CN113698382B - Novel thioxanthone visible light initiator and preparation method and application thereof - Google Patents

Novel thioxanthone visible light initiator and preparation method and application thereof Download PDF

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CN113698382B
CN113698382B CN202110911791.3A CN202110911791A CN113698382B CN 113698382 B CN113698382 B CN 113698382B CN 202110911791 A CN202110911791 A CN 202110911791A CN 113698382 B CN113698382 B CN 113698382B
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thioxanthone
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dihydroxythioxanthone
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ethyl
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唐红定
吴翔
熊英
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Wuhan University WHU
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Abstract

The invention discloses a novel thioxanthone visible light initiator, a preparation method and application thereof, belonging to the field of free radical visible light initiators. The structural formula of the novel thioxanthone is shown as follows. Under the protection of inert gas, dissolving 2, 4-dihydroxythioxanthone in an organic solvent, adding inorganic base, using catalytic amount of 2, 6-di-tert-butyl-p-cresol and/or potassium iodide, adding halogenated hydrocarbon or benzene sulfonate compound in one step or in batches, heating and reacting until the 2, 4-dihydroxythioxanthone completely reacts to obtain the novel thioxanthone. The novel thioxanthone is applied to various free radical photo-polymerization systems of prepolymers containing mercaptan-olefin, acrylate, styrene, vinyl ether and the like, and is used for modifying polyurethane, polyester resin, acrylate resin and epoxy resin. The novel thioxanthone has high photoinitiation efficiency, can participate in polymerization and can modify a photopolymerization material.
Figure DDA0003204001010000011

Description

Novel thioxanthone visible light initiator and preparation method and application thereof
Technical Field
The invention belongs to the field of free radical visible light initiators, and particularly relates to a novel thioxanthone visible light initiator, and a preparation method and application thereof.
Background
Photoreaction is a rapid chemical process triggered by light, and plays an important role in the synthesis and crosslinking curing of polymers. Due to the 5E characteristics of high efficiency, high quality, environmental protection, energy conservation, controllability and the like, the photopolymerization technology is widely applied to the fields of functional coatings, printing ink, adhesives, photoresist, medical treatment, 3D printing and the like, and is a green environment-friendly technology. Photoinitiators are one of the key components in photopolymerization and photocuring formulations. The thioxanthone derivative has lower triplet energy and higher quantum yield, has good absorptivity in the wavelength range of 360-420nm, is easy to match the emission spectrum of a light source through the regulation and control of absorption spectrum (Polymer Chemistry,2015,6(37):6595.), and has great development and application potential. As a high-efficiency photoinitiator, thioxanthone derivatives are widely applied to the processes of free radical and cationic photopolymerization.
The free radical photoinitiator refers to a compound which can generate free radicals under the condition of illumination and initiate free radical polymerization, and is the most widely used photoinitiator. However, problems such as oxygen inhibition, odor, toxicity, migration, yellowing, etc., which are common to radical photoinitiators and systems (Macromolecules,2013,46(9): 3266; Journal of Polymer Research, 2014,21(9): 559), and further, problems such as oxygen inhibition are more prominent in visible light polymerization systems.
The polyacrylate has the advantages of high curing speed, high efficiency, good optical performance, no yellowing, good storage stability, low Volatile Organic Compound (VOC) content and the like; the introduction of the acrylate group into the thioxanthone can improve the curing rate of the polyurethane film and reduce the film mobility, so that the thioxanthone micromolecule photoinitiator has good compatibility.
Disclosure of Invention
The invention aims to overcome the defects of low initiating activity of a dihydroxythioxanthone photoinitiator in the prior art, high photoinitiator mobility in the obtained polymer, easy yellowing of a film, poor water resistance, poor heat resistance and the like, and provides a novel thioxanthone visible light initiator, and a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme:
a novel thioxanthone has the structural formula:
Figure BDA0003203996990000011
wherein:
R1and R2Is one of the following groups, which may be the same or different:
Figure BDA0003203996990000021
wherein R is3And R4Is methyl or hydrogen;
R5、R6and R7Can be one of the groups shown as follows, can be the same or different:
Figure BDA0003203996990000022
R8alkyl groups such as methyl, ethyl, 2-ethyl-hexyl and the like, and alkenyl groups such as allyl and the like are possible.
m is: m is more than or equal to 2 and less than or equal to 5, and m is a natural number;
n is: n is more than or equal to 0 and less than or equal to 3, and n is a natural number;
R9is a straight chain or side chain alkenyl group such as an alkenylhexyl group, a 3-ethyl-1-alkenylhexyl group, an allyl group, etc.
The preparation method of the novel thioxanthone is shown as the reaction formula in the following formula:
Figure BDA0003203996990000023
the preparation method comprises the following steps: under the protection of inert gas, 2, 4-dihydroxythioxanthone is dissolved in an organic solvent, inorganic base is added, 2, 6-di-tert-butyl-p-cresol and/or potassium iodide with catalytic amount are used, halogenated hydrocarbon or benzene sulfonate compound is added in one time or in batches, and the mixture is heated and reacted until the 2, 4-dihydroxythioxanthone is completely reacted (TLC plate detection). The preparation method also comprises the separation and purification steps: cooling the reaction product, filtering, concentrating the filtrate, and purifying to obtain the novel thioxanthone.
In some embodiments, the method of making further comprises the steps of: the above procedure was repeated with the product of the above procedure replacing 2, 4-dihydroxythioxanthone.
The halogenated hydrocarbon or benzene sulfonate compound comprises CH3(CH2)mX、CH2＝C(R3)COO(CH2)nCH2X、 CH2＝C(R3)CO(OCH(R4)CH2)nOCH(R4)CH2X、SiR5R6R7(CH2)3X、SiR5R6R7CH2X、 R8O(OCH(R4)CH2)nOCH(CH3)CH2X or R9And (4) X. Wherein R is3And R4Is methyl or hydrogen; r5、R6、R7Groups include, but are not limited to, CH3-、CH3O-、CH3CH2O-、CH3OCH2CH2-、CH3CH2OCH2CH2-、
Figure BDA0003203996990000024
(CH3)3Si-O-, etc., R5、R6、R7The groups may be the same or different; r8Alkyl groups such as methyl, ethyl, 2-ethyl-hexyl and the like, and alkenyl groups such as allyl and the like; r9Alkenyl groups which may be linear or branched, such as alkenylhexyl, 2-ethyl-1-alkenylhexyl, allyl, etc.; x is one of chlorine, bromine, iodine, benzene sulfonate and alkyl benzene sulfonate.
The organic solvent comprises acetone, tetrahydrofuran, acetonitrile, N-dimethylformamide and N, N-dimethylacetamide; the inorganic base is anhydrous potassium carbonate (K)2CO3) Anhydrous sodium carbonate (Na)2CO3) Anhydrous cesium carbonate (Cs)2CO3) Or anhydrous sodium phosphate (Na)3PO4) And the like.
The novel thioxanthone is applied as a photoinitiator, and the photoinitiator is a visible light initiator.
The novel thioxanthone can be applied to various free radical photopolymerization systems of prepolymers containing mercaptan-olefins, acrylates, styrenes, vinyl ethers and the like.
The novel thioxanthone is used for modified polyurethane, polyester resin, acrylate resin and epoxy resin. The method for preparing the PUA film by the modified polyurethane acrylate resin comprises the following steps: under the protection of inert gas, 100 parts by mass of polyurethane acrylate resin and 5-20 parts by mass of the novel thioxanthone are uniformly mixed and then spread on a glass slide or a glass plate, and after the solvent is placed and volatilized, the glass slide or the glass plate is placed under a xenon lamp light source for irradiation and curing for 10-40 min.
The invention takes 2, 4-dihydroxyl thioxanthone as the basis, introduces functional groups into the molecular structure of the thioxanthone to reduce the toxicity and the mobility of the photoinitiator and provides the modification function of a cross-linked polymer, thereby developing the novel, high-efficiency and wide-application-range photoinitiator. Such photoinitiators show good absorption properties in the visible region (405 nm). Compared with the traditional photoinitiator, the multifunctional photoinitiator not only has higher polymerization efficiency, but also has more excellent service performance of a resin film initiated by the multifunctional photoinitiator, such as low photoinitiator mobility, low odor, no yellowing and good storage stability. If the multifunctional photoinitiator contains an organic silicon chain in the molecular structure, the film is additionally endowed with the characteristics of excellent heat resistance, hydrophobic surface, lower water absorption rate and ethanol absorption rate and the like, so that various performances of the film are improved to a great extent, and the application range of the material is enlarged.
The invention has the advantages and beneficial effects that:
(1) the photoinitiation efficiency is high. The research of photopolymerization kinetics shows that the thioxanthone photoinitiator can efficiently initiate the polymerization of free radical monomers under the irradiation of visible light.
(2) The self-polymerization of the photoinitiator greatly reduces the content of free photoinitiator after polymerization. If the molecular structure contains unsaturated bonds, such as acrylate double bonds, silicon vinyl double bonds or double bonds in unsaturated hydrocarbon, the prepared thioxanthone photoinitiator can participate in polymerization by utilizing the acrylate unsaturated double bonds contained in the thioxanthone photoinitiator when initiating free radical polymerization, so that the content of the free photoinitiator after polymerization is greatly reduced.
(3) Modifying function of the photopolymerisable material. If some modifying groups such as organic silicon chain links are introduced into the molecular structure of the photoinitiator, the surface performance of the photopolymerisable polymer can be changed, the water resistance and ethanol resistance of the film are obviously enhanced, and the thermal stability of the film is improved.
Drawings
FIG. 1 is an FT-IR spectrum of 2, 4-bis (acryloyloxy-1-butoxy) thioxanthone prepared in example 1.
FIG. 2 is a schematic representation of 2, 4-bis (acryloyloxy-1-butoxy) thioxanthone prepared in example 11H-NMR spectrum.
FIG. 3 is a schematic representation of 2, 4-bis (acryloyloxy-1-butoxy) thioxanthone prepared in example 113C-NMR spectrum.
FIG. 4 is a UV-vis spectrum of 2, 4-bis (acryloyloxy-1-butoxy) thioxanthone prepared in example 1.
FIG. 5 is a graph of the kinetics of HDDA initiation by 2, 4-bis (acryloyloxy-1-butoxy) thioxanthone prepared in example 1.
Detailed Description
The features and advantages of the present invention will be further understood from the following detailed description taken in conjunction with the accompanying drawings. The examples provided are merely illustrative of the method of the present invention and do not limit the remainder of the disclosure in any way.
Example 1.
Figure BDA0003203996990000041
Wherein R is1And R2Is composed of
Figure BDA0003203996990000042
R3-H; preparation of m-3
Adding 0.25g (1mmol) of 2, 4-dihydroxythioxanthone and 20mL of acetone into a 50mL two-mouth bottle, stirring the mixture in an argon atmosphere until the mixture is completely dissolved, adding 0.35g of anhydrous potassium carbonate, 0.2g of 2, 6-di-tert-butyl-p-cresol and 0.1g of potassium iodide, stirring the mixture for 30min, adding 0.8g (5mmol) of 4-chlorobutyl acrylate, heating the mixture to 55 ℃ in an argon protective atmosphere, reacting the mixture for 16h, and detecting the reaction by TLC. The reaction system is filtered by suction, the filtrate is concentrated, and silica gel column chromatography (eluent, PE: EA ═ 10:1, v/v) is carried out to obtain the target compound.
FT-IR provided in FIGS. 1-3,1H and13c NMR confirmed the evidence of the structure of the target compound 2, 4-bis (acryloyloxy-1-butoxy) thioxanthone. The FT-IR spectrum of FIG. 1 appears at 1721cm-1And 1635cm-1The absorption peak can be assigned to the ketone carbonyl stretching vibration peak of the ester carbonyl of the acrylate and the thioxanthone in the molecular structure; 1601. 1437cm-1C ═ C stretching vibration characteristic absorption peak of anthracene ring skeleton and unsaturated acrylic ester bond; 1295. 983cm-1C-H bending vibration characteristic peak on C which is unsaturated acrylic ester bond; 1268cm-1The peak is the C-O-C stretching vibration characteristic peak of unsaturated acrylic ester bond. As can be seen from FIG. 2, the peaks at chemical shifts 6.7-9.0ppm can be assigned to the proton peaks on the anthracycline, and the formants at 5.8, 6.1 and 6.4ppm are the-CH ═ CH in the acrylate structure2Upper proton peak, 4.1-4.4ppm is O-CH2A proton peak of-O-CH at 1.8 to 2.1ppm2-CH2Beta-methylene proton peak of (a). In FIG. 3, a carbon peak of C ═ O in the thioxanthone structure at chemical shift of 179.9ppm, a carbon peak of O ═ C in the acrylate structure at 166.5ppm, C ═ C absorptions in the acrylate structure at 127.0 and 130.0ppm, resonance absorptions of two C atoms bonded to adjacent ether bonds in the thioxanthone structure at 158.3 and 155.1ppm, and methylene groups O-CH in the ether structure at 65 to 75ppm can be seen2Absorption peak, 25-30ppm beta-methylene O-CH2-CH2The absorption peak of (1). These results indicate that 2, 4-bis (acryloyloxy-1-butoxy) thioxanthone has been successfully prepared. As can be seen from the UV-vis spectrum of FIG. 4, the maximum absorption wavelength of 2, 4-bis (acryloyloxy-1-butoxy) thioxanthone is 405nm, and the maximum absorption wavelength thereof is in the visible region. FIG. 5 shows the kinetics of initiation of HDDA. 2, 4-bis (acryloyloxy-1-butoxy) thioxanthone can also successfully initiate polymerizationFree radical polymerization of urethane acrylate resin. These photopolymerization experimental results demonstrate that 2, 4-bis (acryloyloxy-1-butoxy) thioxanthone is an excellent visible light initiator.
Example 2.
Figure BDA0003203996990000051
Wherein R is1And R2Is composed of
Figure BDA0003203996990000052
R3＝-CH3(ii) a Preparation of m-2
Adding 0.25g (1mmol) of 2, 4-dihydroxythioxanthone and 20mL of acetonitrile into a 50mL two-mouth bottle, stirring in an argon atmosphere until the materials are completely dissolved, adding 0.27g of anhydrous sodium carbonate and 0.2g of 2, 6-di-tert-butyl-p-cresol, stirring for 30min, adding 1.03g (5mmol) of 3-bromopropyl methacrylate, heating to 55 ℃ in an argon protective atmosphere, reacting for 16h, and detecting the reaction by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 10:1, v/v) to obtain the target compound.
Example 3.
Figure BDA0003203996990000053
Wherein R is1And R2Is composed of
Figure BDA0003203996990000054
R3-H; preparation of m-4
Adding 0.25g (1mmol) of 2, 4-dihydroxythioxanthone and 20mL of tetrahydrofuran into a 50mL two-neck flask, stirring in an argon atmosphere until the materials are completely dissolved, adding 0.35g of anhydrous potassium carbonate, 0.2g of 2, 6-di-tert-butyl-p-cresol and 0.1g of potassium iodide, stirring for 30min, adding 0.88g (5mmol) of 5-chloropentyl acrylate, heating to 60 ℃ in an argon protective atmosphere, reacting for 16h, and detecting the reaction by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 10:1, v/v) to obtain the target compound.
Example 4.
Figure BDA0003203996990000055
Wherein R is1And R2Is composed of
Figure BDA0003203996990000056
R3-H; preparation of m-5
Adding 0.25g (1mmol) of 2, 4-dihydroxythioxanthone and 20mL of N, N-dimethylacetamide into a 50mL two-mouth bottle, stirring in an argon atmosphere until the materials are completely dissolved, adding 0.27g of anhydrous sodium carbonate and 0.2g of 2, 6-di-tert-butyl-p-cresol, stirring for 30min, adding 1.17g (5mmol) of 6-bromon-hexyl acrylate, heating to 85 ℃ in an argon protective atmosphere, reacting for 16h, and detecting the reaction by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 10:1, v/v) to obtain the target compound.
Example 5.
Figure BDA0003203996990000057
Wherein R is1And R2Is composed of
Figure BDA0003203996990000058
R3＝-CH3；R4-H; preparation of n-0
Adding 0.25g (1mmol) of 2, 4-dihydroxythioxanthone and 20mL of N, N-dimethylformamide into a 50mL two-neck flask, stirring the mixture in an argon atmosphere until the mixture is completely dissolved, adding 0.27g of anhydrous sodium carbonate, 0.2g of 2, 6-di-tert-butyl-p-cresol and 0.1g of potassium iodide, stirring the mixture for 30min, adding 0.74g (5mmol) of 2-chloroethyl methacrylate, heating the mixture to 55 ℃ in an argon protective atmosphere, reacting the mixture for 16h, and detecting the reaction completely by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 15:1, and v/v) to obtain the target compound.
Example 6.
Figure BDA0003203996990000061
Wherein R is1And R2Is composed of
Figure BDA0003203996990000062
R3＝-H；R4＝-CH3；nPreparation of ═ 3
A50 mL two-neck flask was charged with 0.25g (1mmol) of 2, 4-dihydroxythioxanthone and 20mL of tetrahydrofuran, stirred under argon atmosphere until completely dissolved, then 0.27g of anhydrous sodium carbonate, 0.2g of 2, 6-di-tert-butyl-p-cresol and 0.1g of potassium iodide were added, stirred for 30min, then 1.57g (5mmol) of 2- (2- (p-toluenesulfonyloxypropoxy) -propoxy) propyl acrylate (obtained by condensing 2- (2- (2- (2-hydroxypropoxy) -propoxy) propyl acrylate with p-toluenesulfonyl chloride) was added, the temperature was raised to 55 ℃ under argon atmosphere for 16h, and the reaction was detected by TLC to be complete. The reaction system is filtered by suction, the filtrate is concentrated, and silica gel column chromatography (eluent, PE: EA ═ 15:1, v/v) is carried out to obtain the target compound.
Example 7.
Figure BDA0003203996990000063
Wherein R is1And R2Is composed of
Figure BDA0003203996990000064
R3＝R4-H; preparation of n-2
Adding 0.25g (1mmol) of 2, 4-dihydroxythioxanthone and 20mL of tetrahydrofuran into a 50mL two-mouth bottle, stirring the mixture in an argon atmosphere until the mixture is completely dissolved, adding 0.27g of anhydrous sodium carbonate, 0.2g of 2, 6-di-tert-butyl-p-cresol and 0.1g of potassium iodide, stirring the mixture for 30min, adding 1.57g (5mmol) of p-toluenesulfonyloxyethoxyethoxyethoxyethyl acrylate, heating the mixture to 55 ℃ in an argon protective atmosphere, reacting the mixture for 16h, and detecting the reaction to be complete by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 15:1, and v/v) to obtain the target compound.
Example 8.
Figure BDA0003203996990000065
Wherein R is1And R2Is composed of
Figure BDA0003203996990000066
R3＝R4＝＊-CH3Preparation of n-1
0.25g (1mmol) of 2, 4-dihydroxythioxanthone and 20mL of tetrahydrofuran are added into a 50mL two-neck flask, stirred in argon atmosphere until the materials are completely dissolved, then 0.27g of anhydrous sodium carbonate, 0.2g of 2, 6-di-tert-butyl-p-cresol and 0.1g of potassium iodide are added, stirred for 30min, then 1.71g (5mmol) of 2-p-toluenesulfonyloxyethoxy propyl methacrylate (obtained by condensing 2-hydroxypropoxy propyl methacrylate and p-toluenesulfonyl chloride) is added, the temperature is raised to 55 ℃ in argon protection atmosphere for reaction for 16h, and TLC detection shows that the reaction is complete. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 10:1, v/v) to obtain the target compound.
Example 9.
Figure BDA0003203996990000067
Wherein R is1And R2Is 3-ethyl-1-alkenylhexyl,
Figure BDA0003203996990000068
preparation of
Adding 0.25g (1mmol) of 2, 4-dihydroxythioxanthone and 20mL of tetrahydrofuran into a 50mL two-mouth bottle, stirring in an argon atmosphere until the materials are completely dissolved, adding 0.27g of anhydrous sodium carbonate and 0.1g of potassium iodide, stirring for 30min, adding 0.73g (5mmol) of 6-chloro-3-ethyl-1-hexene, heating to 55 ℃ in an argon protective atmosphere, reacting for 16h, and detecting the reaction by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 8:1, v/v) to obtain the target compound.
Example 10.
Figure BDA0003203996990000071
Preparation of
(1) 1.2g (4.9mmol) of 2, 4-dihydroxythioxanthone and 40mL of acetone are added into a 250mL single-neck bottle, stirred in argon atmosphere until the materials are completely dissolved, then 0.5g of anhydrous sodium phosphate, 0.15g of potassium iodide and 0.50g (2.5mmol) of 3-chloropropyltrimethoxysilane are added, the temperature is raised to 60 ℃ in argon atmosphere, the reaction is carried out for 3 days, and the TLC detection reaction is complete. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 4:1, v/v) to obtain 2-hydroxy-4- ((trimethoxy) silicon propoxy) thioxanthone.
(2) Adding 0.36g (1mmol) of 2-hydroxy-4- ((trimethoxy) silicopropoxy) thioxanthone and 20mL of acetone into a 50mL two-mouth bottle, stirring the mixture in an argon atmosphere until the mixture is completely dissolved, adding 0.35g of anhydrous potassium carbonate, 0.2g of 2, 6-di-tert-butyl-p-cresol and 0.1g of potassium iodide, stirring the mixture for 30min, adding 0.4g (2.5mmol) of 4-chlorobutyl acrylate, heating the mixture to 55 ℃ in an argon protective atmosphere, reacting the mixture for 16h, and detecting the reaction to be complete by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 20:1, v/v) to obtain the target compound.
Example 11.
Figure BDA0003203996990000072
Wherein R is1And R2Is composed of
Figure BDA0003203996990000073
Preparation of
Adding 0.25g (1mmol) of 2, 4-dihydroxythioxanthone and 20mL of tetrahydrofuran into a 50mL two-neck flask, stirring in an argon atmosphere until the materials are completely dissolved, adding 0.27g of anhydrous sodium carbonate and 0.1g of potassium iodide, stirring for 30min, adding 0.92g (5mmol) of 3-chloropropylmethyldimethoxysilane, heating to 55 ℃ in an argon protective atmosphere, reacting for 16h, and detecting the reaction by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 20:1, v/v) to obtain the target compound.
Example 12.
Figure BDA0003203996990000074
Wherein R is1And R2Is composed of
Figure BDA0003203996990000075
Preparation of
Adding 0.25g (1mmol) of 2, 4-dihydroxythioxanthone and 20mL of tetrahydrofuran into a 50mL two-neck flask, stirring in an argon atmosphere until the materials are completely dissolved, adding 0.27g of anhydrous sodium carbonate and 0.1g of potassium iodide, stirring for 30min, adding 1.61g (5mmol) of 3-chloropropylmethylbis (dimethylvinyl) siloxysilane, heating to 55 ℃ in an argon protective atmosphere, reacting for 16h, and detecting the reaction completion by TLC. The reaction system is filtered by suction, the filtrate is concentrated, and silica gel column chromatography (eluent, PE: EA ═ 20:1, v/v) is carried out to obtain the target compound.
Example 13.
Figure BDA0003203996990000081
Preparation of
(1) 1.2g (4.9mmol) of 2, 4-dihydroxythioxanthone and 40mL of acetone are added into a 250mL single-neck bottle, stirred in an argon atmosphere until the materials are completely dissolved, then 0.5g of anhydrous sodium phosphate, 0.15g of potassium iodide and 0.60g (2.5mmol) of chloropropyltriethoxysilane are added, the temperature is raised to 60 ℃ in an argon protective atmosphere, the reaction is carried out for 3 days, and the TLC detection shows that the reaction is complete. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA ═ 5:1, v/v) to obtain 2-hydroxy-4- ((triethoxy) silicon propoxy) thioxanthone.
(2) Adding 0.45g (1mmol) of 2-hydroxy-4- ((triethoxy) silicon propoxy) thioxanthone and 20mL of acetone into a 50mL two-mouth bottle, stirring the mixture in an argon atmosphere until the materials are completely dissolved, adding 0.35g of anhydrous potassium carbonate, 0.2g of 2, 6-di-tert-butyl-p-cresol and 0.1g of potassium iodide, stirring the mixture for 30min, adding 0.56g (2.5mmol) of 3-chloropropyl methacrylate, heating the mixture to 55 ℃ in an argon protective atmosphere, reacting the mixture for 16h, and detecting the reaction completion by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 15:1, and v/v) to obtain the target compound.
Example 14.
Figure BDA0003203996990000082
Preparation of
(1) 1.2g (4.9mmol) of 2, 4-dihydroxythioxanthone and 40mL of acetone are added into a 250mL single-neck bottle, stirred in an argon atmosphere until the materials are completely dissolved, then 0.5g of anhydrous sodium phosphate, 0.15g of potassium iodide and 0.86g (2.5mmol) of chloromethyl tri (trimethyl) siloxane are added, the temperature is raised to 60 ℃ in an argon protective atmosphere, the reaction is carried out for 3 days, and the TLC detection reaction is complete. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA ═ 5:1, v/v) to obtain 2-hydroxy-4- ((tri (trimethyl) siloxy) silicon methoxyl) thioxanthone.
(2) 0.55g (1mmol) of 2-hydroxy-4- ((tri (trimethyl) siloxy) thioxanthone and 20mL of tetrahydrofuran are added into a 50mL two-neck flask, stirred in an argon atmosphere until the materials are completely dissolved, then 0.27g of anhydrous sodium carbonate, 0.2g of 2, 6-di-tert-butyl-p-cresol and 0.1g of potassium iodide are added, after stirring for 30min, 0.85g (2.5mmol) of 2- (2- (p-toluenesulfonyloxypropoxy) propyl methacrylate (obtained by condensing 2- (2-hydroxypropoxy) propyl methacrylate and p-toluenesulfonyl chloride) is added, the temperature is raised to 60 ℃ in an argon protective atmosphere, the reaction is carried out for 16h, and the reaction is detected to be complete by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 20:1, v/v) to obtain the target compound.
Example 15.
Figure BDA0003203996990000091
Preparation of
(1) 1.2g (4.9mmol) of 2, 4-dihydroxythioxanthone and 40mL of acetone are added into a 250mL single-neck bottle, stirred in argon atmosphere until the materials are completely dissolved, then 0.5g of anhydrous sodium phosphate, 0.15g of potassium iodide and 0.93g (2.5mmol) of 3-chloropropyltris (trimethyl) siloxane are added, the temperature is raised to 60 ℃ in argon atmosphere for reaction for 3 days, and the reaction is detected to be complete by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 5:1, v/v) to obtain 2-hydroxy-4- ((tri (trimethyl) siloxy) silaprop-1-oxy) thioxanthone.
(2) 0.58g (1mmol) of 2-hydroxy-4- ((tri (trimethyl) siloxy) silapropan-1-oxy) thioxanthone and 20mL of tetrahydrofuran are added into a 50mL two-neck flask, stirred in an argon atmosphere until completely dissolved, then 0.27g of anhydrous sodium carbonate, 0.2g of 2, 6-di-tert-butyl-p-cresol and 0.1g of potassium iodide are added, stirred for 30min, then 0.85g (2.5mmol) of 2- (2- (p-tolylsulfonyloxypropoxy) propoxy) propyl methacrylate (obtained by condensing 2- (2-hydroxypropoxy) propyl methacrylate and p-toluenesulfonyl chloride) is added, the temperature is raised to 60 ℃ in an argon protective atmosphere, the reaction is carried out for 16h, and the reaction is detected completely by TLC. The reaction system is filtered by suction, the filtrate is concentrated, and silica gel column chromatography (eluent, PE: EA is 18:1, v/v) is carried out to obtain the target compound.
Example 16.
Figure BDA0003203996990000092
Preparation of (2)
(1) 1.2g (4.9mmol) of 2, 4-dihydroxythioxanthone and 40mL of acetone are added into a 250mL single-neck bottle, stirred in an argon atmosphere until the materials are completely dissolved, then 0.5g of anhydrous sodium phosphate, 0.15g of potassium iodide and 0.82g (2.5mmol) of chloropropyltris (methoxy) ethoxysilane are added, the temperature is raised to 60 ℃ in an argon protective atmosphere, the reaction is carried out for 3 days, and the TLC detection reaction is complete. The reaction system is filtered by suction, the filtrate is concentrated, and silica gel column chromatography (eluent, PE: EA is 4:1, v/v) is carried out to obtain 2-hydroxy-4- (3- (tri (methoxy) ethoxy) silicon propoxy) thioxanthone.
(2) 0.54g (1mmol) of 2-hydroxy-4- (3- (tri (methoxy) ethoxy) silicon propoxy) thioxanthone and 20mLN, N-dimethylacetamide are added into a 50mL two-mouth bottle, stirred in argon atmosphere until completely dissolved, then 0.27g of anhydrous sodium carbonate and 0.2g of 2, 6-di-tert-butyl-p-cresol are added, stirred for 30min, then 0.37g (2.5mmol) of 2-chloroethyl methacrylate is added, the temperature is raised to 85 ℃ in argon protective atmosphere for reaction for 16h, and TLC detection is carried out until the reaction is complete. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 20:1, v/v) to obtain the target compound.
Example 17.
Figure BDA0003203996990000101
Preparation of (2)
(1) 1.2g (4.9mmol) of 2, 4-dihydroxythioxanthone and 40mL of acetone are added into a 250mL single-neck bottle, stirred in an argon atmosphere until the materials are completely dissolved, then 0.5g of anhydrous sodium phosphate, 0.15g of potassium iodide and 0.85g (2.5mmol) of chloromethyl tri (ethoxy) ethoxysilane are added, the temperature is raised to 60 ℃ in an argon protective atmosphere, the reaction is carried out for 3 days, and the TLC detection reaction is complete. The reaction system is filtered by suction, the filtrate is concentrated, and silica gel column chromatography (eluent, PE: EA ═ 5:1, v/v) is carried out to obtain 2-hydroxy-4- (3- (triethoxyethoxy) silicon propoxy) thioxanthone.
(2) 0.59g (1mmol) of 2-hydroxy-4- (3- (triethoxyethoxy) silicopropoxy) thioxanthone and 20mL of tetrahydrofuran are added into a 50mL two-neck flask, stirred in an argon atmosphere until the thioxanthone and the tetrahydrofuran are completely dissolved, then 0.27g of anhydrous sodium carbonate, 0.2g of 2, 6-di-tert-butyl-p-cresol and 0.1g of potassium iodide are added, after stirring for 30min, 0.78g (2.5mmol) of 2- (2- (2- (2- (p-tolylsulfonyloxy) propoxy) propyl acrylate (obtained by condensing 2- (2- (2- (2- (2-hydroxypropoxy) -propoxy) propyl acrylate and p-toluenesulfonyl chloride) are added, the temperature is raised to 55 ℃ in an argon protective atmosphere, reaction is carried out for 16h, the reaction was complete by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 20:1, v/v) to obtain the target compound.
Example 18.
Figure BDA0003203996990000102
Preparation of
(1) 1.2g (4.9mmol) of 2, 4-dihydroxythioxanthone and 40mL of acetone are added into a 250mL single-neck bottle, stirred in an argon atmosphere until the materials are completely dissolved, then 0.5g of anhydrous sodium phosphate, 0.15g of potassium iodide and 0.4g (2.5mmol) of 6-bromo-1-hexene are added, the temperature is raised to 60 ℃ in an argon protective atmosphere, the reaction is carried out for 3 days, and the TLC detection reaction is complete. The reaction system is filtered by suction, the filtrate is concentrated, and silica gel column chromatography is carried out (eluent, PE: EA is 4:1, v/v) to obtain the 2-hydroxy-4- (6-alkenyl hexyl) thioxanthone.
(2) 0.32g (1mmol) of 2-hydroxy-4- (6-alkenylhexyl) thioxanthone and 20mLN, N-dimethylacetamide are added into a 50mL two-mouth bottle, stirred in argon atmosphere until completely dissolved, then 0.27g of anhydrous sodium carbonate and 0.2g of 2, 6-di-tert-butyl-p-cresol are added, stirred for 30min, then 0.56g (2.5mmol) of 6-bromo-N-pentyl acrylate are added, the temperature is raised to 85 ℃ in argon protection atmosphere for reaction for 16h, and TLC detects that the reaction is complete. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 15:1, and v/v) to obtain the target compound.
Example 19.
Figure BDA0003203996990000111
Preparation of
(1) Adding 1.2g (4.9mmol) of 2, 4-dihydroxythioxanthone and 40mL of acetone into a 250mL single-neck bottle, stirring the mixture in an argon atmosphere until the mixture is completely dissolved, adding 0.5g of anhydrous sodium phosphate, 0.15g of potassium iodide and 0.19g (2.5mmol) of chloropropene, heating the mixture to 60 ℃ in an argon protective atmosphere, reacting for 3 days, and detecting the reaction by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA ═ 4:1, v/v) to obtain 2-hydroxy-4-allyloxy thioxanthone.
(2) Adding 0.28g (1mmol) of 2-hydroxy-4-allyloxy thioxanthone and 20mL of N, N-dimethylacetamide into a 50mL two-mouth bottle, stirring the mixture in an argon atmosphere until the mixture is completely dissolved, adding 0.27g of anhydrous sodium carbonate and 0.2g of 2, 6-di-tert-butyl-p-cresol, stirring the mixture for 30min, adding 0.58g (2.5mmol) of 6-bromo-N-hexyl acrylate, heating the mixture to 85 ℃ in an argon protective atmosphere, reacting the mixture for 16h, and detecting the reaction completely by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 15:1, and v/v) to obtain the target compound.
Example 20.
Figure BDA0003203996990000112
Preparation of
A250 mL single neck flask was charged with 1.2g (4.9mmol) of 2, 4-dihydroxythioxanthone and 40mL of acetone, stirred under argon atmosphere to dissolve completely, then 0.5g of anhydrous sodium phosphate, 0.15g of potassium iodide and 6.27g (15mmol) of p-tolylsulfonic acid-1-1- ((((1-methoxy) -2-propoxy) -2-propyl ester (obtained by condensing 1- (2- (2- (2-methoxy-1-methylethoxy) propanol with p-toluenesulfonyl chloride) were added, and the reaction was allowed to warm to 60 ℃ under argon atmosphere for 3 days and complete by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 10:1, v/v) to obtain the target compound.
Example 21.
Figure BDA0003203996990000113
Preparation of
A250 mL single-neck flask was charged with 1.2g (4.9mmol) of 2, 4-dihydroxythioxanthone and 40mL of acetone, stirred under argon atmosphere until completely dissolved, then 0.5g of anhydrous sodium phosphate, 0.15g of potassium iodide and 5.00g (15mmol) of p-toluenesulfonic acid- (2- (2- (2-ethoxyethoxy) -ethoxy) ethyl ester (obtained by condensing 2- (2- (2-ethoxyethoxy) ethoxy) ethanol with p-toluenesulfonyl chloride) were added, the mixture was heated to 60 ℃ under argon atmosphere and reacted for 3 days, and the reaction was detected by TLC to be complete. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 10:1, v/v) to obtain the target compound.
Example 22.
Figure BDA0003203996990000121
Preparation of
1.2g (4.9mmol) of 2, 4-dihydroxythioxanthone and 40mL of acetone are added into a 250mL single-neck flask, stirred in argon atmosphere until completely dissolved, then 0.5g of anhydrous sodium phosphate, 0.15g of potassium iodide and 5.00g (15mmol) of p-toluenesulfonic acid-2- (2- (2-ethyl-1-hexyloxy) -ethoxy) ethyl ester (obtained by condensing diethylene glycol mono (2-ethyl-1-hexyloxy) ether and p-toluenesulfonyl chloride) are added, the temperature is raised to 60 ℃ in argon atmosphere for reaction for 3 days, and the reaction is completely detected by TLC. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 12:1, v/v) to obtain the target compound.
Example 23.
Figure BDA0003203996990000122
Preparation of
A250 mL single-neck flask was charged with 1.2g (4.9mmol) of 2, 4-dihydroxythioxanthone and 40mL of acetone, stirred under argon atmosphere until completely dissolved, and then charged with 0.5g of anhydrous sodium phosphate, 0.15g of potassium iodide and 3.84g (15mmol) of 2- (allyloxy) ethyl p-toluenesulfonate, and heated to 60 ℃ under argon atmosphere for reaction for 3 days, followed by TLC detection of complete reaction. And (3) carrying out suction filtration on the reaction system, concentrating the filtrate, and carrying out silica gel column chromatography (eluent, PE: EA is 12:1, v/v) to obtain the target compound.
Application example 1.2- (Acryloxy-1-butoxy) -4- ((trimethoxy) silapropoxy) thioxanthone (example 10) initiation of urethane acrylate film preparation and Properties
100 parts by mass of urethane acrylate resin and 5-20 parts by mass of the 2- (acryloyloxy-1-butoxy) -4- ((trimethoxy) silicopropoxy) thioxanthone photoinitiator prepared in the example 10 are uniformly mixed and then are spread on a polytetrafluoroethylene template or a glass plate, after the solvent is basically volatilized after the mixture is placed for 10min, the mixture is placed under a xenon lamp light source to be irradiated and cured for 40min, and then the film is formed.
The water absorption and ethanol absorption data of the silicone-free urethane acrylate resin and the 2- (acryloyloxy-1-butoxy) -4- ((trimethoxy) silyloxy) thioxanthone-modified urethane acrylate resin films containing different mass fractions are shown in table 1. As can be seen from Table 1, as the content of the multifunctional photoinitiator increases, i.e., the content of the organosilicon increases, the water absorption and ethanol absorption of the corresponding PUA film decreases. This indicates that such photoinitiators can introduce silicone chains and thus serve to modify the water and ethanol resistance of polyurethane resins.
TABLE 1 Water absorption and ethanol absorption of PUA films
Figure BDA0003203996990000123
Figure BDA0003203996990000131
1: the mass fraction of the photoinitiator;2: percent organosilicon;3: after 24h, the water absorption of the PUA photocuring film is reduced;4: ethanol absorption rate of the PUA photocured film after 24 hours.
The water contact angle and thermogravimetric analysis data for the silicone-free urethane acrylate resin and the films containing different mass fractions of 2- (acryloyloxy-1-butoxy) -4- ((trimethoxy) silyloxy) thioxanthone-modified urethane acrylate resin are presented in table 2. As is clear from Table 2, the contact angle of the silicone-free PUA film was less than 90 ℃ and hydrophilicity was exhibited. With the increase of the content of the multifunctional photoinitiator, namely the increase of the content of the organic silicon, the contact angles of the correspondingly obtained PUA films are gradually increased and are all larger than 90 degrees, and the PUA films are hydrophobic, which shows that the hydrophobic property of the polyurethane resin can be effectively increased by introducing a small amount of organic silicon chain-containing compound; it can also be seen from Table 2 that with increasing content of multifunctional photoinitiator, i.e.with increasing organosilicon content, the thermal stability of the corresponding PUA film is increased, expressed as T5% all rising gradually, indicating a small amount of siliconeThe introduction of the chain compound can effectively improve the heat resistance and the stability resistance of the polyurethane resin.
TABLE 2 Water contact Angle and thermogravimetric analysis of PUA films
Figure BDA0003203996990000132
1: the mass fraction of the photoinitiator;2: percent organosilicon;3：T5the temperature at which 5% of the weight loss on heating occurred.
Application example 2.2 preparation and Properties of 2, 4-bis ((methyldimethoxy) Silropoxy) thioxanthone (example 11) initiated urethane acrylate film
100 parts by mass of urethane acrylate resin and 5-20 parts by mass of the 2, 4-bis ((methyldimethoxy) silicon propoxy) thioxanthone photoinitiator prepared in the above example 11 are uniformly mixed and then are spread on a polytetrafluoroethylene template or a glass plate, and after the solvent is basically volatilized after the mixture is placed for 10min, the mixture is placed under a xenon lamp light source to be irradiated and cured for 30min, so that a film can be formed.
The water absorption and ethanol absorption data for silicone-free urethane acrylate resins and films containing different mass fractions of 2, 4-bis ((methyldimethoxy) silicon propoxy) thioxanthone-modified urethane acrylate resin are shown in table 3. As can be seen from Table 3, as the content of the multifunctional photoinitiator increases, i.e., the content of the organosilicon increases, the water absorption and ethanol absorption of the corresponding PUA film decreases. This indicates that such photoinitiators can introduce silicone chains and thus serve to modify the water and ethanol resistance of polyurethane resins.
Table 3 Water absorption and ethanol absorption of PUA film
Figure BDA0003203996990000141
1: the mass fraction of the photoinitiator;2: partial percentage of organosilicon;3: after 24h, the water absorption of the PUA photocuring film is reduced;4: ethanol absorption rate of the PUA photocured film after 24 hours.
The water contact angles and thermogravimetric analysis data for silicone-free urethane acrylate resins and films containing different mass fractions of 2, 4-bis ((methyldimethoxy) silapropoxy) thioxanthone-modified urethane acrylate resin are shown in table 4. As is clear from Table 4, the contact angle of the silicone-free PUA film was less than 90 ℃ and hydrophilicity was exhibited. With the increase of the content of the multifunctional photoinitiator, namely the increase of the content of the organic silicon, the contact angles of the correspondingly obtained PUA films are gradually increased and are all larger than 90 degrees, and the PUA films are hydrophobic, which shows that the hydrophobic property of the polyurethane resin can be effectively increased by introducing a small amount of organic silicon chain-containing compound; it can also be seen from Table 4 that, with increasing content of multifunctional photoinitiator, i.e.with increasing organosilicon content, the thermal stability of the corresponding PUA film is increased, which is expressed as T5The percent is gradually increased, which shows that the introduction of a small amount of the compound containing the organosilicon chain can effectively improve the heat resistance and the stability resistance of the polyurethane resin.
TABLE 4 Water contact Angle and thermogravimetric analysis of PUA films
Figure BDA0003203996990000142
1: the mass fraction of the photoinitiator;2: percent organosilicon;3：T5is the temperature at which 5% of the weight loss on heating occurs.
Application example 3.2- (3- (heptamethyltrisiloxy) propoxy) -4- (triethylene glycol acrylate) oxy thioxanthone (example 14) preparation and Properties of initiated urethane acrylate films
100 parts by mass of urethane acrylate resin and 5-20 parts by mass of the 2- (3- (heptamethyltrisiloxy) propoxy) -4- (triethylene glycol acrylate) oxy thioxanthone photoinitiator prepared in the example 14 are uniformly mixed and then are laid on a polytetrafluoroethylene template or a glass plate, after the solvent is basically volatilized after the mixture is placed for 10min, the mixture is placed under a xenon lamp light source to be irradiated and cured for 10min, and then the film can be formed.
The water absorption and ethanol absorption data of the silicone-free urethane acrylate resin and the 2- (3- (heptamethyltrisiloxy) propoxy) -4- (triethylene glycol acrylate) oxy thioxanthone modified urethane acrylate resin films containing different mass fractions are shown in table 5. As can be seen from the table, as the content of the multifunctional photoinitiator increases, i.e., the content of the organosilicon increases, the water absorption rate and the ethanol absorption rate of the corresponding PUA film decrease. This indicates that such photoinitiators can introduce silicone chains and thus serve to modify the water and ethanol resistance of polyurethane resins.
TABLE 5 Water absorption and ethanol absorption of PUA films
Figure BDA0003203996990000151
1: the mass fraction of the photoinitiator;2: percent organosilicon;3: after 24h, the water absorption of the PUA photocuring film is reduced;4: ethanol absorption rate of the PUA photocured film after 24 hours.
The water contact angle and thermogravimetric analysis data of the silicone-free urethane acrylate resin and the 2- (3- (heptamethyltrisiloxy) propoxy) -4- (triethylene glycol acrylate) oxysulfoanthrone-modified urethane acrylate resin films containing different mass fractions are listed in table 6. As is clear from Table 6, the contact angle of the silicone-free PUA film was less than 90 ℃ and hydrophilicity was exhibited. With the increase of the content of the multifunctional photoinitiator, namely the increase of the content of the organic silicon, the contact angles of the correspondingly obtained PUA films are gradually increased and are all larger than 90 degrees, and the PUA films are hydrophobic, which shows that the hydrophobic property of the polyurethane resin can be effectively increased by introducing a small amount of organic silicon chain-containing compound; it can also be seen from Table 6 that, with increasing content of multifunctional photoinitiator, i.e.with increasing organosilicon content, the thermal stability of the corresponding PUA film is increased, which is expressed as T5The percent is gradually increased, which shows that the introduction of a small amount of the compound containing the organosilicon chain can effectively improve the heat resistance and the stability resistance of the polyurethane resin.
TABLE 6 Water contact Angle and thermogravimetric analysis of PUA films
Figure BDA0003203996990000152
Figure BDA0003203996990000161
1: the mass fraction of the photoinitiator;2: percent organosilicon;3：T5the temperature at which 5% of the weight loss on heating occurred.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (7)

1. A novel thioxanthone is characterized in that: the structural formula of the thioxanthone is as follows:
Figure FDA0003611733020000011
wherein:
R1and R2Is one of the groups shown as follows:
Figure FDA0003611733020000012
Figure FDA0003611733020000013
R9
wherein R is3And R4Is methyl or hydrogen; r is5、R6And R7Is one of the groups shown as follows:
Figure FDA0003611733020000014
R8is methyl, ethyl, 2-ethyl-hexyl or allyl;
m is: m is more than or equal to 2 and less than or equal to 5, and m is a natural number;
n is: n is more than or equal to 0 and less than or equal to 3, and n is a natural number;
R9is an alkenylhexyl, 3-ethyl-1-alkenylhexyl or allyl group.
2. A process for the preparation of a novel thioxanthone according to claim 1, characterized in that it comprises the following steps: under the protection of inert gas, dissolving 2, 4-dihydroxythioxanthone in an organic solvent, adding inorganic base, using catalytic amount of 2, 6-di-tert-butyl-p-cresol and/or potassium iodide, adding halogenated hydrocarbon or benzene sulfonate compound in one step or in batches, heating and reacting until the 2, 4-dihydroxythioxanthone completely reacts to obtain novel thioxanthone;
the halogenated hydrocarbon or benzene sulfonate compound is selected from CH3(CH2)mX、CH2＝C(R3)COO(CH2)nCH2X、CH2＝C(R3)CO(OCH(R4)CH2)nOCH(R4)CH2X、SiR5R6R7(CH2)3X、SiR5R6R7CH2X、R8O(OCH(R4)CH2)nOCH(CH3)CH2X or R9X；
Wherein R is3And R4Is methyl or hydrogen; r is5、R6、R7The group being selected from CH3-、CH3O-、CH3CH2O-、CH3OCH2CH2-、CH3CH2OCH2CH2-、
Figure FDA0003611733020000015
(CH3)3Si-O-；R8Is methyl,Ethyl, 2-ethyl-hexyl or allyl; r9Is an alkenylhexyl, 3-ethyl-1-alkenylhexyl or allyl group; x is one of chlorine, bromine, iodine, benzene sulfonate and alkyl benzene sulfonate.
3. The process for the preparation of the novel thioxanthones according to claim 2, characterized in that: the organic solvent is selected from acetone, tetrahydrofuran, acetonitrile, N-dimethylformamide and N, N-dimethylacetamide; the inorganic base is anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous cesium carbonate or anhydrous sodium phosphate.
4. Use of the novel thioxanthones according to claim 1 as photoinitiators.
5. Use according to claim 4, characterized in that: the novel thioxanthone is applied to a free radical photopolymerization system of prepolymer containing mercaptan-olefin, acrylate, styrene and vinyl ether.
6. Use according to claim 4, characterized in that: the novel thioxanthone is used for modified polyurethane, polyester resin, acrylate resin and epoxy resin.
7. Use according to claim 6, characterized in that: the method for preparing the PUA film by the modified polyurethane acrylate resin comprises the following steps: under the protection of inert gas, 100 parts by mass of polyurethane acrylate resin and 5-20 parts by mass of the novel thioxanthone are uniformly mixed and then spread on a glass slide or a glass plate, and after the solvent is placed and volatilized, the glass slide or the glass plate is placed under a xenon lamp light source for irradiation and curing for 10-40 min.
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