃, stirring for 3-15h, cooling, and standing to obtain an intermediate product II;

the dosage of the catalyst is the percentage of the total mass of I and the fluorine-containing acid anhydride;

(3) adding 1mol of 4-hydroxymethyl-1, 3-dioxo-2-thione to a solution containing 0.5-3 wt.% of BF₃Heating to 40-80 ℃ in 1-1.2mol of epichlorohydrin of ether, and reacting for 2-8 h; standing, and distilling at 40 ℃ under reduced pressure to obtain an intermediate product III;

the BF₃The amount of the ether is 0.5 to 3 weight percent of the mass of the epichlorohydrin;

(4) adding 1-1.2mol of sodium hydroxide into 1mol of III, stirring for 0.5-5h at 40-80 ℃, and washing for 3 times by using deionized water to obtain an epoxidation product; taking 1 weight part of epoxidation product, adding 1-5 weight parts of 0.5-10% sodium hydroxide aqueous solution, and stirring at 30-90 ℃ for 0.5-10h to obtain an intermediate product IV;

(5) dripping 1-1.1mol of II into 30mol of DMSO containing 1mol of IV, introducing nitrogen, heating to 170-; slowly adding deionized water at 90 ℃, stirring for 10min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product V;

(6) adding 1mol of V and 1.1-1.5mol of triethylamine into 50mol of DMSO, carrying out ice-water bath, stirring, slowly dripping 1.1-1.5mol of acryloyl chloride into the solution, and stirring for 6-12 h; washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated salt solution, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and vacuum drying to obtain the photopolymerisable single-component thioxanthone photoinitiator, namely the target product VI.

3. The method of claim 2 for preparing a photopolymerizable mono-component thioxanthone photoinitiator, wherein the photoinitiator comprises: the fluorine-containing acid anhydride is tetrafluorosuccinic anhydride or perfluoroglutaric anhydride.

4. The method of claim 2 for preparing a photopolymerizable mono-component thioxanthone photoinitiator, wherein the photoinitiator comprises: the catalyst is tetrabutyl titanate, p-toluenesulfonic acid, palygorskite solid acid or sodium aluminate.

5. A photocuring coating is prepared from the following raw materials in parts by weight: 65-69 parts of acrylate resin, 10 parts of TMPTA, 8 parts of TPGDA, 12 parts of butyl acrylate and 1-5 parts of target product VI.

6. A photocurable coating according to claim 5, prepared by a process comprising: mixing the raw materials according to the parts by weight, coating the mixture on PET containing a base coat, and irradiating the mixture for 30-180s under UV light to obtain a coating with the thickness of 2 mu m of a dry film.

Technical Field

The invention relates to a photopolymerisable single-component thioxanthone photoinitiator. The invention belongs to the field of light-cured materials.

Background

Photocuring (photopolymerization) refers to a process in which a photoinitiator is excited and finally converted into active species such as radicals having photoinitiating activity under irradiation of light, thereby initiating crosslinking polymerization of the active species. The photocureable coating is developed for the first time from Germany Bayer company, and the photocureable technology realizes industrialization and is rapidly developed and applied. Compared with thermal curing, the light curing technology has the following characteristics: the preparation method has the advantages of no solvent, high curing speed, energy conservation, environmental protection, good product performance, suitability for high-speed automatic production lines, and wide application in the fields of coating, paint, printing ink, electronic communication, adhesives, dental curing, 3D printing and the like.

The light-cured material mainly comprises functionalized oligomer, monomer, photoinitiator and the like. The photoinitiator is an important component of the photocuring system, and the proportion of the photoinitiator is small but plays a role in determining the photocuring speed. The photoinitiator generates active species with the capability of initiating polymerization after absorbing light energy, thereby initiating active species crosslinking polymerization. At present, the photoinitiator has more actual types and is mainly divided into free radicals and cationic types. Among them, the radical type has a strong application range and can be mainly classified into a hydrogen abstraction type and a cleavage type. Wherein, the cracking type photoinitiator has the problem of oxygen inhibition in the using process; the hydrogen abstraction photoinitiator needs to be used in conjunction with a co-initiator, with tertiary amines being the most commonly used co-initiators.

At present, the hydrogen abstraction type photoinitiator belongs to a micromolecular photoinitiator, and has the defects of high viscosity, easy yellowing, easy migration, easy volatilization, low initiation efficiency, odor and the like. In order to solve the above problems, CN105693888B discloses a polymerizable thioxanthone visible light initiator containing acrylate or methacrylate and a preparation method thereof, which has the advantages of good compatibility with a photocuring system, no need of adding any solvent or auxiliary agent during use, high initiation efficiency, environmental friendliness, low energy consumption and the like, but does not solve the yellowing problem by using tertiary amine as a hydrogen donor. Shoumina and the like (coating industry, 2020,50(1):9-13) prepare 2-hydroxy thioxanthone by using 2, 2-dithiodibenzoic acid and phenol as raw materials, then react with epoxy chloropropane to prepare 2- (2, 3-epoxy propoxy) -thioxanthone, and then react with DAA monomer to obtain 2- (3-diallyl amino-2-hydroxy propoxy) -thioxanthone (marked as DAHTX), the ultraviolet absorption peak is red-shifted by 15-20nm, the intramolecular charge transfer is relatively fast, and the mobility is reduced from 17.6% to 6.2%. The yellowing problem is likewise not solved.

In view of the above, an environmentally friendly photoinitiator with low migration, high initiation, and low or no yellowing has been developed as a heat generation point.

Disclosure of Invention

The invention aims to solve the problems that a double-component photoinitiator in the prior art is low in initiation efficiency and yellowing is caused by the need of adding an auxiliary initiator, and provides a photopolymerizable single-component thioxanthone photoinitiator. The single-component thioxanthone photoinitiator material capable of realizing photopolymerization is prepared by taking hydroxy thioxanthone, bromoethanol, fluorine-containing anhydride, 4-hydroxymethyl-1, 3-dioxo-2-thioketone, epichlorohydrin and acryloyl chloride as raw materials and performing multi-step reactions such as coupling, esterification, epoxy ring opening, epoxidation and the like, has the advantages of high-efficiency photoinitiation efficiency, no yellowing, difficult migration, wide application, environmental protection and the like, and is particularly suitable for the fields of 3C products, 3D printing and the like.

The technical scheme adopted by the invention for solving the technical problems is as follows:

a photopolymerisable single-component thioxanthone photoinitiator has a structural formula shown as follows:

wherein-R-is-CF₂-or-C₂F₄-。

A preparation method of a photopolymerizable single-component thioxanthone photoinitiator comprises the following steps:

(1) adding 1mol of hydroxy thioxanthone, 1-1.2mol of bromoethanol and 1-1.2mol of potassium carbonate into 50mol of DMF, heating to 110-; slowly adding 60mol of water, stirring for 30min, adding 50mol of DMSO, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product I;

(2) adding 1mol of I, 1.1-1.4mol of fluorine-containing acid anhydride and 0.5-4 wt% of catalyst into 50mol of DMSO, introducing nitrogen, heating to 80-110 ℃, stirring for 3-15h, cooling, and standing to obtain an intermediate product II;

the dosage of the catalyst is the percentage of the total mass of I and the fluorine-containing acid anhydride;

(3) adding 1mol of 4-hydroxymethyl-1, 3-dioxo-2-thione to a solution containing 0.5-3 wt.% of BF₃Heating to 40-80 ℃ in 1-1.2mol of epichlorohydrin of ether, and reacting for 2-8 h; standing, and distilling at 40 ℃ under reduced pressure to obtain an intermediate product III;

the BF₃The amount of the ether is 0.5 to 3 weight percent of the mass of the epichlorohydrin;

(4) adding 1-1.2mol of sodium hydroxide into 1mol of III, stirring for 0.5-5h at 40-80 ℃, and washing for 3 times by using deionized water to obtain an epoxidation product; taking 1 weight part of epoxidation product, adding 1-5 weight parts of 0.5-10% sodium hydroxide aqueous solution, and stirring at 30-90 ℃ for 0.5-10h to obtain an intermediate product IV;

(5) dripping 1-1.1mol of II into 30mol of DMSO containing 1mol of IV, introducing nitrogen, heating to 170-; slowly adding deionized water at 90 ℃, stirring for 10min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product V;

(6) adding 1mol of V and 1.1-1.5mol of triethylamine into 50mol of DMSO, carrying out ice-water bath, stirring, slowly dripping 1.1-1.5mol of acryloyl chloride into the solution, and stirring for 6-12 h; washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated salt solution, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and vacuum drying to obtain the photopolymerisable single-component thioxanthone photoinitiator, namely the target product VI.

Preferably, the fluorine-containing acid anhydride is tetrafluorosuccinic anhydride or perfluoroglutaric anhydride.

Preferably, the catalyst is tetrabutyl titanate, p-toluenesulfonic acid, palygorskite solid acid or sodium aluminate.

A photocuring coating is prepared from the following raw materials in parts by weight: 65-69 parts of acrylate resin, 10 parts of TMPTA, 8 parts of TPGDA, 12 parts of butyl acrylate and 1-5 parts of target product VI.

Preferably, the preparation method of the photocuring coating comprises the following steps: mixing the raw materials according to the parts by weight, coating the mixture on PET containing a base coat, and irradiating the mixture for 30-180s under UV light to obtain a coating with the thickness of 2 mu m of a dry film.

The novel photopolymerisable single-component thioxanthone photoinitiator provided by the invention has the following preparation process:

the invention has the beneficial effects that:

(1) the photopolymerisable single-component thioxanthone photoinitiator provided by the invention can be used in all the existing photopolymerisable systems and has the advantage of wide applicability.

(2) The invention provides a photopolymerisable single-component thioxanthone photoinitiator. The single-component thioxanthone photoinitiator simultaneously contains a thioxanthone initiator, a hydrogen donor five-membered ring thioketone structure and an acryloxy group, so that the inherent inverse electron transfer problem of a conventional double-component system is avoided, the initiation efficiency is high, and the yellowing problem caused by amine serving as a common auxiliary initiator is avoided; in addition, the acryloxy can directly participate in the reaction, and the acryloxy enters the system in a chemical bond form, so that the migration problem of the initiator does not exist.

(3) The photopolymerisable single-component thioxanthone photoinitiator provided by the invention contains F element in the structure, wherein the F element has lower atomic surface energy and has the characteristic of migrating to the surface of a system, and the photopolymerisable single-component thioxanthone photoinitiator has the functions of overcoming oxygen inhibition and resisting pollution.

(4) The photopolymerisable single-component thioxanthone photoinitiator provided by the invention has wide applicability in UV-LEDs and can be widely applied to the fields of 3C, 3D printing, microelectronics and the like.

The specific implementation mode is as follows:

the present invention will be described in detail with reference to examples. It is to be understood, however, that the following examples are illustrative of embodiments of the present invention and are not to be construed as limiting the scope of the invention.

Example 1

A preparation method of a photopolymerizable single-component thioxanthone photoinitiator comprises the following steps:

(1) adding 1mol of hydroxy thioxanthone, 1.2mol of bromoethanol and 1.2mol of potassium carbonate into 50mol of DMF, heating to 110 ℃, strongly stirring for 3 hours, cooling, standing, carrying out vacuum concentration on the solution, and enriching residual components; slowly adding 60mol of water, stirring for 30min, adding 50mol of DMSO, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product I;

the infrared data are as follows: 3512cm^-1: -OH is present; 1562cm^-1、1250cm^-1、762cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 582cm^-1: -C-Br is absent.

(2) Adding 1mol of I, 1.2mol of perfluoroglutaric anhydride and 0.5 wt% of tetrabutyl titanate into 50mol of DMSO, introducing nitrogen, heating to 110 ℃, stirring for 3 hours, cooling, and standing to obtain an intermediate product II;

the using amount of the tetrabutyl titanate is the percentage of the total mass of the I and the fluorine-containing acid anhydride;

the infrared data are as follows: 3483cm^-1: -OH is present; 1562cm^-1、1250cm^-1、762cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present.

(3) 1mol of 4-hydroxymethyl-1, 3-dioxo-2-thione was added to a solution containing 3% by weight of BF₃Heating to 80 ℃ in 1mol of epichlorohydrin of ether, and reacting for 2 h; standing, and distilling at 40 ℃ under reduced pressure to obtain an intermediate product III;

the BF₃The amount of the ether is 3 wt% of the mass of the epichlorohydrin;

the infrared data are as follows: 3512cm^-1: -OH is present; 1162cm^-1: -C ═ S is present; 910cm^-1: epoxy groups are absent; 741cm^-1: -C-Cl.

(4) Adding 1.2mol of sodium hydroxide into 1mol of III, stirring for 2h at 60 ℃, and washing for 3 times by using deionized water to obtain an epoxidation product; taking 1 part by weight of epoxidation product, adding 4 parts by weight of 2% sodium hydroxide aqueous solution, and stirring at 60 ℃ for 5 hours to obtain an intermediate product IV;

the infrared data are as follows: 3512cm^-1: -OH is present; 1162cm^-1: -C ═ S is present; 741cm^-1: disappearance of-C-Cl.

(5) Dripping 1.1mol of II into 30mol of DMSO containing 1mol of IV, introducing nitrogen, heating to 200 ℃, stirring for 1h, cooling, standing, and vacuum concentrating; slowly adding deionized water at 90 ℃, stirring for 10min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product V;

the infrared data are as follows: 3501cm^-1: -OH is present; 1562cm^-1、1250cm^-1、762cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present; 1162cm^-1: -C ═ S is present.

(6) Adding 1mol of V and 1.4mol of triethylamine into 50mol of DMSO, carrying out ice-water bath, stirring, slowly dripping 1.4mol of acryloyl chloride into the solution, and stirring for 8 hours; washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated salt solution, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and vacuum drying to obtain the photopolymerisable single-component thioxanthone photoinitiator, namely the target product VI.

The infrared data are as follows: 3501cm^-1: -OH disappearance; 1562cm^-1、1250cm^-1、762cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present; 1162cm^-1: -C ═ S is present; 1611cm^-1、810cm^-1: -C ═ C-is present.

The nuclear magnetic hydrogen spectrum data is as follows:¹h NMR (400MHz, DMSO,. delta.ppm): 7.2-8.5(14H, benzene ring); 4.02(2H, -CH)₂-)；4.23(2H，-CH₂-)；3.64(6H，-CH₂-)；4.41(2H，-CH-)；3.05(2H，-CH₂-)；5.96(1H，-CH＝)；5.61/6.30(2H，CH₂＝)。

Example 2

A preparation method of a photopolymerizable single-component thioxanthone photoinitiator comprises the following steps:

(1) adding 1mol of hydroxy thioxanthone, 1mol of bromoethanol and 1mol of potassium carbonate into 50mol of DMF, heating to 130 ℃, stirring strongly for 1h, cooling, standing, and concentrating the solution in vacuum to enrich the residual components; slowly adding 60mol of water, stirring for 30min, adding 50mol of DMSO, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product I;

the infrared data are as follows: 3511cm^-1: -OH is present; 1561cm^-1、1250cm^-1、761cm^-1: a benzene ring is present; 1721cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 582cm^-1: -C-Br is absent.

(2) Adding 1mol of I, 1.4mol of tetrafluorosuccinic anhydride and 2 wt% of p-toluenesulfonic acid into 50mol of DMSO, introducing nitrogen, heating to 100 ℃, stirring for 5 hours, cooling, and standing to obtain an intermediate product II;

the dosage of the catalyst p-toluenesulfonic acid is the percentage of the total mass of I and tetrafluorosuccinic anhydride;

the infrared data are as follows: 3481cm^-1: -OH is present; 1561cm^-1、1250cm^-1、761cm^-1: a benzene ring is present; 1720cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present.

(3) 1mol of 4-hydroxymethyl-1, 3-dioxo-2-thione was added to a solution containing 0.5% by weight of BF₃Heating to 40 ℃ in 1.2mol of epichlorohydrin with ether, and reacting for 8 h; standing, and distilling at 40 ℃ under reduced pressure to obtain an intermediate product III;

the BF₃The amount of the ether is 0.5 wt% of the mass of the epichlorohydrin;

the infrared data are as follows: 3509cm^-1: -OH is present; 1161cm^-1: -C ═ S is present; 910cm^-1: epoxy groups are absent; 740cm^-1: -C-Cl.

(4) Adding 1.1mol of sodium hydroxide into 1mol of III, stirring for 0.5h at 80 ℃, and washing for 3 times by using deionized water to obtain an epoxidation product; taking 1 part by weight of epoxidation product, adding 2 parts by weight of 8% sodium hydroxide aqueous solution, and stirring at 90 ℃ for 0.5h to obtain an intermediate product IV;

the infrared data are as follows: 3509cm^-1: -OH is present; 1161cm^-1: -C ═ S is present; 740cm^-1: disappearance of-C-Cl.

(5) Dripping 1mol of II into 30mol of DMSO containing 1mol of IV, introducing nitrogen, heating to 170 ℃, stirring for 6h, cooling, standing, and vacuum concentrating; slowly adding deionized water at 90 ℃, stirring for 10min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product V;

the infrared data are as follows: 3501cm^-1: -OH is present; 1561cm^-1、1250cm^-1、761cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present; 1162cm^-1: -C ═ S is present.

(6) Adding 1mol of V and 1.3mol of triethylamine into 50mol of DMSO, carrying out ice-water bath, stirring, slowly dripping 1.3mol of acryloyl chloride into the solution, and stirring for 10 hours; washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated salt solution, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and vacuum drying to obtain the photopolymerisable single-component thioxanthone photoinitiator, namely the target product VI.

The infrared data are as follows: 3501cm^-1: -OH disappearance; 1561cm^-1、1250cm^-1、761cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present; 1161cm^-1: -C ═ S is present; 1610cm^-1、810cm^-1: -C ═ C-is present.

The nuclear magnetic hydrogen spectrum data is as follows:¹h NMR (400MHz, DMSO,. delta.ppm): 7.2-8.5(14H, benzene ring); 4.02(2H, -CH)₂-)；4.23(2H，-CH₂-)；3.64(6H，-CH₂-)；4.41(2H，-CH-)；3.05(2H，-CH₂-)；5.96(1H，-CH＝)；5.61/6.30(2H，CH₂＝)。

Example 3

A preparation method of a photopolymerizable single-component thioxanthone photoinitiator comprises the following steps:

(1) adding 1mol of hydroxy thioxanthone, 1.1mol of bromoethanol and 1.1mol of potassium carbonate into 50mol of DMF, heating to 120 ℃, strongly stirring for 2 hours, cooling, standing, carrying out vacuum concentration on the solution, and enriching residual components; slowly adding 60mol of water, stirring for 30min, adding 50mol of DMSO, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product I;

the infrared data are as follows: 3508cm^-1: -OH is present; 1555cm^-1、1248cm^-1、760cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 987cm^-1: -C-S-is present; 582cm^-1: -C-Br is absent.

(2) Adding 1mol of I, 1.1mol of perfluoroglutaric anhydride and 3 wt% of palygorskite solid acid into 50mol of DMSO, introducing nitrogen, heating to 90 ℃, stirring for 8 hours, cooling, and standing to obtain an intermediate product II;

the dosage of the catalyst palygorskite solid acid is the percentage of the total mass of I and perfluoroglutaric anhydride;

the infrared data are as follows: 3483cm^-1: -OH is present; 1556cm^-1、1250cm^-1、760cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present.

(3) 1mol of 4-hydroxymethyl-1, 3-dioxo-2-thione was added to a solution containing 1% by weight of BF₃Heating to 70 ℃ in 1.1mol of epichlorohydrin with ether, and reacting for 4 h; standing, and distilling at 40 ℃ under reduced pressure to obtain an intermediate product III;

the BF₃The amount of the ether is 1 wt% of the mass of the epichlorohydrin;

the infrared data are as follows: 3512cm^-1: -OH is present; 1162cm^-1: -C ═ S is present; 910cm^-1: epoxy groups are absent; 741cm^-1: -C-Cl.

(4) Adding 1mol of sodium hydroxide into 1mol of III, stirring for 2h at 70 ℃, and washing for 3 times by using deionized water to obtain an epoxidation product; taking 1 part by weight of epoxidation product, adding 1 part by weight of 10% sodium hydroxide aqueous solution, and stirring at 30 ℃ for 10 hours to obtain an intermediate product IV;

the infrared data are as follows: 3512cm^-1: -OH is present; 1162cm^-1: -C ═ S is present; 741cm^-1: disappearance of-C-Cl.

(5) Dripping 1.1mol of II into 30mol of DMSO containing 1mol of IV, introducing nitrogen, heating to 190 ℃, stirring for 2h, cooling, standing, and vacuum concentrating; slowly adding deionized water at 90 ℃, stirring for 10min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product V;

the infrared data are as follows: 3501cm^-1: -OH is present; 1562cm^-1、1250cm^-1、762cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present; 1162cm^-1: -C ═ S is present.

(6) Adding 1mol of V and 1.1mol of triethylamine into 50mol of DMSO, carrying out ice-water bath, stirring, slowly dripping 1.1mol of acryloyl chloride into the solution, and stirring for 12 hours; washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated salt solution, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and vacuum drying to obtain the photopolymerisable single-component thioxanthone photoinitiator, namely the target product VI.

The infrared data are as follows: 3501cm^-1: -OH disappearance; 1562cm^-1、1250cm^-1、762cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present; 1162cm^-1: -C ═ S is present; 1611cm^-1、810cm^-1: -C ═ C-is present.

The nuclear magnetic hydrogen spectrum data is as follows:¹h NMR (400MHz, DMSO,. delta.ppm): 7.2-8.5(14H, benzene ring); 4.02(2H, -CH)₂-)；4.23(2H，-CH₂-)；3.64(6H，-CH₂-)；4.41(2H，-CH-)；3.05(2H，-CH₂-)；5.96(1H，-CH＝)；5.61/6.30(2H，CH₂＝)。

Example 4

A preparation method of a photopolymerizable single-component thioxanthone photoinitiator comprises the following steps:

(1) adding 1mol of hydroxy thioxanthone, 1.2mol of bromoethanol and 1.2mol of potassium carbonate into 50mol of DMF, heating to 120 ℃, strongly stirring for 2 hours, cooling, standing, carrying out vacuum concentration on the solution, and enriching residual components; slowly adding 60mol of water, stirring for 30min, adding 50mol of DMSO, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product I;

the infrared data are as follows: 3512cm^-1: -OH is present; 1562cm^-1、1250cm^-1、762cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 582cm^-1: -C-Br is absent.

(2) Adding 1mol of I, 1.3mol of perfluoroglutaric anhydride and 4 wt% of sodium aluminate into 50mol of DMSO, introducing nitrogen, heating to 100 ℃, stirring for 15 hours, cooling, and standing for later use to obtain an intermediate product II;

the amount of the sodium aluminate catalyst is the percentage of the total mass of I and perfluoroglutaric anhydride;

the infrared data are as follows: 3483cm^-1: -OH is present; 1562cm^-1、1250cm^-1、762cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present.

(3) 1mol of 4-hydroxymethyl-1, 3-dioxo-2-thione was added to a solution containing 2% by weight of BF₃Heating to 50 ℃ in 1.1mol of epichlorohydrin with ether, and reacting for 6 h; standing, and distilling at 40 ℃ under reduced pressure to obtain an intermediate product III;

the BF₃The amount of the ether is 2 wt% of the mass of the epichlorohydrin;

the infrared data are as follows: 3512cm^-1: -OH is present; 1160cm^-1: -C ═ S is present; 910cm^-1: epoxy groups are absent; 741cm^-1: -C-Cl.

(4) Adding 1.2mol of sodium hydroxide into 1mol of III, stirring for 5h at 40 ℃, and washing for 3 times by using deionized water to obtain an epoxidation product; taking 1 part by weight of epoxidation product, adding 5 parts by weight of 0.5% sodium hydroxide aqueous solution, and stirring at 50 ℃ for 5 hours to obtain an intermediate product IV;

the infrared data are as follows: 3512cm^-1: -OH is present; 1160cm^-1: -C ═ S is present; 741cm^-1: disappearance of-C-Cl.

(5) Dripping 1.1mol of II into 30mol of DMSO containing 1mol of IV, introducing nitrogen, heating to 180 ℃, stirring for 3h, cooling, standing, and vacuum concentrating; slowly adding deionized water at 90 ℃, stirring for 10min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product V;

the infrared data are as follows: 3501cm^-1: -OH is present; 1562cm^-1、1250cm^-1、762cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present; 1161cm^-1: -C ═ S is present.

(6) Adding 1mol of V and 1.5mol of triethylamine into 50mol of DMSO, carrying out ice-water bath, stirring, slowly dripping 1.5mol of acryloyl chloride into the solution, and stirring for 6 hours; washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated salt solution, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and vacuum drying to obtain the photopolymerisable single-component thioxanthone photoinitiator, namely the target product VI.

The infrared data are as follows: 3501cm^-1: -OH disappearance; 1562cm^-1、1250cm^-1、762cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present; 1161cm^-1: -C ═ S is present; 1611cm^-1、810cm^-1: -C ═ C-is present.

The nuclear magnetic hydrogen spectrum data is as follows:¹h NMR (400MHz, DMSO,. delta.ppm): 7.2-8.5(14H, benzene ring); 4.02(2H, -CH)₂-)；4.23(2H，-CH₂-)；3.64(6H，-CH₂-)；4.41(2H，-CH-)；3.05(2H，-CH₂-)；5.96(1H，-CH＝)；5.61/6.30(2H，CH₂＝)。

Example 5

A preparation method of a photopolymerizable single-component thioxanthone photoinitiator comprises the following steps:

(1) adding 1mol of hydroxy thioxanthone, 1.1mol of bromoethanol and 1.1mol of potassium carbonate into 50mol of DMF, heating to 130 ℃, strongly stirring for 1h, cooling, standing, carrying out vacuum concentration on the solution, and enriching residual components; slowly adding 60mol of water, stirring for 30min, adding 50mol of DMSO, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product I;

the infrared data are as follows: 3512cm^-1: -OH is present; 1560cm^-1、1249cm^-1、761cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 582cm^-1: -C-Br is absent.

(2) Adding 1mol of I, 1.2mol of tetrafluorosuccinic anhydride and 1 wt% of tetrabutyl titanate into 50mol of DMSO, introducing nitrogen, heating to 80 ℃, stirring for 10 hours, cooling, and standing to obtain an intermediate product II;

the dosage of the catalyst tetrabutyl titanate is the percentage of the total mass of I and tetrafluorosuccinic anhydride;

the infrared data are as follows: 3483cm^-1: -OH is present; 1560cm^-1、1249cm^-1、761cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present.

(3) 1mol of 4-hydroxymethyl-1, 3-dioxo-2-thione was added to a solution containing 1.5% by weight of BF₃Heating to 60 ℃ in 1.2mol of epichlorohydrin with ether, and reacting for 4 h; standing, and distilling at 40 ℃ under reduced pressure to obtain an intermediate product III;

the BF₃The amount of the ether is 1.5 wt% of the mass of the epichlorohydrin;

the infrared data are as follows: 3512cm^-1: -OH is present; 1162cm^-1: -C ═ S is present; 910cm^-1: epoxy groups are absent; 741cm^-1: -C-Cl.

(4) Adding 1.1mol of sodium hydroxide into 1mol of III, stirring for 4h at 50 ℃, and washing for 3 times by using deionized water to obtain an epoxidation product; taking 1 part by weight of epoxidation product, adding 5 parts by weight of 3% sodium hydroxide aqueous solution, and stirring at 80 ℃ for 2 hours to obtain an intermediate product IV;

the infrared data are as follows: 3512cm^-1: -OH is present; 1162cm^-1: -C ═ S is present; 741cm^-1: disappearance of-C-Cl.

(5) Dripping 1mol of II into 30mol of DMSO containing 1mol of IV, introducing nitrogen, heating to 190 ℃, stirring for 3h, cooling, standing, and vacuum concentrating; slowly adding deionized water at 90 ℃, stirring for 10min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product V;

the infrared data are as follows: 3501cm^-1: -OH is present; 1560cm^-1、1249cm^-1、761cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present; 1162cm^-1: -C ═ S is present.

(6) Adding 1mol of V and 1.2mol of triethylamine into 50mol of DMSO, carrying out ice-water bath, stirring, slowly dripping 1.2mol of acryloyl chloride into the solution, and stirring for 10 hours; washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated salt solution, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and vacuum drying to obtain the photopolymerisable single-component thioxanthone photoinitiator, namely the target product VI.

The infrared data are as follows: 3501cm^-1: -OH disappearance; 1560cm^-1、1249cm^-1、761cm^-1: a benzene ring is present; 1723cm^-1: -C ═ O is present; 988cm^-1: -C-S-is present; 1187cm^-1: -C-F is present; 1162cm^-1: -C ═ S is present; 1611cm^-1、810cm^-1: -C ═ C-is present.

The nuclear magnetic hydrogen spectrum data is as follows:¹h NMR (400MHz, DMSO,. delta.ppm): 7.2-8.5(14H, benzene ring); 4.02(2H, -CH)₂-)；4.23(2H，-CH₂-)；3.64(6H，-CH₂-)；4.41(2H，-CH-)；3.05(2H，-CH₂-)；5.96(1H，-CH＝)；5.61/6.30(2H，CH₂＝)。

The photoinitiator obtained in specific example 1 was used as a base material in practical examples and applied to a photocurable coating.

Application example 1

The photocuring coating comprises the following raw materials in parts by weight: acrylate resin SM 620267 parts, TMPTA 10 parts, TPGDA 8 parts, butyl acrylate 12 parts and target product VI 3 parts.

The preparation method comprises the following steps: the raw materials are mixed according to the parts by weight, coated on PET containing a base coat, and irradiated for 60s under UV light to obtain a coating with the thickness of 2 mu m of a dry film.

Application example 2

The photocuring coating comprises the following raw materials in parts by weight: acrylate resin SM 620265 parts, TMPTA 10 parts, TPGDA 8 parts, butyl acrylate 12 parts and a target product VI 5 parts.

The preparation method comprises the following steps: the raw materials are mixed according to the parts by weight, coated on PET containing a base coat, and irradiated for 30s under UV light to obtain a coating with the thickness of 2 mu m of a dry film.

Application example 3

A photocuring coating is prepared from the following raw materials in parts by weight: acrylate resin SM 620269, TMPTA 10, TPGDA 8, butyl acrylate 12 and target product VI 1.

Preferably, the preparation method of the photocuring coating comprises the following steps: the raw materials are mixed according to the parts by weight, coated on PET containing a base coat, and irradiated for 180s under UV light to obtain a dry film coating with the thickness of 2 mu m.

Application example 4

The photocuring coating comprises the following raw materials in parts by weight: acrylate resin SM 620267 parts, TMPTA 10 parts, TPGDA 8 parts, butyl acrylate 12 parts and target product VI 3 parts.

The preparation method comprises the following steps: the raw materials are mixed according to the parts by weight, coated on PET containing a base coat, and irradiated for 120s under UV light to obtain a coating with the thickness of 2 mu m of a dry film.

Application examples comparative examples 1-3 application example 1 was used as a control.

Practical example comparative example 1

The photocuring coating comprises the following raw materials in parts by weight: acrylate resin SM 620267 parts, TMPTA 10 parts, TPGDA 8 parts, butyl acrylate 12 parts and ITX 3 parts.

The preparation method comprises the following steps: the raw materials are mixed according to the parts by weight, coated on PET containing a base coat, and irradiated for 60s under UV light to obtain a coating with the thickness of 2 mu m of a dry film.

Practical example comparative example 2

The photocuring coating comprises the following raw materials in parts by weight: acrylate resin SM 620267 parts, TMPTA 10 parts, TPGDA 8 parts, butyl acrylate 12 parts, ITX 3 parts and EDAB 3 parts.

The preparation method comprises the following steps: the raw materials are mixed according to the parts by weight, coated on PET containing a base coat, and irradiated for 60s under UV light to obtain a coating with the thickness of 2 mu m of a dry film.

Physical properties including migration, yellowing, initiation efficiency, etc. of the macro photoinitiators prepared in application examples 1 to 4 of the present invention and comparative examples 1 to 3 were measured, respectively, and the results are shown in table 1.

Table 1 physical test properties of the examples

Firstly, as can be seen from table 1, the photopolymerizable single-component thioxanthone photoinitiator of the invention is compared with the currently commonly used small-molecule photoinitiator ITX and two-component ITX + EDAB; the product of the invention can self-initiate self-crosslinking, has no migration problem, and has no odor; meanwhile, the thioketone ring structure is used as an intramolecular hydrogen donor, so that the problem of yellowing of tertiary amine is avoided, and the initiation efficiency is higher. Therefore, the product has the advantages of no odor, no yellowing, difficult migration, more environmental protection and the like;

secondly, compared with the conventional common small-molecule photoinitiator, the polyurethane photoinitiator has a larger water contact angle and certain water repellency;

in summary, compared with the existing photoinitiator, the photopolymerizable single-component thioxanthone photoinitiator not only overcomes the defects of low initiation efficiency, requirement of an auxiliary initiator, easy migration and precipitation and yellowing of the traditional double-component micromolecule photoinitiator, but also has high initiation efficiency and certain water repellency.

The test method comprises the following steps:

(1) odor: the lower the odor, the less migration is indicated, as evaluated by the direct fan-smelling method.

(2) Mobility: and (3) soaking the sample to be tested in acetonitrile for 24h in a 40 ℃ oven, preparing the same concentration, and testing the molar absorption coefficient of the sample under the corresponding photoinitiator by using an ultraviolet-visible spectrometer. Migration representation method: 5 is optimal and 1 is worst.

(3) Yellowing: the film was evaluated by visual observation, and the darker the color of the film, the more severe the yellowing. Method for expression of yellowing: 5 is colorless, most preferably, 1 is dark, worst.

(4) Oxygen inhibition and initiation efficiency test of double bond:

the test method comprises the following steps: the polymerization kinetics of the photocurable resin was monitored by a series of real-time infrared spectroscopy. Coating a sample containing photoinitiator on a KBr salt sheet, then putting into RTIR, irradiating with an ultraviolet point source for 120s for curing, wherein the light intensity is measured by a UV-A ultraviolet radiometer and is set to 80mW/cm². By monitoring the near infrared region C-H at 776-828 cm-^-1The change in the absorption peak area of (2) intuitively reflects the degree of progress of polymerization. The double bond conversion rate (DC) of the polymerization system can be calculated by combining OMNIC 8.2 infrared software and Excel data processing software with a formula, each sample is tested and repeated for 3 times, and an average value is taken.

Wherein DC represents the conversion rate of carbon-carbon double bonds when the illumination time is t, A₀Represents the initial area of the double bond absorption peak before illumination, A_tRepresents the double bond absorption peak area at the time of illumination t.

(5)t(R_p(max)) S: i.e. to achieve maximum polymerizationThe time required by the rate is monitored by series real-time infrared spectrums in the polymerization kinetic process of the light-cured resin, and a time t-polymerization rate R is obtained by deriving a time-conversion curve_pCurve line.

(6) Contact angle: the test was carried out according to the method described in ASTM D7334-2008 (2013). The larger the water contact angle value, the lower the surface tension, and the more excellent the stain resistance.

In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.