阅读说明：本技术 一种硫杂蒽酮有机锆配合物光引发剂及其制备方法和应用 (Thioxanthone organic zirconium complex photoinitiator and preparation method and application thereof ) 是由 张玉贞 华叶莹 于 2019-08-28 设计创作，主要内容包括：本发明属于有机功能材料领域,具体涉及一种硫杂蒽酮有机锆配合物光引发剂及其制备方法和应用。该光引发剂结构式如(I),本发明的一种硫杂蒽酮有机锆配合物光引发剂具有优异的光引发活性,活性锆作为中心配体,可以有效的克服氧阻聚,用来引发聚合单体,转化率较高；其制备方法操作简单,反应原料来源方便,成本低,环境友好无污染,适合规模化工业化生产；其应用于光固化领域时,不仅光引发活性优异,而且具有低迁移性、低气味性、低毒性、耐黄变等优点。<Image he="593" wi="700" file="DDA0002182471000000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention belongs to the field of organic functional materials, and particularly relates to a thioxanthone organic zirconium complex photoinitiator, and a preparation method and application thereof. The photoinitiator has a structural formula shown in (I), has excellent photoinitiation activity, can effectively overcome oxygen inhibition by taking active zirconium as a central ligand, is used for initiating a polymerization monomer, and has high conversion rate; the preparation method is simple to operate, the reaction raw materials are convenient to obtain, the cost is low, the environment is friendly, no pollution is caused, and the preparation method is suitable for large-scale industrial production; when the photoinitiator is applied to the field of photocuring, the photoinitiator has excellent photoinitiation activity and has the advantages of low migration, low odor, low toxicity, yellowing resistance and the like.)

1. A thioxanthone organozirconium complex photoinitiator has the following structural formula:

2. the method of claim 1, wherein the preparation of the thioxanthone organozirconium complex photoinitiator comprises: the method specifically comprises the following steps:

1) under the protection of inert gas, placing 2-chlorothioxanthone in 0.1mol/L sodium hydroxide ethanol solution, wherein the mass concentration of the 2-chlorothioxanthone in the solution is 100-125 mg/L, dropwise adding ethylene glycol under mechanical stirring, carrying out reflux reaction for 24 hours, after the reaction is finished, dissolving and washing with dichloromethane, concentrating, and crystallizing and purifying to obtain an intermediate product;

2) under the protection of inert gas, placing the intermediate product prepared in the step 1) in a polar aprotic organic solvent, adding triethylamine, dropwise adding a zirconium n-propoxide solution while stirring, reacting at the temperature of 100-110 ℃ for 12-18h, after the reaction is finished, washing with water, concentrating, crystallizing and purifying to obtain the photoinitiator thioxanthone organic zirconium complex.

3. The method of claim 2, wherein the preparation of the thioxanthone organozirconium complex photoinitiator comprises: the inert gas in the steps 1) to 2) is nitrogen or argon.

4. The method of claim 2, wherein the preparation of the thioxanthone organozirconium complex photoinitiator comprises: the molar ratio of the 2-chlorothioxanthone to the ethylene glycol in the step 1) is 1: 1.1-1.5.

5. The method of claim 2, wherein the preparation of the thioxanthone organozirconium complex photoinitiator comprises: the polar aprotic organic solvent in the step 2) is one of DMF and DMSO.

6. The method of claim 2, wherein the preparation of the thioxanthone organozirconium complex photoinitiator comprises: the molar ratio of the intermediate product in the step 2) to zirconium n-propoxide is 4-5: 1; the molar ratio of the zirconium n-propoxide to the triethylamine is 1: 1.5-3.

7. A thioxanthone organic zirconium complex photocuring varnish is prepared from the following raw materials in parts by weight: acrylate copolymer SM 6324100 parts, propoxylated neopentyl glycol diacrylate 50 parts, thioxanthone organic zirconium complex 1-3 parts, and butyl acetate 300 parts.

Technical Field

The invention belongs to the field of organic functional materials, and particularly relates to a thioxanthone organic zirconium complex photoinitiator, and a preparation method and application thereof.

Background

The ultraviolet curing technology is a process for rapidly converting a liquid substance with chemical reaction activity into a solid substance by utilizing ultraviolet initiation. The technology has the characteristics of high efficiency, wide adaptability, economy, energy conservation and environmental friendliness, and is widely applied to the fields of printing plate making, stereolithography, printing ink, coating, adhesive, food packaging and medical biomaterials.

The nature of the ultraviolet light photocuring reaction is polymerization and crosslinking reaction initiated by ultraviolet light, and any photocuring system at least comprises the following three components: (1) resins, which impart basic physicochemical properties to the material; (2) monomers, mainly used for adjusting the viscosity of the whole system, but also having influence on the curing rate of the whole formula system and the performance of materials; (3) the ultraviolet light initiator generates active species for initiating polymerization reaction under the irradiation of ultraviolet light. Although the content of the ultraviolet initiator in the whole formula system is very small, most monomers except the ultraviolet initiator in the formula can not generate effective initiating active species under the irradiation of ultraviolet light, so the ultraviolet initiator becomes an indispensable key component in the whole ultraviolet curing formula and determines whether the oligomer and the monomer can rapidly generate crosslinking curing reaction when the whole formula system is irradiated by the ultraviolet light. The photoinitiator is an important component in a photopolymerization system, and free radical photopolymerization is the most widely applied polymerization system at present and has the advantage of high polymerization rate. However, radical photopolymerization has a serious problem of oxygen inhibition, and the presence of oxygen can consume radicals, so that the conversion rate of a polymer system is reduced, the surface curing is incomplete, and the performance of the material is influenced. Although increasing the light intensity or the initiator concentration can effectively solve the problem of oxygen inhibition, too high light intensity or initiator concentration may aggravate volume shrinkage or cause a light shielding effect.

Disclosure of Invention

Aiming at the problem of severe oxygen inhibition in free radical photopolymerization, the invention provides a thioxanthone organic zirconium complex photoinitiator and a preparation method and application thereof, wherein the thioxanthone organic zirconium complex photoinitiator has excellent photoinitiation activity, active zirconium is used as a central ligand, oxygen inhibition can be effectively overcome, the thioxanthone organic zirconium complex photoinitiator is used for initiating a polymerization monomer, and the conversion rate is high; the reaction raw materials are convenient to obtain and low in cost; is environment-friendly and pollution-free, and is suitable for large-scale industrial production.

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

a thioxanthone organozirconium complex photoinitiator has a structure shown in the following structural formula:

a preparation method of a thioxanthone organic zirconium complex photoinitiator specifically comprises the following steps:

1) under the protection of inert gas, placing 2-chlorothioxanthone in 0.1mol/L sodium hydroxide ethanol solution, wherein the mass concentration of the 2-chlorothioxanthone in the solution is 100-125 mg/L, dropwise adding ethylene glycol under mechanical stirring, carrying out reflux reaction for 24 hours, after the reaction is finished, dissolving and washing with dichloromethane, concentrating, and crystallizing and purifying to obtain an intermediate product;

2) under the protection of inert gas, placing the intermediate product prepared in the step 1) in a polar aprotic organic solvent, adding triethylamine, dropwise adding a zirconium n-propoxide solution while stirring, reacting at the temperature of 100-110 ℃ for 12-18h, after the reaction is finished, washing with water, concentrating, crystallizing and purifying to obtain the photoinitiator thioxanthone organic zirconium complex.

Further, the inert gas in the steps 1) to 2) is nitrogen or argon.

Further, the molar ratio of the 2-chlorothioxanthone to the ethylene glycol in the step 1) is 1: 1.1-1.5.

Further, the polar aprotic organic solvent in the step 2) is one of DMF and DMSO.

Further, the molar ratio of the intermediate product in the step 2) to zirconium n-propoxide is 4-5: 1; the molar ratio of the zirconium n-propoxide to the triethylamine is 1: 1.5-3.

A thioxanthone organic zirconium complex photocuring varnish is prepared from the following raw materials in parts by weight: acrylate copolymer SM 6324100 parts, propoxylated neopentyl glycol diacrylate 50 parts, thioxanthone organozirconium complex 1-3 parts, and butyl acetate (solvent) 300 parts.

The equation for the above reaction is as follows:

the invention has the following beneficial effects:

(1) the thioxanthone organic zirconium complex photoinitiator has excellent photoinitiation activity, active zirconium is used as a central ligand, oxygen inhibition can be effectively overcome, the thioxanthone organic zirconium complex photoinitiator is used for initiating polymerization monomers, and the conversion rate is high.

(2) The preparation method of the thioxanthone organic zirconium complex photoinitiator has the advantages of mild and easily controlled reaction conditions and simple operation; the reaction raw materials are convenient to obtain and low in cost; is environment-friendly and pollution-free, and is suitable for large-scale industrial production.

(3) When the thioxanthone organic zirconium complex photoinitiator is applied to the field of photocuring, the photoinitiator has excellent photoinitiation activity and has the advantages of low migration, low odor, low toxicity, yellowing resistance and the like.

Drawings

The invention is further illustrated with reference to the following figures and examples.

FIG. 1 is a nuclear magnetic spectrum of a thioxanthone organozirconium complex photoinitiator according to example 1 of the present invention.

FIG. 2 is a real-time infrared image of the thioxanthone organozirconium complex photoinitiator prepared according to the present invention with conventional 907, 1173, 184, ITX photoinitiators.

Detailed Description

The present invention will now be described in further detail with reference to the following examples.