阅读说明：本技术 一种氯醋树脂基的二苯甲酮大分子光引发剂及其制备方法 (Chloroacetate resin-based benzophenone macromolecular photoinitiator and preparation method thereof ) 是由 张玉贞 华叶莹 于 2019-08-28 设计创作，主要内容包括：本发明涉及一种氯醋树脂基的二苯甲酮大分子光引发剂及其制备方法,其制备方法是以N-甲基二乙醇胺、二异氰酸酯合成异氰酸根封端的含有氨基甲酸酯结构的中间物PU-1,将PU-1依次与羟基三元氯醋树脂、对羟基二苯甲酮反应得到目标产物PV-PU。本发明制得的这种大分子光引发剂,其结构通式如(I),因在同一分子链上同时含有二苯甲酮和叔胺结构,可提高光敏分解产生活性物种效率,又由于其同时含有氯醋、聚氨酯结构,不仅增加与引发体系的相容性,大大降低光引发剂的表面迁移,同时对颜料有优异的展色性,对底材的附着力俱佳,可作为氯醋树脂特种功能材料使用,在UV光固化、木器漆、PVC基材、油墨印刷等领域可以有广泛应用。<Image he="275" wi="700" file="DDA0002182605020000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention relates to a vinyl chloride-vinyl acetate-based benzophenone macromolecular photoinitiator and a preparation method thereof, wherein the preparation method comprises the steps of synthesizing an intermediate PU-1 containing an isocyanic acid ester structure and an end capping end by N-methyldiethanolamine and diisocyanate, and reacting the PU-1 with hydroxyl ternary vinyl chloride-vinyl acetate resin and p-hydroxybenzophenone in sequence to obtain a target product PV-PU. The macromolecular photoinitiator prepared by the invention has a structural general formula shown in (I), can improve the efficiency of generating active species by photosensitive decomposition due to the fact that the macromolecular photoinitiator contains benzophenone and tertiary amine structures on the same molecular chain, also has excellent color development performance on pigments and good adhesion to substrates due to the fact that the macromolecular photoinitiator contains chlorine vinegar and polyurethane structures, not only increases the compatibility with an initiation system and greatly reduces the surface migration of the photoinitiator, but also can be used as a special functional material of the chlorine vinegar resin, and can be widely applied to the fields of UV photocuring, wood lacquer, PVC substrates, ink printing and the like.)

1. A chlorine-acetate resin-based benzophenone macromolecular photoinitiator has a chemical structural formula as follows:

wherein R is₁-OH is a hydroxyl or hydroxyalkyl structure.

2. A preparation method of a vinyl chloride-vinyl benzophenone macromolecular photoinitiator is characterized by comprising the following steps: the method comprises the following steps (introducing nitrogen for protection in the whole reaction process):

(a) 4-4.5 parts of diisocyanate and 2 parts of catalyst are dissolved in 40 parts of ethyl acetate, 2 parts of N-methyldiethanolamine are dissolved in 20 parts of ethyl acetate and added into a constant pressure dropping funnel, the dropping speed is controlled to be 4-5 s/drop, after magnetic stirring is carried out for 2-4h at room temperature, the reaction is stopped when hydroxyl is detected to disappear by infrared, and the ethyl acetate solution of the intermediate product PU-1 is obtained.

(b) Dissolving 1.5-1.7 parts of p-hydroxybenzophenone in 20 parts of ethyl acetate, adding the solution into a constant-pressure dropping funnel, controlling the dropping speed to be 4-5 s/drop, dropping the solution into a completely dissolved ethyl acetate solution of PU-1, continuing to stir by magnetic force for 0.5h after dropping, continuing to use the constant-pressure dropping funnel to drop 10 parts of ethyl acetate solution in which 1 part of hydroxyl ternary vinyl chloride-acetate resin is dissolved, controlling the dropping speed to be 4-5 s/drop, stopping reaction when an infrared detection-NCO group disappears after the magnetic stirring is carried out for 12-24h at room temperature, drying an organic layer by anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure to remove the solvent, and carrying out vacuum drying to obtain a target product PV-PU.

3. The method for preparing a vinyl chloride-vinyl benzophenone macro-photoinitiator according to claim 2, wherein the method comprises the following steps: the diisocyanate is any one of MDI, TDI, HDI and IPDI.

4. The method for preparing a vinyl chloride-vinyl benzophenone macro-photoinitiator according to claim 2, wherein the method comprises the following steps: the molar ratio of the diisocyanate to the N-methyldiethanolamine is as follows: 4-4.5:2, and the molar ratio of the hydroxyl ternary vinyl chloride-acetate copolymer resin to the p-hydroxybenzophenone is 1: 1.5-1.7.

5. The method for preparing a vinyl chloride-vinyl benzophenone macro-photoinitiator according to claim 2, wherein the method comprises the following steps: the catalyst is any one of zinc isooctanoate, stannous octoate, dibutyltin dilaurate and dimethyl tin maleate.

6. The method for preparing a vinyl chloride-vinyl benzophenone macro-photoinitiator according to claim 2, wherein the method comprises the following steps: the molar ratio of the PU-1 to the p-hydroxybenzophenone is 1:1.

Technical Field

The invention relates to a chlorine-acetate resin based benzophenone macromolecular photoinitiator and a preparation method thereof.

Background

The ultraviolet curing technology is a representative starting in the development process of coatings, adhesives and printing ink, is a novel green technology which is appeared in the 60 s of the 20 th century, and is a process of initiating a liquid substance with chemical reaction activity to be rapidly converted into a solid state by using light (ultraviolet light or visible light) as an energy source. Compared with the traditional solution forming, the ultraviolet curing technology is summarized as having the characteristics of '5E', such as high efficiency (efficiency), wide adaptability (Enabling), economy (Economical), energy conservation (energy-saving) and Environmental friendliness (Environmental friendliness). The photocurable system generally includes a reactive monomer, a prepolymer, and a photoinitiator. Under ultraviolet radiation, the photolytic reaction of the photoinitiator produces reactive species that initiate polymerization of the monomers and prepolymers. With the continuous development of science and technology and the increasing attention on environmental protection, the photocuring technology is rapidly developed, and the technology is widely applied to the fields of coatings, printing ink, adhesives, biological materials, nano materials and the like.

In the course of the technological progress of photocuring systems, the research and development of novel photoinitiator systems has always taken a very important position. In radical photopolymerization, benzophenone derivatives are the most widely used photoinitiators. The Chinese patent of invention (publication No. CN 107163206A) discloses a preparation method of high molecular benzophenone compound and its application in resisting light pollution, and is characterized by that it utilizes benzophenone and excess alkali metal sodium to produce benzophenone disodium initiator, and makes it react with toluene-2, 4-diisocyanate under the action of catalyst, then makes it react with 4, 4' -dihydroxy benzophenone to prepare high molecular benzophenone compound.

In recent years, there has been much interest in hydrogen abstraction-type photoinitiation systems consisting of photoinitiators and co-initiator amines. However, with the development of science and technology, people put forward higher requirements on photoinitiators, including good photoinitiation performance, good compatibility with a system, low mobility, low toxicity, good environmental compatibility and high storage stability. Therefore, there is a need to develop a photo-initiation system that is stable, low-toxicity, efficient, environmentally friendly, and has good compatibility with the curing system. In addition, the photoinitiator is made to be large molecules, and has many advantages, such as: (1) low odor and low volatility; (2) the anti-migration performance is good, the toxicity is low, and the environmental compatibility is better; (3) the compatibility of the resin is good; (4) reduce yellowing, etc.

The development of vinyl chloride-vinyl acetate copolymer started in the 20 th century and generally has high pigment dispersibility, excellent film-forming property and solvent release property, flexibility, high wear resistance, chemical resistance, flame retardance, good solubility and manufacturability and wide adjustability. Therefore, vinyl chloride-vinyl acetate copolymer is a preferred binder resin for industrial coating materials and inks. Especially, the UV-curable UV-.

Disclosure of Invention

Aiming at the problems of low photoinitiation efficiency, poor compatibility with a system and high surface mobility of the traditional micromolecule photoinitiation performance. The invention provides a vinyl chloride-vinyl benzophenone macromolecular photoinitiator and a preparation method thereof.

The vinyl chloride-vinyl benzophenone macromolecular photoinitiator prepared by the method contains benzophenone and tertiary amine structures on the same molecular chain, so that the efficiency of generating active species by photosensitive decomposition can be improved, the photoinitiation efficiency is higher, the compatibility with an initiation system is increased due to the vinyl chloride-vinyl benzophenone macromolecular photoinitiator contains vinyl chloride and polyurethane structures, and the surface migration of the photoinitiator is greatly reduced due to the macromolecular structure of the photoinitiator.

The technical scheme of the invention is as follows:

the invention starts from the molecular structure design, generates a polyurethane molecular structure blocked by diisocyanate through the molecular design, and reacts with vinyl chloride-vinyl acetate copolymer containing hydroxyl and p-hydroxybenzophenone to synthesize the vinyl chloride-vinyl benzophenone macromolecular photoinitiator with the two ends of a polyurethane molecular chain connected with tertiary amine structures.

The chemical structural formula of the macromolecular photoinitiator prepared by the invention is as follows:

wherein R1-OH is hydroxyl or hydroxyalkyl structure.

The invention provides a vinyl chloride-vinyl benzophenone macromolecular photoinitiator and a preparation method thereof, comprising the following steps (expressed by the mole fraction of functional groups, and nitrogen is introduced for protection in the whole reaction process):

(a) 4-4.5 parts of diisocyanate and 2 parts of catalyst are dissolved in 40 parts of ethyl acetate, 2 parts of N-methyldiethanolamine are dissolved in 20 parts of ethyl acetate and added into a constant pressure dropping funnel, the dropping speed is controlled to be 4-5 s/drop, after magnetic stirring is carried out for 2-4h at room temperature, the reaction is stopped when hydroxyl is detected to disappear by infrared, and the ethyl acetate solution of the intermediate product PU-1 is obtained.

(b) Dissolving 1.5-1.7 parts of p-hydroxybenzophenone in 20 parts of ethyl acetate, adding the solution into a constant-pressure dropping funnel, controlling the dropping speed to be 4-5 s/drop, dropping the solution into a completely dissolved ethyl acetate solution of PU-1, continuing to stir by magnetic force for 0.5h after dropping, continuing to use the constant-pressure dropping funnel to drop 10 parts of ethyl acetate solution in which 1 part of hydroxyl ternary vinyl chloride-acetate resin is dissolved, controlling the dropping speed to be 4-5 s/drop, stopping reaction when an infrared detection-NCO group disappears after the magnetic stirring is carried out for 12-24h at room temperature, drying an organic layer by anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure to remove the solvent, and carrying out vacuum drying to obtain a target product PV-PU.

The reaction formula of the macromolecular photoinitiator is as follows:

the molar ratio of diisocyanate to N-methyldiethanolamine is as follows: 4-4.5:2, and the molar ratio of the hydroxyl ternary vinyl chloride-acetate copolymer resin to the p-hydroxybenzophenone is 1: 1.5-1.7.

The catalyst is any one of zinc isooctanoate, stannous octoate, dibutyltin dilaurate and dimethyl tin maleate.

The diisocyanate is any one of 4, 4' -diphenylmethane diisocyanate (MDI), toluene-2, 4-diisocyanate (TDI), Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI).

The molar ratio of the PU-1 to the p-hydroxybenzophenone is 1:1.

The invention has the beneficial effects that:

the prepared vinyl chloride-vinyl benzophenone macromolecular photoinitiator has the following advantages: (1) the benzophenone and the tertiary amine structure are simultaneously contained on the same molecular chain, so that the photoinitiation efficiency is higher; (2) simultaneously contains a vinyl chloride-vinyl acetate copolymer and a polyurethane structure, and increases the compatibility with an initiation system; (3) the vinyl chloride-vinyl acetate resin group introduced into the molecular structure of the photoinitiator has rich-OH, and the introduced tertiary amine structure has more-NH-which can form a hydrogen bond structure with water molecules, so that the solubility of the photoinitiator in water is improved; (4) the vinyl chloride-vinyl acetate resin group is introduced into the molecular structure of the photoinitiator, so that the flexibility of the aqueous photocureable coating can be improved; (5) the surface migration of the photoinitiator is greatly reduced by the macro-polymerization of the photoinitiator; (6) the molecular structure is designable; (7) the adhesive has better adhesive force to base materials such as PVC and the like; (8) has excellent color developing property to the pigment.

Detailed Description

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