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WO2024140063A1 - Thioxanthene sulfonium salt photoinitiator as well as preparation method therefor and use thereof - Google Patents

Thioxanthene sulfonium salt photoinitiator as well as preparation method therefor and use thereof Download PDF

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Publication number
WO2024140063A1
WO2024140063A1 PCT/CN2023/136475 CN2023136475W WO2024140063A1 WO 2024140063 A1 WO2024140063 A1 WO 2024140063A1 CN 2023136475 W CN2023136475 W CN 2023136475W WO 2024140063 A1 WO2024140063 A1 WO 2024140063A1
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optionally
group
salt photoinitiator
independently selected
thioxanthenolsulfonium
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PCT/CN2023/136475
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French (fr)
Chinese (zh)
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钱彬
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常州强力电子新材料股份有限公司
常州强力先端电子材料有限公司
常州强力光电材料有限公司
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Publication of WO2024140063A1 publication Critical patent/WO2024140063A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12—Sulfonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • CN104628540A discloses a method for preparing a cationic photoinitiator (4-octyloxyphenyl) benzyl iodonium hexafluoroantimonate.
  • the preparation method comprises the following steps: in a solvent, iodobenzene diacetate is reacted with 4-octyloxybenzene in the presence of p-toluenesulfonic acid in a one-step process, the reaction temperature is room temperature, the reaction time is 4-24 hours, after the reaction is completed, the solvent is concentrated and removed, and then petroleum ether is added to crystallize to obtain (4-octyloxyphenyl) benzyl iodonium p-toluenesulfonate, and finally ion exchange is performed with sodium hexafluoroantimonate to obtain the product.
  • CN110819203A discloses a cationic photocurable composition and its application in the field of photocuring.
  • the cationic photocurable composition comprises: (A) a cationic reactive compound; (B) an auxiliary agent; and (C) a cationic photoinitiator.
  • cationic photoinitiators In the related art, although more and more attention has been paid to cationic photoinitiators, the types of cationic photoinitiators are still relatively small, and the initiators commonly used in the market are sulfonium salts or iodonium salts. Aromatic sulfides and toxic byproducts are decomposed during the curing process. Aromatic sulfides such as phenylene sulfide have an unpleasant odor, and toxic byproducts such as benzene and toluene are harmful to the human body. Commonly used iodonium salts will also decompose to produce volatile substances such as benzene, toluene or isobutylbenzene, which are harmful to the human body. This seriously limits the application of cationic initiators. For example, such cationic initiators cannot be used in printing inks on food or packaging that comes into contact with food, or in packaging that consumers come into direct contact with.
  • the present application provides a thioxanthene sulfonium salt photoinitiator and a preparation method and application thereof.
  • the prepared thioxanthene sulfonium salt photoinitiator has low mobility, which solves the problem that the existing photoinitiator releases toxic and unpleasant photolysis products.
  • the present application provides a thioxanthone sulfonium salt photoinitiator, wherein the thioxanthone sulfonium salt photoinitiator has a structure as shown in the following formula I:
  • R'1 , R1 , R2 , R3 , R4 , R5 are each independently selected from hydrogen, substituted or unsubstituted C1-C30 alkane C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C2-C20 alkenyl, C2-C20 alkynyl, C6-C14 aryl, C3-C20 heteroaryl, or a substituent having 2 to 30 carbon atoms and containing a CR′′-C structure;
  • the substituted substituents include C6-C14 aryl
  • ⁇ - represents an inorganic anion or an organic anion.
  • a C2-C20 chain alkenyl group containing a C-R"-C structure wherein R" is selected from O, S, an ester group, a thioester group, an amide group or a carbamate group, for example 1, 2, 3, 4, 5, 6, 7 or 8 of the above C-R"-C structures, i.e., the ends of the chain alkenyl group are formed by carbon atoms. If a plurality of these C-R"-C structures are present, they are generally the same.
  • R' 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are independently selected from C3-C10 (eg, C3, C4, C5, C6, C7, C8, C9 or C10) heteroaryl groups.
  • X is selected from F or Cl
  • the catalyst is selected from any one of sulfuric acid, aluminum chloride, ferric chloride, zinc chloride, phosphorus pentoxide-methanesulfonic acid, or a combination of at least two thereof.
  • the organic salt or inorganic salt is selected from any one of potassium hexafluorophosphate, potassium fluoroborate, potassium hexafluoroantimonate, sodium tetrakis(pentafluorophenyl)borate, sodium hexafluoroantimonate, and sodium hexafluoroarsenate.
  • the anion exchange reaction time is 1 to 3 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours.
  • the Friedel-Crafts reaction and the anion exchange reaction are both carried out in the presence of a solvent.
  • the compound containing a vinyl ether group is selected from any one or a combination of at least two of triethylene glycol divinyl ether, 1,4-cyclohexyl dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, glycerol carbonate vinyl ether and dodecyl vinyl ether.
  • the photocurable composition further comprises an auxiliary agent.
  • the weight proportions of the compound containing ethylene oxide group and/or the compound containing vinyl ether group can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts or 60 parts.
  • the weight parts of the oxetane compound can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts.
  • the weight proportions of the thioxanthonesulfonium salt photoinitiator can be 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, or 20 parts.
  • the weight proportions of the auxiliary agent can be 0 parts, 1 parts, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts.
  • the preparation method of the photocurable composition there is no special limitation on the preparation method of the photocurable composition, and the methods commonly used in the art for preparing the photocurable composition are applicable, including but not limited to: mixing and stirring the components in the photocurable composition to obtain the photocurable composition.
  • the photocurable composition can be used to prepare a coating, and the preparation method thereof comprises: coating (including roller coating, brush coating, scraper coating, dip coating, spray coating) the photocurable composition on one side of the substrate, and then irradiating The source is cured to form a coating.
  • the material of the substrate is selected from glass, plastic, ceramic or metal.
  • the present application does not have any special restrictions on the radiation source.
  • the photocurable composition provided in the present application can undergo polymerization reaction and achieve rapid curing.
  • the radiation source illustratively includes, but is not limited to, ultra-high pressure mercury lamp, high pressure mercury lamp, medium pressure mercury lamp, mercury xenon lamp, low pressure mercury lamp, metal halide lamp, xenon lamp, deuterium lamp, chemical lamp, LED lamp, fluorescent lamp, tungsten lamp, Nd-YAG 3 times wave laser, He-Cd laser, nitrogen laser, Xe-C1 excimer laser, Xe-F excimer laser, semiconductor excited solid laser, i-ray, h-ray, g-ray and other active light with a wavelength of 200-500nm; the curing of the composition can also use electron beam, ⁇ -ray, ⁇ -ray, ⁇ -ray, X-ray and neutron ray energy curing, etc., and
  • the thickness of the coating can be designed according to the application, and the thickness of the coating after drying can be selected to be 1 to 200 ⁇ m (for example, 1 ⁇ m, 2 ⁇ m, 5 ⁇ m, 10 ⁇ m, 20 ⁇ m, 40 ⁇ m, 60 ⁇ m, 80 ⁇ m, 100 ⁇ m, 120 ⁇ m, 140 ⁇ m, 160 ⁇ m, 180 ⁇ m or 200 ⁇ m, etc.). If the thickness is less than 1 ⁇ m, there is a tendency for insufficient mechanical strength; if it exceeds 200 ⁇ m, there is a tendency for insufficient sensitivity due to reduced light transmittance, resulting in reduced photocurability of the photocurable composition after mixing.
  • the structure of the thioxanthone sulfonium salt photoinitiator is designed, and the prepared thioxanthone sulfonium salt photoinitiator has low mobility. After the mobility test, the thioxanthone sulfonium salt photoinitiator precipitates The content is less than 0.0085%, specifically 0.0063% to 0.0083%, and after the odor test, no odor is present, thus solving the problem of existing photoinitiators releasing toxic and unpleasant photolysis products.
  • This embodiment provides a thioxanthone sulfonium salt photoinitiator and a preparation method thereof, and the preparation method is as follows:
  • the thioxanthone sulfonium salt photoinitiator provided in this embodiment was characterized by nuclear magnetic resonance testing.
  • the thioxanthene sulfonium salt photoinitiators provided in Examples 2-10 can be prepared by referring to the preparation method of the thioxanthene sulfonium salt photoinitiator provided in Example 1.
  • 2-isopropyl-9,9-dimethyl-9H-thioxanthene (2.68 g) and chloroform (30 mL) were added to a 100 mL four-necked flask. After stirring and dissolving, the system began to cool down to 10-15°C, and then a chloroform solution (30 mL) containing 85% by mass of m-chloroperbenzoic acid (2.1 g) was slowly added dropwise. After the addition was completed, the temperature was maintained and stirred for 2-3 h. Sampling was performed for HPLC detection and analysis.
  • the corresponding photoinitiator is dissolved in the solvent propylene carbonate, and then evenly mixed with other components (A1, A2, A3) to prepare a photocurable composition.
  • the solvent is propylene carbonate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Provided in the present application are a thioxanthene sulfonium salt photoinitiator as well as a preparation method therefor and the use thereof. The thioxanthene sulfonium salt photoinitiator has a structure as shown in following formula I. The thioxanthene sulfonium salt photoinitiator provided by the present application has relatively low mobility, solving the problem of existing photoinitiators releasing toxic and unpleasant photolysis products.

Description

一种噻吨硫鎓盐光引发剂及其制备方法和应用A thioxanthonesulfonium salt photoinitiator and its preparation method and application 技术领域Technical Field
本申请涉及光固化材料技术领域，例如一种噻吨硫鎓盐光引发剂及其制备方法和应用。The present application relates to the technical field of photocurable materials, for example, a thioxanthone sulfonium salt photoinitiator and a preparation method and application thereof.
背景技术Background technique
随着光固化技术的发展，光固化组合物被广泛应用于涂层、印刷、食品包装等领域。而随着光固化组合物的广泛应用，人们对光引发剂的关注也越来越多。With the development of photocuring technology, photocurable compositions are widely used in coating, printing, food packaging and other fields. With the widespread application of photocurable compositions, people are paying more and more attention to photoinitiators.
CN104628540A公开了一种阳离子光引发剂(4-辛烷氧基苯基)苯碘鎓六氟锑酸盐的制备方法。所述制备方法包括如下步骤：在溶剂中，将二乙酸碘苯在对甲苯磺酸存在下与4-辛烷氧基苯一步法进行反应制得，反应温度为室温，反应时间为4-24小时，反应结束后浓缩去掉溶剂，然后加石油醚结晶得(4-辛烷氧基苯基)苯碘鎓对甲苯磺酸盐，最后与六氟锑酸钠进行离子交换得产品。CN104628540A discloses a method for preparing a cationic photoinitiator (4-octyloxyphenyl) benzyl iodonium hexafluoroantimonate. The preparation method comprises the following steps: in a solvent, iodobenzene diacetate is reacted with 4-octyloxybenzene in the presence of p-toluenesulfonic acid in a one-step process, the reaction temperature is room temperature, the reaction time is 4-24 hours, after the reaction is completed, the solvent is concentrated and removed, and then petroleum ether is added to crystallize to obtain (4-octyloxyphenyl) benzyl iodonium p-toluenesulfonate, and finally ion exchange is performed with sodium hexafluoroantimonate to obtain the product.
CN110819203A公开了一种阳离子光固化组合物及其在光固化领域中的应用。该阳离子光固化组合物包括：(A)阳离子反应型化合物；(B)助剂；(C)阳离子光引发剂。该技术方案提供的阳离子光固化组合物中的阳离子光引发剂中至少包含两个苯环和一个烯基形成的共轭体系结构，使得该阳离子引发剂的吸收峰能够与LED固化光源进行很好的匹配，有利于缩短阳离子光固化组合物对固化光源的响应时间；同时上述阳离子光引发剂还与阳离子反应型化合物、助剂等具有良好的相容性，从而有利于提高阳离子光固化组合物对基材的附着力。CN110819203A discloses a cationic photocurable composition and its application in the field of photocuring. The cationic photocurable composition comprises: (A) a cationic reactive compound; (B) an auxiliary agent; and (C) a cationic photoinitiator. The cationic photoinitiator in the cationic photocurable composition provided by the technical solution comprises at least a conjugated system structure formed by two benzene rings and one alkenyl group, so that the absorption peak of the cationic initiator can be well matched with the LED curing light source, which is beneficial to shortening the response time of the cationic photocurable composition to the curing light source; at the same time, the above-mentioned cationic photoinitiator also has good compatibility with the cationic reactive compound, the auxiliary agent, etc., so as to improve the adhesion of the cationic photocurable composition to the substrate.
相关技术中，虽然对阳离子光引发剂的关注越来越多，但是阳离子光引发剂的种类仍较少，且目前市场上常使用的引发剂为硫鎓盐或碘鎓盐，硫鎓盐在 固化过程中会分解出芳香族硫化物和有毒副产物，芳香族硫化物如苯硫醚具有难闻的气味，有毒副产物如苯、甲苯等对人体有害。常使用的碘鎓盐也会分解产生挥发性物质如苯、甲苯或异丁基苯，对人体产生危害。这严重限制了阳离子引发剂的应用，例如该类阳离子引发剂无法用于食物或与食物接触的包装上的印刷油墨中，或消费者直接接触的包装中。In the related art, although more and more attention has been paid to cationic photoinitiators, the types of cationic photoinitiators are still relatively small, and the initiators commonly used in the market are sulfonium salts or iodonium salts. Aromatic sulfides and toxic byproducts are decomposed during the curing process. Aromatic sulfides such as phenylene sulfide have an unpleasant odor, and toxic byproducts such as benzene and toluene are harmful to the human body. Commonly used iodonium salts will also decompose to produce volatile substances such as benzene, toluene or isobutylbenzene, which are harmful to the human body. This seriously limits the application of cationic initiators. For example, such cationic initiators cannot be used in printing inks on food or packaging that comes into contact with food, or in packaging that consumers come into direct contact with.
因此，扩展阳离子光引发剂的种类，以解决现有的光引发剂释放有毒和难闻的光解产物的问题，已成为人们关注的重点。Therefore, expanding the types of cationic photoinitiators to solve the problem of existing photoinitiators releasing toxic and unpleasant photolysis products has become a focus of attention.
发明内容Summary of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.
本申请提供一种噻吨硫鎓盐光引发剂及其制备方法和应用。本申请中通过对噻吨硫鎓盐光引发剂的结构进行设计，制备得到的噻吨硫鎓盐光引发剂具有较低的迁移性，解决了现有的光引发剂释放有毒和难闻的光解产物的问题。The present application provides a thioxanthene sulfonium salt photoinitiator and a preparation method and application thereof. In the present application, by designing the structure of the thioxanthene sulfonium salt photoinitiator, the prepared thioxanthene sulfonium salt photoinitiator has low mobility, which solves the problem that the existing photoinitiator releases toxic and unpleasant photolysis products.
第一方面，本申请提供一种噻吨硫鎓盐光引发剂，所述噻吨硫鎓盐光引发剂具有如下式I所示结构：
In a first aspect, the present application provides a thioxanthone sulfonium salt photoinitiator, wherein the thioxanthone sulfonium salt photoinitiator has a structure as shown in the following formula I:
其中，M表示硫原子、S＝O；Wherein, M represents a sulfur atom, S＝O;
R′1、R1、R2、R3、R4、R5各自独立地选自氢、取代或未取代的C1-C30烷 基、C1-C20烷氧基、C1-C20烷硫基、C2-C20烯基、C2-C20炔基、C6-C14芳基、C3-C20杂芳基、含有C-R″-C结构的碳原子个数为2～30的取代基； R'1 , R1 , R2 , R3 , R4 , R5 are each independently selected from hydrogen, substituted or unsubstituted C1-C30 alkane C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C2-C20 alkenyl, C2-C20 alkynyl, C6-C14 aryl, C3-C20 heteroaryl, or a substituent having 2 to 30 carbon atoms and containing a CR″-C structure;
所述取代的取代基包括C6-C14芳基；The substituted substituents include C6-C14 aryl;
所述R″选自O、S、酯基、硫酯基、酰胺基或氨基甲酸酯基；The R″ is selected from O, S, an ester group, a thioester group, an amide group or a carbamate group;
γ-表示无机阴离子或有机阴离子。γ- represents an inorganic anion or an organic anion.
本申请中，通过对噻吨硫鎓盐光引发剂的结构进行设计，制备得到的噻吨硫鎓盐光引发剂具有较低的迁移性，解决了现有的光引发剂释放有毒和难闻的光解产物的问题。In the present application, by designing the structure of the thioxanthone sulfonium salt photoinitiator, the prepared thioxanthone sulfonium salt photoinitiator has lower mobility, thereby solving the problem of existing photoinitiators releasing toxic and unpleasant photolysis products.
本申请中，具有通式I的噻吨硫鎓盐光引发剂中引入如羟基这样的阳离子可聚合基团，在光固化中参与聚合交联反应，因此涂层固化后残留的光引发剂和光解产物不会向涂层表面迁移，不会使涂层发生黄变，其光解产物中没有难闻的硫醚产生，光解产物无对人体有害的影响。In the present application, a cationic polymerizable group such as a hydroxyl group is introduced into the thioxanthone sulfonium salt photoinitiator having the general formula I, and participates in the polymerization cross-linking reaction during photocuring. Therefore, the residual photoinitiator and photolysis product after the coating is cured will not migrate to the surface of the coating, will not cause the coating to turn yellow, and no unpleasant sulfide is produced in the photolysis product, and the photolysis product has no harmful effect on the human body.
本申请中，C1-C30可以是C1、C2、C4、C6、C8、C10、C12、C14、C16、C18、C20、C22、C24、C26、C28或C30等。In the present application, C1-C30 can be C1, C2, C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 or C30, etc.
C1-C20可以是C1、C2、C4、C6、C8、C10、C12、C14、C16、C18或C20等。C1-C20 can be C1, C2, C4, C6, C8, C10, C12, C14, C16, C18 or C20, etc.
C2-C20可以是C2、C4、C6、C8、C10、C12、C14、C16、C18或C20等。C2-C20 can be C2, C4, C6, C8, C10, C12, C14, C16, C18 or C20, etc.
C6-C14可以是C6、C7、C8、C9、C10、C11、C12、C13或C14。C6-C14 can be C6, C7, C8, C9, C10, C11, C12, C13 or C14.
C3-C20可以是C3、C4、C6、C8、C10、C12、C14、C16、C18或C20等。C3-C20 can be C3, C4, C6, C8, C10, C12, C14, C16, C18 or C20, etc.
以下作为本申请的可选技术方案，但不作为对本申请提供的技术方案的限制，通过以下可选的技术方案，可以更好的达到和实现本申请的目的和有益效果。The following are optional technical solutions for this application, but are not intended to limit the technical solutions provided in this application. Through the following optional technical solutions, the objectives and beneficial effects of this application can be better achieved and realized.
在一实施方式中，所述含有C-R″-C结构的碳原子个数为2～30的取代基选 自：含有C-R″-C结构的C2-C20直链或支链烷基、含有C-R″-C结构的C3-C20环烷基、含有C-R″-C结构的被C3～C8环烷基取代的C1-C10的链状烷基、含有C-R″-C结构的被C1-C20链状烷基取代的C3-C8环烷基、含有C-R″-C结构的被C6-C14芳基取代的C1-C10烷基、含有C-R″-C结构的C2-C20链状烯基、含有C-R″-C结构的C2-C20炔基；In one embodiment, the substituent having 2 to 30 carbon atoms containing the CR″-C structure is selected from From: C2-C20 straight or branched chain alkyl containing CR"-C structure, C3-C20 cycloalkyl containing CR"-C structure, C1-C10 chain alkyl containing CR"-C structure substituted by C3-C8 cycloalkyl, C3-C8 cycloalkyl containing CR"-C structure substituted by C1-C20 chain alkyl, C1-C10 alkyl containing CR"-C structure substituted by C6-C14 aryl, C2-C20 chain alkenyl containing CR"-C structure, C2-C20 alkynyl containing CR"-C structure;
其中，R″具有与上述相同的保护范围。Wherein, R″ has the same protection scope as above.
含有C-R″-C结构的C2-C20直链或支链烷基，其中R″选自O、S、酯基、硫酯基、酰胺基或氨基甲酸酯基，所述含有C-R″-C结构的C2-C20直链或支链烷基中含有至少1个(例如1、2、3、4、5、6、7、8等)上述C-R″-C结构，即烷基的端部由碳原子形成。若在烷基中存在多个C-R″-C结构，则这些基团通常相同。A C2-C20 straight or branched chain alkyl group containing a C-R"-C structure, wherein R" is selected from O, S, an ester group, a thioester group, an amide group or a carbamate group, and the C2-C20 straight or branched chain alkyl group containing a C-R"-C structure contains at least 1 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, etc.) of the above C-R"-C structure, that is, the end of the alkyl group is formed by carbon atoms. If there are multiple C-R"-C structures in the alkyl group, these groups are usually the same.
含有C-R″-C结构的C2-C20直链或支链烷基的包括-(CH2CH2O)2CH3、-(CH2CH2O)2CH2CH3、含有C-O-C结构的烷基还可以称为烷氧基烷基或者含有2个C-O-C结构的烷基还可以称为烷氧基烷氧基烷基。同样，含有C-S-C结构的烷基还可以称为烷基-S-烷基(烷硫基烷基)或者含有2个C-S-C结构的烷基还可以称为烷基-S-烷基-S-烷基(烷硫基烷硫基烷基)。The C2-C20 straight or branched chain alkyl groups containing the CR″-C structure include -(CH 2 CH 2 O) 2 CH 3 , -(CH 2 CH 2 O) 2 CH 2 CH 3 , An alkyl group containing a COC structure may also be referred to as an alkoxyalkyl group, or an alkyl group containing two COC structures may also be referred to as an alkoxyalkoxyalkyl group. Similarly, an alkyl group containing a CSC structure may also be referred to as an alkyl-S-alkyl group (alkylthioalkyl group), or an alkyl group containing two CSC structures may also be referred to as an alkyl-S-alkyl-S-alkyl group (alkylthioalkylthioalkyl group).
含有C-R″-C结构的C2-C20链状烯基，其中R″选自O、S、酯基、硫酯基、酰胺基或氨基甲酸酯基，例如1、2、3、4、5、6、7或8个上述C-R″-C结构，即链烯基的端部由碳原子形成。若存在多个这些C-R″-C结构，则它们通常相同。A C2-C20 chain alkenyl group containing a C-R"-C structure, wherein R" is selected from O, S, an ester group, a thioester group, an amide group or a carbamate group, for example 1, 2, 3, 4, 5, 6, 7 or 8 of the above C-R"-C structures, i.e., the ends of the chain alkenyl group are formed by carbon atoms. If a plurality of these C-R"-C structures are present, they are generally the same.
含有C-R″-C结构的C2-C20炔基，其中R″选自O、S、酯基、硫酯基、酰胺基或氨基甲酸酯基，所述含有C-R″-C结构的C2-C20炔基含有至少1个(例如1、2、3、4、5、6、7、8等)C-R″-C结构，即炔基的端部由碳原子形成。 若在炔基中存在多个上述C-R″-C结构，则它们通常相同。A C2-C20 alkynyl group containing a CR"-C structure, wherein R" is selected from O, S, an ester group, a thioester group, an amide group or a carbamate group, and the C2-C20 alkynyl group containing a CR"-C structure contains at least 1 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, etc.) CR"-C structure, that is, the end of the alkynyl group is formed by a carbon atom. If a plurality of the above-mentioned CR"-C structures are present in the alkynyl group, they are generally the same.
可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自氢、卤素、氰基、未取代的C1-C20(例如可以是C1、C2、C4、C6、C8、C10、C12、C14、C16、C18或C20等)直链或支链烷基、未取代的C3-C20(例如可以是C3、C4、C6、C8、C10、C12、C14、C16、C18或C20等)环烷基、C3～C8(例如可以是C3、C4、C5、C6、C7或C8)环烷基取代的C1-C10(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9或C10)的链状烷基、C1-C20(例如可以是C1、C2、C4、C6、C8、C10、C12、C14、C16、C18或C20等)链状烷基取代的C3-C8(例如可以是C3、C4、C5、C6、C7或C8)环烷基、C6-C14(例如可以是C4、C5、C6、C7、C8、C9、C10、C11、C12、C13或C14)芳基取代的C1-C10(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9或C10)烷基、C1-C15(例如可以是C1、C2、C4、C6、C8、C10、C12、C14或C15等)烷氧基、C1-C15(例如可以是C1、C2、C4、C6、C8、C10、C12、C14或C15等)烷硫基、C2-C20(例如可以是C2、C4、C6、C8、C10、C12、C14、C16、C18或C20等)链状烯基、C5-C20(例如可以是C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19或C20)环烯基、C2-C16(例如可以是C2、C4、C6、C8、C10、C12、C14或C16等)炔基、C6-C14(例如可以是C6、C7、C8、C9、C10、C11、C12、C13或C14)芳基、C3-C20(例如可以是C3、C4、C6、C8、C10、C12、C14、C16、C18或C20等)杂芳基、含有C-R″-C结构的C2-C20直链或支链烷基；Optionally, R'1 , R1 , R2 , R3 , R4 , and R5 are each independently selected from hydrogen, halogen, cyano, unsubstituted C1-C20 (for example, C1, C2, C4, C6, C8, C10, C12, C14, C16, C18, or C20, etc.) straight or branched alkyl, unsubstituted C3-C20 (for example, C3, C4, C6, C8, C10, C12, C14, C16, C18, or C20, etc.) cycloalkyl, C3-C8 (for example, C3, C4, C5, C6, C7, or C8) cycloalkyl-substituted C1-C10 (for example, C1, C2, C3, C4, C5, C6, C7, or C8, etc.) , C7, C8, C9 or C10) chain alkyl, C3-C8 (for example, C3, C4, C5, C6, C7 or C8) cycloalkyl substituted with a C1-C20 (for example, C1, C2, C4, C6, C8, C10, C12, C14, C16, C18 or C20, etc.) chain alkyl, C6-C14 (for example, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13 or C14) aryl substituted with a C1-C10 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13 or C14) C1-C15 (for example, C1, C2, C4, C6, C8, C10, C12, C14 or C15, etc.) alkyl, C1-C15 (for example, C1, C2, C4, C6, C8, C10, C12, C14 or C15, etc.) alkylthio, C2-C20 (for example, C2, C4, C6, C8, C10, C12, C14, C16, C18 or C20, etc.) chain alkenyl, C5-C20 (for example, C5, C6, C7, C8, C9, C10, C11, C12, C14, C15, etc.) C3-C20 (for example, C3, C4, C6, C8, C10, C12, C14, C16, C18, or C20) cycloalkenyl, C2-C16 (for example, C2, C4, C6, C8, C10, C12, C14, C16, etc.) alkynyl, C6-C14 (for example, C6, C7, C8, C9, C10, C11, C12, C13, or C14) aryl, C3-C20 (for example, C3, C4, C6, C8, C10, C12, C14, C16, C18, or C20) heteroaryl, C2-C20 straight or branched alkyl containing a CR″-C structure;
其中，R″具有与上述相同的保护范围。Wherein, R″ has the same protection scope as above.
在一实施方式中，所述R′1、R1、R2、R3、R4、R5各自独立地选自未取代的C1-C10(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9或C10)的直 链或支链烷基。In one embodiment, R'1 , R1 , R2 , R3, R4, and R5 are each independently selected from unsubstituted C1-C10 (e.g., C1, C2, C3 , C4 , C5, C6, C7, C8, C9, or C10) Chain or branched chain alkyl.
可选地，所述C1-C10的直链或支链烷基包括甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、异戊基、新戊基、2-甲基丁基、1-乙基丙基、己基、异己基、庚基、辛基、壬基。Optionally, the C1-C10 straight or branched alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, 2-methylbutyl, 1-ethylpropyl, hexyl, isohexyl, heptyl, octyl, and nonyl.
可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自未取代的C3-C8(例如可以是C3、C4、C5、C6、C7或C8)环烷基。Optionally, R' 1 , R 1 , R 2 , R 3 , R 4 , and R5 are each independently selected from unsubstituted C3-C8 (eg, C3, C4, C5, C6, C7 or C8) cycloalkyl.
可选地，所述C3-C8环烷基包括环丙基、环丁基、环戊基、环己基、环庚基、环辛基。Optionally, the C3-C8 cycloalkyl group includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自C3-C8(例如可以是C3、C4、C5、C6、C7或C8)环烷基取代的C1-C7(例如可以是C1、C2、C3、C4、C5、C6或C7)链状烷基。Optionally, R'1 , R1 , R2 , R3 , R4 , R5 are each independently selected from C3-C8 (eg C3, C4, C5, C6, C7 or C8) cycloalkyl-substituted C1-C7 (eg C1, C2, C3, C4, C5, C6 or C7) chain alkyl.
可选地，所述C3-C8环烷基取代的C1-C7链状烷基包括环戊基乙基、环戊基甲基、环己基甲基、环己基乙基。Optionally, the C1-C7 chain alkyl substituted by the C3-C8 cycloalkyl group includes cyclopentylethyl, cyclopentylmethyl, cyclohexylmethyl, and cyclohexylethyl.
可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自C1-C10(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9或C10)链状烷基取代的C3-C7(例如可以是C3、C4、C5、C6或C7)环烷基。Optionally, R'1 , R1 , R2 , R3, R4 , R5 are each independently selected from C1-C10 (e.g., C1, C2, C3 , C4, C5, C6, C7, C8, C9 or C10) chain alkyl-substituted C3-C7 (e.g., C3, C4, C5, C6 or C7) cycloalkyl.
可选地，所述C1-C10链状烷基取代的C3-C7环烷基包括2-甲基-1-环戊基、3-甲基-1-环戊基、2-甲基-1-环己基、3-甲基-1-环己基、4-甲基-1-环己基。Optionally, the C3-C7 cycloalkyl substituted by the C1-C10 chain alkyl group includes 2-methyl-1-cyclopentyl, 3-methyl-1-cyclopentyl, 2-methyl-1-cyclohexyl, 3-methyl-1-cyclohexyl, and 4-methyl-1-cyclohexyl.
可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自C6-C10(例如可以是C6、C7、C8、C9或C10)芳基取代的C1-C6(例如可以是C1、C2、C3、C4、C5或C6)烷基。Optionally, R'1 , R1 , R2 , R3 , R4 , R5 are each independently selected from C6-C10 (eg, C6, C7, C8, C9 or C10) aryl-substituted C1-C6 (eg, C1, C2, C3, C4, C5 or C6) alkyl.
可选地，所述C6-C10芳基取代的C1-C6烷基包括苄基、α-苯基乙基、β-苯基乙基、3-苯基丙基、4-苯基丁基、1-萘基甲基、2-萘基甲基。 Optionally, the C1-C6 alkyl substituted by the C6-C10 aryl group includes benzyl, α-phenylethyl, β-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 1-naphthylmethyl, and 2-naphthylmethyl.
在一实施方式中，所述R′1、R1、R2、R3、R4、R5各自独立地选自C1-C10(例如可以是C1、C2、C3、C4、C5、C6、C7、C8、C9或C10)烷氧基。In one embodiment, R'1 , R1 , R2 , R3, R4 , and R5 are each independently selected from C1-C10 (eg, C1, C2, C3 , C4, C5, C6, C7, C8, C9, or C10) alkoxy groups.
可选地，所述C1-C10烷氧基包括甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、叔丁氧基、戊氧基、异戊氧基、新戊氧基、2-乙基己氧基、4-甲基戊氧基、己氧基、庚氧基、辛氧基、壬氧基。Optionally, the C1-C10 alkoxy group includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, 2-ethylhexyloxy, 4-methylpentyloxy, hexyloxy, heptyloxy, octyloxy, and nonyloxy.
可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自C1-C10烷硫基；Optionally, said R′ 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from C1-C10 alkylthio;
可选地，所述C1-C10烷硫基包括甲硫基、乙硫基、丙硫基、异丙硫基、正丁硫基、仲丁硫基、异丁硫基和叔丁硫基。Optionally, the C1-C10 alkylthio group includes methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio and tert-butylthio.
可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自C2-C10(例如可以是C2、C3、C4、C5、C6、C7、C8、C9或C10)链状烯基。Optionally, R'1 , R1 , R2 , R3 , R4 , and R5 are each independently selected from C2-C10 (eg, C2, C3, C4, C5, C6, C7, C8, C9, or C10) chain alkenyl groups.
可选地，所述C2-C10链状烯基包括乙烯基、1-丙烯基、烯丙基、异丙烯基、甲代烯丙基、丁烯基、戊烯基、己烯基、异己烯基、庚烯基、辛烯基、壬烯基。Optionally, the C2-C10 chain alkenyl group includes vinyl, 1-propenyl, allyl, isopropenyl, methallyl, butenyl, pentenyl, hexenyl, isohexenyl, heptenyl, octenyl, nonenyl.
可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自C5-C10(例如可以是C5、C6、C7、C8、C9或C10)环烯基。Optionally, R' 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from C5-C10 (eg, C5, C6, C7, C8, C9 or C10) cycloalkenyl groups.
可选地，所述C5-C10环烯基包括环戊烯基、环己烯基、环庚烯基、环辛烯基、降冰片烯基。Optionally, the C5-C10 cycloalkenyl group includes cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, and norbornene.
可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自C2-C10(例如可以是C2、C3、C4、C5、C6、C7、C8、C9或C10)炔基。Optionally, R'1 , R1 , R2 , R3 , R4 , R5 are each independently selected from C2-C10 (eg, C2, C3, C4, C5, C6, C7, C8, C9 or C10) alkynyl.
可选地，所述C2-C10炔基包括乙炔基、1-丙炔基、异丙炔基、丁炔基、戊炔基、己炔基、庚炔基、辛炔基、壬炔基。Optionally, the C2-C10 alkynyl group includes ethynyl, 1-propynyl, isopropynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, and nonynyl.
可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自C6-C10(例如可以是C6、C7、C8、C9或C10)芳基。Optionally, R' 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from C6-C10 (eg, C6, C7, C8, C9 or C10) aryl groups.
可选地，所述C6-C10芳基包括苯基、1-萘基、2-萘基。 Optionally, the C6-C10 aryl group includes phenyl, 1-naphthyl, and 2-naphthyl.
可选地，所述R′1、R1、R2、R3、R4、R5分别独立地选自C3-C10(例如可以是C3、C4、C5、C6、C7、C8、C9或C10)杂芳基。Optionally, R' 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are independently selected from C3-C10 (eg, C3, C4, C5, C6, C7, C8, C9 or C10) heteroaryl groups.
可选地，所述C3-C10杂芳基包括噻吩基、噻吩-2-甲基、吡啶基、2-呋喃基、喹啉基、吡喃基、咪唑基、哌啶基、吗啉基、噻吨基、吲哚基。Optionally, the C3-C10 heteroaryl group includes thienyl, thien-2-methyl, pyridyl, 2-furyl, quinolyl, pyranyl, imidazolyl, piperidinyl, morpholinyl, thioxanthenyl, and indolyl.
可选地，所述R′1、R1、R2、R3、R4、R5分别独立地选自含有C-R″-C结构的C2-C10(例如可以是C2、C3、C4、C5、C6、C7、C8、C9或C10)直链或支链烷基；Optionally, R'1 , R1 , R2 , R3 , R4 , R5 are independently selected from C2-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight or branched alkyl groups containing a CR"-C structure;
可选地，所述含有C-R″-C结构的C2-C10直链或支链烷基包括-(CH2CH2O)2CH3、-(CH2CH2O)2CH2CH3、 Optionally, the C2-C10 straight or branched alkyl group containing a CR″-C structure includes -(CH 2 CH 2 O) 2 CH 3 , -(CH 2 CH 2 O) 2 CH 2 CH 3 ,
在一实施方式中，所述γ-表示X-、C1O4 -、CN-、HSO4 -、CF3COO-、(BX4)-、(SbX6)-、(AsX6)-、(PX6)-、Al[OC(CF3)3]4 -、磺酸根离子、B(C6X5)4 -或[(Rf)bPF6-b]-中的任一种；In one embodiment, the γ- represents any one of X- , C1O4- , CN- , HSO4- , CF3COO- , ( BX4 ) - , ( SbX6 ) - , ( AsX6 ) - , ( PX6 ) - , Al[OC( CF3 ) 3 ] 4- , sulfonate ion, B( C6X5 ) 4- , or [(Rf) bPF6 -b ] - ;
其中，X选自F或Cl；wherein X is selected from F or Cl;
Rf表示C1-C6(例如可以是C1、C2、C3、C4、C5或C6)氟代烷基，b表示1～5的整数(例如可以是1、2、3、4或5)，且b表示2～5的整数时，Rf基团相同或不相同。Rf represents a C1-C6 (for example, it can be C1, C2, C3, C4, C5 or C6) fluoroalkyl group, b represents an integer of 1 to 5 (for example, it can be 1, 2, 3, 4 or 5), and when b represents an integer of 2 to 5, the Rf groups are the same or different.
可选地，所述C1～C6氟代烷基中氟原子的个数：(氟原子的个数+氢原子的个数)×100％≥80％，例如可以是80％、82％、84％、86％、88％、90％、92％、94％、96％、98％或100％等。Optionally, the number of fluorine atoms in the C1-C6 fluoroalkyl group is: (the number of fluorine atoms + the number of hydrogen atoms)×100%≥80%, for example, it can be 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96%, 98% or 100%, etc.
可选地，所述γ-选自PF6 -、SbF6 -、AsF6 -、BF4 -、B(C6F5)4 -中的任一种。Optionally, the γ- is selected from any one of PF 6 - , SbF 6 - , AsF 6 - , BF 4 - , and B(C 6 F 5 ) 4 - .
在一实施方式中，所述噻吨硫鎓盐光引发剂的阳离子部分选自阳离子结构1-12中的任意一种：
In one embodiment, the cationic portion of the thioxanthenolsulfonium salt photoinitiator is selected from any one of the cationic structures 1-12:
第二方面，本申请提供一种如第一方面所述的噻吨硫鎓盐光引发剂的制备方法，其特征在于，所述制备方法包括如下步骤：In a second aspect, the present application provides a method for preparing the thioxanthenolsulfonium salt photoinitiator as described in the first aspect, characterized in that the preparation method comprises the following steps:
在催化剂的作用下，化合物1与化合物2进行傅克反应，反应结束后，向其中加入有机盐或无机盐进行阴离子交换反应，得到所述噻吨硫鎓盐光引发剂；Under the action of a catalyst, compound 1 and compound 2 undergo a Friedel-Crafts reaction, and after the reaction is completed, an organic salt or an inorganic salt is added thereto to perform an anion exchange reaction to obtain the thioxanthenolsulfonium salt photoinitiator;
其中，化合物1为 Among them, compound 1 is
化合物2为 Compound 2 is
M、R′1、R1、R2、R3、R4、R5具有与第一方面相同的保护范围。M, R' 1 , R 1 , R 2 , R 3 , R 4 , and R5 have the same protection scope as the first aspect.
所述噻吨硫鎓盐光引发剂的制备过程如下所示：
The preparation process of the thioxanthonesulfonium salt photoinitiator is as follows:
其中，M、R′1、R1、R2、R3、R4、R5、γ-具有与第一方面相同的保护范围。Wherein, M, R′ 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and γ- have the same protection scope as that of the first aspect.
需要说明的是，本申请中使用的化合物1和化合物2均可通过商业购得或者经已知的合成方法制备而成。It should be noted that Compound 1 and Compound 2 used in the present application can be purchased commercially or prepared by known synthesis methods.
在一实施方式中，所述催化剂选自硫酸、三氯化铝、三氯化铁、氯化锌、五氧化二磷-甲烷磺酸中的任意一种或至少两种的组合。In one embodiment, the catalyst is selected from any one of sulfuric acid, aluminum chloride, ferric chloride, zinc chloride, phosphorus pentoxide-methanesulfonic acid, or a combination of at least two thereof.
可选地，所述傅克反应的温度≤25℃，进一步可选为-5～15℃，例如可以是-5℃、-2℃、0℃、2℃、5℃、7℃、8℃、10℃、12℃、13℃、15℃、18℃、20℃、22℃或25℃等。Optionally, the temperature of the Friedel-Crafts reaction is ≤25°C, and may further be -5 to 15°C, for example, -5°C, -2°C, 0°C, 2°C, 5°C, 7°C, 8°C, 10°C, 12°C, 13°C, 15°C, 18°C, 20°C, 22°C or 25°C, etc.
可选地，所述傅克反应的时间为1～5h，例如可以是1h、2h、3h、4h或5h等。Optionally, the Friedel-Crafts reaction time is 1 to 5 h, for example, 1 h, 2 h, 3 h, 4 h or 5 h.
可选地，所述有机盐或无机盐选自六氟磷酸钾、氟硼酸钾、六氟锑酸钾、四(五氟苯基)硼酸钠、六氟锑酸钠、六氟砷酸钠中的任意一种。Optionally, the organic salt or inorganic salt is selected from any one of potassium hexafluorophosphate, potassium fluoroborate, potassium hexafluoroantimonate, sodium tetrakis(pentafluorophenyl)borate, sodium hexafluoroantimonate, and sodium hexafluoroarsenate.
可选地，所述阴离子交换反应的温度为20～25℃，例如可以是20℃、21℃、22℃、23℃、24℃或25℃等。 Optionally, the temperature of the anion exchange reaction is 20-25°C, for example, 20°C, 21°C, 22°C, 23°C, 24°C or 25°C.
可选地，所述阴离子交换反应的时间为1～3h，例如可以是1h、1.5h、2h、2.5h或3h等。Optionally, the anion exchange reaction time is 1 to 3 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours.
可选地，所述阴离子交换反应后还包括后处理的步骤。Optionally, the anion exchange reaction further includes a post-treatment step.
可选地，所述后处理的方法包括洗涤、减压浓缩、结晶。Optionally, the post-treatment method includes washing, concentration under reduced pressure, and crystallization.
可选地，所述傅克反应和阴离子交换反应均在溶剂存在下进行。Optionally, the Friedel-Crafts reaction and the anion exchange reaction are both carried out in the presence of a solvent.
本申请中对于傅克反应和阴离子交换反应使用的溶剂不做任何特殊的限制，只需其能够溶解反应试剂且对反应无不良影响即可。所述傅克反应和阴离子交换反应使用的溶剂各自独立地包括但不限于：乙酸、硫酸、多磷酸、甲烷磺酸、气态氯化氢、甲烷磺酸和五氧化二磷的混合物、乙酸酐和硫酸的混合物或甲烷磺酸酐。The solvents used in the Friedel-Crafts reaction and the anion exchange reaction are not subject to any special restrictions in the present application, as long as they can dissolve the reaction reagents and have no adverse effects on the reaction. The solvents used in the Friedel-Crafts reaction and the anion exchange reaction independently include, but are not limited to, acetic acid, sulfuric acid, polyphosphoric acid, methanesulfonic acid, gaseous hydrogen chloride, a mixture of methanesulfonic acid and phosphorus pentoxide, a mixture of acetic anhydride and sulfuric acid, or methanesulfonic anhydride.
第三方面，本申请提供一种如第一方面所述的噻吨硫鎓盐光引发剂的应用，所述噻吨硫鎓盐光引发剂用于制备涂料、油墨或粘合剂。In a third aspect, the present application provides a use of the thioxanthonesulfonium salt photoinitiator as described in the first aspect, wherein the thioxanthonesulfonium salt photoinitiator is used to prepare coatings, inks or adhesives.
第四方面，本申请提供一种光固化组合物，所述光固化组合物包括如第一方面所述的噻吨硫鎓盐光引发剂。In a fourth aspect, the present application provides a photocurable composition, wherein the photocurable composition comprises the thioxanthenolsulfonium salt photoinitiator as described in the first aspect.
可选地，所述光固化组合物包括如下组分：含环氧乙烷基团的化合物和/或含乙烯基醚基团的化合物、氧杂环丁烷化合物、如第一方面所述的噻吨硫鎓盐光引发剂。Optionally, the photocurable composition comprises the following components: a compound containing an oxirane group and/or a compound containing a vinyl ether group, an oxetane compound, and the thioxanthenolsulfonium salt photoinitiator as described in the first aspect.
可选地，所述含环氧乙烷基团的化合物选自脂环族环氧化合物、芳香族环氧化合物、链状脂肪族环氧化合物，从可进一步提高固化速度的方面考虑，所述含环氧乙烷基团的化合物进一步可选为脂环族环氧化合物，更进一步可选为具有2个以上脂环族环氧基的多官能脂环族环氧化合物。Optionally, the compound containing an ethylene oxide group is selected from alicyclic epoxy compounds, aromatic epoxy compounds, and chain aliphatic epoxy compounds. In order to further increase the curing speed, the compound containing an ethylene oxide group can be further selected as an alicyclic epoxy compound, and can be further selected as a multifunctional alicyclic epoxy compound having two or more alicyclic epoxy groups.
可选地，所述脂环族环氧化合物选自3，4-环氧环己烯甲基-3，4-环氧环己烯酸酯、3，4，3′，4′-二环氧基双环己烷、2，2-双(3，4-环氧基环己基)丙烷、2，2-双(3，4-环氧 基环己基)-1，3-六氟丙烷、双(3，4-环氧基环己基)甲烷、1-[1，1-双(3，4-环氧基环己基)]乙基苯、双((3，4-环氧环己基)甲基)己二酸酯或乙二酸双(3，4-环氧环己基甲酯)中的任意一种或至少两种的组合。Optionally, the alicyclic epoxy compound is selected from 3,4-epoxycyclohexenemethyl-3,4-epoxycyclohexene ester, 3,4,3′,4′-diepoxybiscyclohexane, 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis(3,4-epoxycyclohexyl)propane, Any one of or a combination of at least two of bis(3,4-epoxycyclohexyl)-1,3-hexafluoropropane, bis(3,4-epoxycyclohexyl)methane, 1-[1,1-bis(3,4-epoxycyclohexyl)]ethylbenzene, bis((3,4-epoxycyclohexyl)methyl)adipate or bis(3,4-epoxycyclohexylmethyl)oxalate.
所述芳香族环氧化合物为在分子中具有芳香环和环氧基的化合物。The aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in a molecule.
可选地，所述芳香族环氧化合物选自具有双酚骨架、芴骨架、联苯骨架、萘环、蒽环的芳香环共轭系的环氧化合物中的任意一种或至少两种的组合。了实现更快的固化速率、更优异的基材附着力，所述芳香族环氧化合物进一步可选具有双酚骨架和/或芴骨架的环氧化合物。Optionally, the aromatic epoxy compound is selected from any one or a combination of at least two of the aromatic ring conjugated epoxy compounds having a bisphenol skeleton, a fluorene skeleton, a biphenyl skeleton, a naphthalene ring, and an anthracene ring. In order to achieve a faster curing rate and better substrate adhesion, the aromatic epoxy compound may further be an epoxy compound having a bisphenol skeleton and/or a fluorene skeleton.
可选地，所述芳香族环氧化合物选自双酚A型环氧化合物、双酚F型环氧化合物、芴系环氧化合物中的任意一种或至少两种的组合，进一步可选为双酚A型环氧化合物和芴系环氧化合物的组合。Optionally, the aromatic epoxy compound is selected from any one of bisphenol A epoxy compounds, bisphenol F epoxy compounds, and fluorene epoxy compounds, or a combination of at least two thereof, and may further be a combination of bisphenol A epoxy compounds and fluorene epoxy compounds.
可选地，所述双酚A型环氧化合物包括日本三菱化学株式会社生产的JER-828EL、JER-YL980、JER-827、JER-828。Optionally, the bisphenol A epoxy compound includes JER-828EL, JER-YL980, JER-827, and JER-828 produced by Mitsubishi Chemical Corporation of Japan.
可选地，所述芴系环氧化合物包括OSAKA GAS CHEMICALS生产的OGSOL EG-200、OGSOL EG-28。Optionally, the fluorene-based epoxy compounds include OGSOL EG-200 and OGSOL EG-28 produced by OSAKA GAS CHEMICALS.
所述链状脂肪族环氧化合物包括脂肪族缩水甘油醚型环氧树脂。The chain aliphatic epoxy compound includes an aliphatic glycidyl ether type epoxy resin.
可选地，所述脂肪族缩水甘油醚型环氧树脂包括三羟甲基丙烷缩水甘油醚、乙二醇双缩水甘油醚。Optionally, the aliphatic glycidyl ether type epoxy resin includes trimethylolpropane glycidyl ether and ethylene glycol bisglycidyl ether.
可选地，所述含乙烯基醚基团的化合物选自三甘醇二乙烯基醚、1，4-环己基二甲醇二乙烯基醚、4-羟丁基乙烯基醚、甘油碳酸酯乙烯基醚和十二烷基乙烯基醚中的任意一种或至少两种的组合。Optionally, the compound containing a vinyl ether group is selected from any one or a combination of at least two of triethylene glycol divinyl ether, 1,4-cyclohexyl dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, glycerol carbonate vinyl ether and dodecyl vinyl ether.
可选地，所述氧杂环丁烷化合物选自3-羟甲基-3-乙基氧杂环丁烷、3-苄氧甲基-3-乙基氧杂环丁烷、3-乙基-3-[[(2-乙基己基)氧基]甲基]氧杂环丁烷、3，3′-[氧 基双亚甲基]双[3-乙基]氧杂环丁烷、3-乙基-3-[(氧化乙烯-2-甲氧基)甲基]氧杂环丁烷中的任意一种或至少两种的组合。Optionally, the oxetane compound is selected from 3-hydroxymethyl-3-ethyloxetane, 3-benzyloxymethyl-3-ethyloxetane, 3-ethyl-3-[[(2-ethylhexyl)oxy]methyl]oxetane, 3,3′-[ Any one of [(oxyethylene-2-methoxy)methyl]oxetane or a combination of at least two thereof.
可选地，所述光固化组合物还包括助剂。Optionally, the photocurable composition further comprises an auxiliary agent.
需要说明的是，本申请中对于助剂的种类不做任何特殊的限制，本领域常用的助剂均适用，示例性地包括但不限于：颜料、填料、流平剂、分散剂、固化剂、表面活性剂、消泡剂、储存增强剂。It should be noted that the present application does not impose any special restrictions on the types of additives, and all commonly used additives in the field are applicable, including but not limited to: pigments, fillers, leveling agents, dispersants, curing agents, surfactants, defoaming agents, and storage enhancers.
可选地，所述光固化组合物包括如下重量份数的组分：含环氧乙烷基团的化合物和/或含乙烯基醚基团的化合物10～60份、氧杂环丁烷化合物5～40份、如第一方面所述的噻吨硫鎓盐光引发剂1～20份、助剂0～10份。Optionally, the photocurable composition comprises the following components in parts by weight: 10 to 60 parts of a compound containing an ethylene oxide group and/or a compound containing a vinyl ether group, 5 to 40 parts of an oxetane compound, 1 to 20 parts of a thioxanthenium salt photoinitiator as described in the first aspect, and 0 to 10 parts of an auxiliary agent.
本申请中，所述含环氧乙烷基团的化合物和/或含乙烯基醚基团的化合物的重量份数可以是10份、15份、20份、25份、30份、35份、40份、45份、50份、55份后60份等。In the present application, the weight proportions of the compound containing ethylene oxide group and/or the compound containing vinyl ether group can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts or 60 parts.
所述氧杂环丁烷化合物的重量份数可以是5份、10份、15份、20份、25份、30份、35份或40份。The weight parts of the oxetane compound can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts.
所述噻吨硫鎓盐光引发剂的重量份数可以是1份、2份、4份、6份、8份、10份、12份、14份、16份、18份后20份等。The weight proportions of the thioxanthonesulfonium salt photoinitiator can be 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, or 20 parts.
所述助剂的重量份数可以是0份、1份、2份、3份、4份、5份、6份、7份、8份、9份后10份等。The weight proportions of the auxiliary agent can be 0 parts, 1 parts, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts.
本申请中，对于光固化组合物的制备方法没有任何特殊的限制，本领域常用的制备光固化组合物的方法均适用，示例性地包括但不限于：将光固化组合物中各组分混合、搅拌均匀，得到所述光固化组合物。In the present application, there is no special limitation on the preparation method of the photocurable composition, and the methods commonly used in the art for preparing the photocurable composition are applicable, including but not limited to: mixing and stirring the components in the photocurable composition to obtain the photocurable composition.
本申请中，所述光固化组合物可用于制备涂层，其制备方法包括：将光固化组合物涂布(包括辊涂、刷涂、刮涂、浸涂、喷涂)与基材一侧，再经辐射 源固化形成涂层。In the present application, the photocurable composition can be used to prepare a coating, and the preparation method thereof comprises: coating (including roller coating, brush coating, scraper coating, dip coating, spray coating) the photocurable composition on one side of the substrate, and then irradiating The source is cured to form a coating.
可选地，所述基材的材料选自玻璃、塑料、陶瓷或金属。Optionally, the material of the substrate is selected from glass, plastic, ceramic or metal.
本申请对于辐射源没有任何特别限制，在紫外线、可见光、红外线、电子束、激光等能量辐射下，本申请提供的光固化组合物均可发生聚合反应，并实现快速固化。所述辐射源示例性地包括但不限于：具有波长为200～500nm的超高压汞灯、高压汞灯、中压汞灯、汞氙灯、低压汞灯、金属卤化物灯、氙灯、氘灯、化学灯、LED灯、荧光灯、钨灯、Nd-YAG3倍波激光、He-Cd激光、氮激光、Xe-C1准分子激光、Xe-F准分子激光、半导体激发固体激光、i射线、h射线、g射线等活性光线；组合物的固化还可使用电子束、α射线、β射线、γ射线、X射线及中子射线能量固化等，可选为波长范围在200～500nm(例如可以是200nm、250nm、300nm、340nm、370nm、400nm、450nm或500nm等)的汞灯紫外灯或UV-LED灯，辐射源的辐射能量为20～1000mj/cm2(例如可以是20mj/cm2、50mj/cm2、100mj/cm2、200mj/cm2、300mj/cm2、400mj/cm2、500mj/cm2、600mj/cm2、700mj/cm2、800mj/cm2、900mj/cm2或1000mj/cm2等)。The present application does not have any special restrictions on the radiation source. Under the energy radiation of ultraviolet light, visible light, infrared light, electron beam, laser, etc., the photocurable composition provided in the present application can undergo polymerization reaction and achieve rapid curing. The radiation source illustratively includes, but is not limited to, ultra-high pressure mercury lamp, high pressure mercury lamp, medium pressure mercury lamp, mercury xenon lamp, low pressure mercury lamp, metal halide lamp, xenon lamp, deuterium lamp, chemical lamp, LED lamp, fluorescent lamp, tungsten lamp, Nd-YAG 3 times wave laser, He-Cd laser, nitrogen laser, Xe-C1 excimer laser, Xe-F excimer laser, semiconductor excited solid laser, i-ray, h-ray, g-ray and other active light with a wavelength of 200-500nm; the curing of the composition can also use electron beam, α-ray, β-ray, γ-ray, X-ray and neutron ray energy curing, etc., and can be selected from mercury lamp ultraviolet lamp or UV-LED lamp with a wavelength range of 200-500nm (for example, 200nm, 250nm, 300nm, 340nm, 370nm, 400nm, 450nm or 500nm, etc.), and the radiation energy of the radiation source is 20-1000mj/ cm2 (for example, 20mj/cm2). mj / cm2 , 50mj/cm2, 100mj/cm2, 200mj/cm2, 300mj/ cm2 , 400mj/ cm2 , 500mj/ cm2 , 600mj/ cm2 , 700mj/ cm2 , 800mj/ cm2 , 900mj/ cm2 or 1000mj/ cm2 , etc.).
所述涂层的厚度可根据用途进行设计，干燥后涂层的厚度可选为1～200μm(例如可以是1μm、2μm、5μm、10μm、20μm、40μm、60μm、80μm、100μm、120μm、140μm、160μm、180μm或200μm等)。如果该厚度不足1μm，则存在机械强度不足的倾向；如果超过200μm，则存在因光透过的降低而导致灵敏度变得不充分，导致光固化组合物混合后的光固化性降低的倾向。The thickness of the coating can be designed according to the application, and the thickness of the coating after drying can be selected to be 1 to 200 μm (for example, 1 μm, 2 μm, 5 μm, 10 μm, 20 μm, 40 μm, 60 μm, 80 μm, 100 μm, 120 μm, 140 μm, 160 μm, 180 μm or 200 μm, etc.). If the thickness is less than 1 μm, there is a tendency for insufficient mechanical strength; if it exceeds 200 μm, there is a tendency for insufficient sensitivity due to reduced light transmittance, resulting in reduced photocurability of the photocurable composition after mixing.
与相关技术相比，本申请具有以下有益效果：Compared with the related art, this application has the following beneficial effects:
本申请中通过对噻吨硫鎓盐光引发剂的结构进行设计，制备得到的噻吨硫鎓盐光引发剂具有较低的迁移性，经迁移性测试后，噻吨硫鎓盐光引发剂析出 的含量＜0.0085％，具体为0.0063％～0.0083％，且经气味性测试后，没有异味出现，解决了现有的光引发剂释放有毒和难闻的光解产物的问题。In the present application, the structure of the thioxanthone sulfonium salt photoinitiator is designed, and the prepared thioxanthone sulfonium salt photoinitiator has low mobility. After the mobility test, the thioxanthone sulfonium salt photoinitiator precipitates The content is less than 0.0085%, specifically 0.0063% to 0.0083%, and after the odor test, no odor is present, thus solving the problem of existing photoinitiators releasing toxic and unpleasant photolysis products.
在阅读并理解了详细描述后，可以明白其他方面。Still other aspects will be apparent upon reading and understanding the detailed description.
具体实施方式Detailed ways
为便于理解本申请，本申请列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。To facilitate understanding of the present application, the present application lists the following embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.
实施例1Example 1
本实施例提供一种噻吨硫鎓盐光引发剂及其制备方法，所述制备方法如下：This embodiment provides a thioxanthone sulfonium salt photoinitiator and a preparation method thereof, and the preparation method is as follows:
(1)2-异丙基-9，9-二甲基-9H-硫杂蒽的合成
(1) Synthesis of 2-isopropyl-9,9-dimethyl-9H-thioxanthine
在250mL三口烧瓶中加入化合物ITX(2.54g)和甲苯(40mL)，搅拌溶解，使用氮气对反应体系中的气体置换三次后，冰水浴降温至～0℃，向反应体系中滴加2.5M三甲基铝甲苯溶液(22mL)，滴加结束后保持～0℃继续搅拌1h，之后自然升至室温继续搅拌24h，TLC(EA∶Hex＝1∶20)和HPLC同步跟踪反应，待反应结束后，将体系降至～0℃，滴加饱和食盐水(25mL)，滴加结束后继续搅拌30min，分液，用饱和食盐水洗涤上层有机相两次(25mL×2)，有机相减压浓缩除去溶剂，得淡黄色油状产物2-异丙基-9，9-二甲基-9H-硫杂蒽(2.5g，收率93.2％，HPLC 92.98％)，其核磁氢谱数据如下所示：Compound ITX (2.54 g) and toluene (40 mL) were added to a 250 mL three-necked flask, stirred and dissolved, and the gas in the reaction system was replaced three times with nitrogen. The reaction system was cooled to ~0°C in an ice-water bath, and 2.5 M trimethylaluminum toluene solution (22 mL) was added dropwise to the reaction system. After the addition was completed, the mixture was kept at ~0°C and stirred for 1 h, then naturally warmed to room temperature and stirred for 24 h. TLC (EA: Hex = 1: 20) and HPLC were used to track the reaction simultaneously. After the reaction was completed, the system was cooled to ~0°C, saturated brine (25 mL) was added dropwise, and stirring was continued for 30 min after the addition was completed. The upper organic phase was washed twice with saturated brine (25 mL × 2), and the organic phase was concentrated under reduced pressure to remove the solvent to obtain a light yellow oily product 2-isopropyl-9,9-dimethyl-9H-thioxanthine (2.5 g, yield 93.2%, HPLC 92.98%), and its nuclear magnetic hydrogen spectrum data are shown as follows:
1H-NMR(CDCl3，500MHz)：1.14-1.15(d，6H)，1.58(s，6H)，2.76-2.83(m，1H)，6.94-6.96(dd，1H)，7.04-7.06(dd，2H)，7.12-7.13(dd，1H)，7.24-7.26(d，1H)，7.30-7.32(dd，1H)，7.38-7.40(dd，1H)。 1 H-NMR (CDCl 3 , 500 MHz): 1.14-1.15 (d, 6H), 1.58 (s, 6H), 2.76-2.83 (m, 1H), 6.94-6.96 (dd, 1H), 7.04-7.06 (dd, 2H), 7.12-7.13 (dd, 1H), 7.24-7.26 (d, 1H), 7.30-7.32 (dd, 1H), 7.38-7.40 (dd, 1H).
(2)合成亚砜化合物B
(2) Synthesis of sulfoxide compound B
将苯氧乙醇(138g，1mol)、DCM(二氯甲烷，200g)、碳酸钾(75.9g，0.55mol)混合搅拌，冰水浴下滴加(86.3g，1.1mol)乙酰氯，反应1小时，将反应液缓慢加入到300g冰水中，分出有机相，水洗至pH＝7，浓缩得到类白色固体中间产物2(170g，纯度99％，收率95％)；Phenoxyethanol (138 g, 1 mol), DCM (dichloromethane, 200 g), and potassium carbonate (75.9 g, 0.55 mol) were mixed and stirred, and acetyl chloride (86.3 g, 1.1 mol) was added dropwise under an ice-water bath. The mixture was reacted for 1 hour, and the reaction solution was slowly added into 300 g of ice water. The organic phase was separated, washed with water until pH = 7, and concentrated to obtain an off-white solid intermediate product 2 (170 g, purity 99%, yield 95%);
将1000mL反应瓶中加入中间产物2(90g，0.5mol)、DCM(450g)、氯化亚砜(44.5g，0.374mol)，降至0℃，向其中分批加入三氯化铝(107g，0.8mol)，反应2时后，将反应液加入到质量百分含量为10％盐酸冰水溶液(500g)中水解，分出有机相，水洗多次至pH＝7，浓缩得到104g白色固体，加80g甲苯重结晶，得到白色固体中间产物3(90g，纯度98％，收率88.6％)；The intermediate product 2 (90 g, 0.5 mol), DCM (450 g), and thionyl chloride (44.5 g, 0.374 mol) were added to a 1000 mL reaction bottle, and the temperature was lowered to 0° C., aluminum chloride (107 g, 0.8 mol) was added thereto in batches, and after reacting for 2 hours, the reaction solution was added to a 10% by weight hydrochloric acid ice water solution (500 g) for hydrolysis, and the organic phase was separated, washed with water for several times until pH=7, and concentrated to obtain 104 g of a white solid, which was recrystallized by adding 80 g of toluene to obtain a white solid intermediate product 3 (90 g, purity 98%, yield 88.6%);
将中间产物3(90g)、乙醇(150g)、纯水(150g)、片碱(40g)混合云军，在50℃反应4小时后，减压蒸干，得到白色固体，加纯水打浆多次烘干得到白色固体亚砜化合物B(71g，纯度98％，收率98％)。The intermediate product 3 (90 g), ethanol (150 g), pure water (150 g) and caustic soda (40 g) were mixed and reacted at 50° C. for 4 hours, and then evaporated to dryness under reduced pressure to obtain a white solid. Pure water was added to the mixture and the mixture was pulped and dried several times to obtain a white solid sulfoxide compound B (71 g, purity 98%, yield 98%).
(3)噻吨硫鎓盐光引发剂的合成
(3) Synthesis of Thioxanthenesulfonium Salt Photoinitiator
将2-异丙基-9，9-二甲基-9H-硫杂蒽(2.68g)、亚砜化合物B(3.22g)、DCM(10g)混合搅拌溶清后，降温至0℃，滴加98％质量浓度的浓硫酸(16g)，保温反应5小时，将反应液加入到20g冰水中水解，并分去水相，加入1.86g六氟磷酸钾和10g纯水搅拌半小时，分去水相，有机相水洗至pH＝7，减压浓缩蒸出溶剂，加甲苯结晶，得到类白色噻吨硫鎓盐光引发剂(5.7g，HPLC含量98％，收率80.5％)。2-isopropyl-9,9-dimethyl-9H-thioxanthene (2.68 g), sulfoxide compound B (3.22 g), and DCM (10 g) were mixed and stirred to dissolve, then cooled to 0°C, 98% mass concentration of concentrated sulfuric acid (16 g) was added dropwise, and the reaction was kept warm for 5 hours. The reaction solution was added into 20 g of ice water for hydrolysis, and the water phase was separated. 1.86 g of potassium hexafluorophosphate and 10 g of pure water were added and stirred for half an hour, the water phase was separated, and the organic phase was washed with water to pH = 7, concentrated under reduced pressure to evaporate the solvent, and toluene was added for crystallization to obtain an off-white thioxanthenol sulfonium salt photoinitiator (5.7 g, HPLC content 98%, yield 80.5%).
对本实施例提供的噻吨硫鎓盐光引发剂进行核磁测试表征，The thioxanthone sulfonium salt photoinitiator provided in this embodiment was characterized by nuclear magnetic resonance testing.
1H NMR(500MHz，Chloroform-d)δ7.98(dd，J＝7.1，2.3Hz，1H)，7.87-7.79(m，5H)，7.48(d，J＝7.1Hz，1H)，7.16-7.09(m，7H)，4.32(t，J＝7.3Hz，2H)，4.10(t，J＝6.5Hz，4H)，3.76(dt，J＝7.4，6.5Hz，4H)，2.96(p，J＝4.4Hz，1H)，1.61(s，6H)，1.28(d，J＝4.4Hz，6H). 1 H NMR (500 MHz, Chloroform-d) δ 7.98 (dd, J = 7.1, 2.3 Hz, 1H), 7.87-7.79 (m, 5H), 7.48 (d, J = 7.1 Hz, 1H), 7.16-7.09 (m, 7H), 4.32 (t, J = 7.3 Hz, 2H), 4.10 (t, J = 6.5 Hz, 4H), 3.76 (dt, J = 7.4, 6.5 Hz, 4H), 2.96 (p, J = 4.4 Hz, 1H), 1.61 (s, 6H), 1.28 (d, J = 4.4 Hz, 6H).
实施例2-10Example 2-10
实施例2-10依次提供一种噻吨硫鎓盐光引发剂及其制备方法，所述噻吨硫鎓盐光引发剂的制备原料(化合物2的结果详见下表1，亚砜化合物与实施例1相同)、以及制备得到的相应噻吨硫鎓盐光引发剂的结构及其核磁数据如下表1所示。Examples 2-10 provide a thioxanthone sulfonium salt photoinitiator and a preparation method thereof in turn. The raw materials for preparing the thioxanthone sulfonium salt photoinitiator (the results of compound 2 are detailed in Table 1 below, and the sulfoxide compound is the same as in Example 1), and the structures of the corresponding thioxanthone sulfonium salt photoinitiators prepared and their nuclear magnetic resonance data are shown in Table 1 below.
实施例2-10提供的噻吨硫鎓盐光引发剂可参照实施例1提供的噻吨硫鎓盐光引发剂的制备方法进行制备。 The thioxanthene sulfonium salt photoinitiators provided in Examples 2-10 can be prepared by referring to the preparation method of the thioxanthene sulfonium salt photoinitiator provided in Example 1.
表1



Table 1



其中，实施例2-10中使用的部分原料组分的制备方法如下：The preparation methods of some raw material components used in Examples 2-10 are as follows:
(1)硫化合物的制备(1) Sulfur compounds Preparation
向500mL三口烧瓶中加入无水四氢呋喃(100mL)，在冰水浴下，向其中缓慢添加氢化锂铝(3.2g)，滴加完毕后，向溶液中缓慢滴加三氯化铝溶液(11.2g三氯化铝溶解于100mL无水四氢呋喃中)，随后，逐次少量地向反应系中添加 2，4-二乙基硫杂蒽酮(13.0g)，回流搅拌30分钟，反应结束后，向烧瓶中加入乙酸乙酯，缓慢加入5wt％的HCl水溶液使残留物溶解，用二氯甲烷萃取，有机层用碳酸氢钠水溶液、氯化钠水溶液各洗3次，硫酸镁干燥，减压蒸馏除去溶剂，得到11.0g黄色黏性液体所述硫化合物(收率92％)，其核磁氢谱数据如下：Anhydrous tetrahydrofuran (100 mL) was added to a 500 mL three-necked flask. Lithium aluminum hydride (3.2 g) was slowly added thereto in an ice-water bath. After the addition was complete, aluminum chloride solution (11.2 g aluminum chloride dissolved in 100 mL anhydrous tetrahydrofuran) was slowly added to the solution. Subsequently, small amounts of 2,4-Diethylthioxanthone (13.0 g) was stirred under reflux for 30 minutes. After the reaction was completed, ethyl acetate was added to the flask, and a 5 wt% aqueous solution of HCl was slowly added to dissolve the residue. The mixture was extracted with dichloromethane, and the organic layer was washed with an aqueous sodium bicarbonate solution and an aqueous sodium chloride solution three times each, dried with magnesium sulfate, and the solvent was removed by distillation under reduced pressure to obtain 11.0 g of the sulfur compound as a yellow viscous liquid (yield 92%). The H NMR spectrum data are as follows:
1H-NMR(300MHz，CDCl3)：δ：1.21(t，3H)，1.26(t，3H)，2.60(q，2H)，2.80(q，2H)，3.81(s，2H)，6.9-7.4(m，6H)。 1 H-NMR (300 MHz, CDCl 3 ): δ: 1.21 (t, 3H), 1.26 (t, 3H), 2.60 (q, 2H), 2.80 (q, 2H), 3.81 (s, 2H), 6.9-7.4 (m, 6H).
(2)硫化合物的制备(2) Sulfur compounds Preparation
①9，10-二氢噻吨的合成
①Synthesis of 9,10-dihydrothioxanthene
在2L四口烧瓶中加入9-噻吨酮(53g)和THF(500mL)，搅拌均匀后，使用氮气对反应体系中的气体置换三次，冰水浴降温至0～10℃，向反应体系中滴加四氢呋喃硼烷络合物(1L)，滴加结束后保持0～10℃继续搅拌1h；将反应体系升温至回流反应(外温设置75℃)，TLC(EA∶Hex＝1∶20)和HPLC同步跟踪反应，待反应结束后(约回流3h反应结束)，停止反应；将反应体系降至室温，反应液减压浓缩至干，残留物中加入甲醇(250mL)析晶，抽滤，滤饼用少量甲醇漂洗，得白色固体产物9，10-二氢噻吨(45.5g，收率91.9％，HPLC99.37％)。9-thioxanthone (53 g) and THF (500 mL) were added to a 2L four-necked flask. After stirring, the gas in the reaction system was replaced three times with nitrogen. The temperature was cooled to 0-10°C in an ice-water bath. Tetrahydrofuran borane complex (1 L) was added dropwise to the reaction system. After the addition was completed, the temperature was maintained at 0-10°C and stirring was continued for 1 h. The reaction system was heated to reflux reaction (the external temperature was set to 75°C). TLC (EA: Hex = 1: 20) and HPLC were used to track the reaction simultaneously. After the reaction was completed (the reaction was completed after about 3 hours of reflux), the reaction was stopped. The reaction system was cooled to room temperature, the reaction solution was concentrated to dryness under reduced pressure, methanol (250 mL) was added to the residue for crystallization, and suction filtration was performed. The filter cake was rinsed with a small amount of methanol to obtain a white solid product 9,10-dihydrothioxanthene (45.5 g, yield 91.9%, HPLC 99.37%).
②9-丁基-9H-硫杂蒽的合成
②Synthesis of 9-butyl-9H-thioxanthine
在1L四口烧瓶中加入9，10-二氢噻吨(39.61g)和THF(400mL)，搅拌溶解后，使用氮气对反应体系中的气体置换三次，冰水浴降温至-10～0℃，向反应体系中滴加正丁基锂的四氢呋喃溶液(120mL，2.5M)，滴加结束后保持-10～0℃继续搅拌1h；然后在-10～0℃下，向其中滴入正溴丁烷(41.1g，1.5eq)，滴加结束后撤去冰水浴，自然升至室温保温反应，TLC(EA∶Hex＝1∶20)和HPLC同步跟踪反应，待反应结束后，停止反应；将体系降温至-10～0℃，滴入250mL水淬灭反应，反应液减压浓缩至干，残留物中加入100mL二氯甲烷萃取，水层继续萃取两次，合并有机相，使用饱和食盐水洗涤有机相一次，减压浓缩除去溶剂得淡黄色液体产物(37g，收率72.8％，HPLC 95.74％)，其核磁氢谱图如图3所示。9,10-dihydrothioxanthene (39.61 g) and THF (400 mL) were added to a 1L four-necked flask. After stirring and dissolving, the gas in the reaction system was replaced three times with nitrogen. The temperature was cooled to -10-0°C in an ice-water bath. A tetrahydrofuran solution of n-butyl lithium (120 mL, 2.5 M) was added dropwise to the reaction system. After the addition was completed, stirring was continued at -10-0°C for 1 h. Then, n-bromobutane (41.1 g, 1.5 eq) was added dropwise at -10-0°C. After the addition was completed, the ice-water bath was removed and the temperature was naturally raised to room temperature for insulation. The reaction was tracked synchronously by TLC (EA: Hex = 1: 20) and HPLC. After the reaction was completed, the reaction was stopped; the system was cooled to -10 ~ 0 ° C, 250 mL of water was added dropwise to quench the reaction, the reaction solution was concentrated to dryness under reduced pressure, 100 mL of dichloromethane was added to the residue for extraction, the water layer was extracted twice, the organic phases were combined, the organic phases were washed once with saturated brine, and the solvent was removed by concentration under reduced pressure to obtain a light yellow liquid product (37 g, yield 72.8%, HPLC 95.74%), and its H NMR spectrum is shown in Figure 3.
1H-NMR(CDCl3，500MHz)：0.72-0.75(t，3H)，1.04-1.16(m，4H)，1.60-1.66(q，2H)，3.83-3.87(t，1H)，7.06-7.13(m，4H)，7.14-7.16(m，2H)，7.29-7.31(m，2H)。 1 H-NMR (CDCl 3 , 500 MHz): 0.72-0.75 (t, 3H), 1.04-1.16 (m, 4H), 1.60-1.66 (q, 2H), 3.83-3.87 (t, 1H), 7.06-7.13 (m, 4H), 7.14-7.16 (m, 2H), 7.29-7.31 (m, 2H).
(3)硫化合物的制备(3) Sulfur compounds Preparation
参照硫化合物的制备方法，将其中的反应物正溴丁烷分别替换为烯丙基溴和环己基溴即可，其它反应条件不变。 Reference sulfur compounds The preparation method is as follows, wherein the reactant n-butyl bromide is replaced by allyl bromide and cyclohexyl bromide, respectively, and other reaction conditions remain unchanged.
LC-MS(M+H)+：239.2LC-MS(M+H)+：281.8。 LC-MS (M+H) + ：239.2 LC-MS (M+H) + : 281.8.
(4)亚砜化合物的制备(4) Sulfoxide compounds Preparation
①2-异丙基-9H-硫杂蒽的合成
①Synthesis of 2-isopropyl-9H-thioxanthine
在250mL三口烧瓶中加入化合物ITX(2.54g)和THF(四氢呋喃，40mL)，搅拌溶解，使用氮气对反应体系中的气体置换三次后，冰水浴降温至0～10℃，向反应体系中滴加四氢呋喃硼烷络合物(40mL)，滴加结束后保持0～10℃继续搅拌1h；然后将反应体系升温至回流反应(外温设置75℃)，TLC(EA∶Hex＝1∶20)和HPLC同步跟踪反应，待反应结束后(约回流3h反应结束)，将反应体系降至室温，将反应液减压浓缩至干，向残留物中加入甲醇(25mL)析晶，抽滤，得到的滤饼用少量甲醇漂洗，得白色固体产物2-异丙基-9H-硫杂蒽(2.2g，收率91.6％，HPLC 98.46％)，其核磁氢谱数据如下：Compound ITX (2.54 g) and THF (tetrahydrofuran, 40 mL) were added to a 250 mL three-necked flask, stirred and dissolved, and the gas in the reaction system was replaced three times with nitrogen. The reaction system was cooled to 0-10°C in an ice-water bath, and tetrahydrofuran borane complex (40 mL) was added dropwise to the reaction system. After the addition was completed, the temperature was maintained at 0-10°C and stirred for 1 h. The reaction system was then heated to reflux reaction (the external temperature was set to 75°C), and TLC (EA: Hex = 1: 20) and HPLC were used to track the reaction simultaneously. After the reaction was completed (the reaction was completed after about 3 h of reflux), the reaction system was cooled to room temperature, the reaction solution was concentrated to dryness under reduced pressure, methanol (25 mL) was added to the residue for crystallization, and the filter cake was rinsed with a small amount of methanol to obtain a white solid product 2-isopropyl-9H-thioxanthene (2.2 g, yield 91.6%, HPLC 98.46%), and its nuclear magnetic hydrogen spectrum data are as follows:
1H-NMR(CDCl3，500MHz)：1.15-1.17(d，6H)，2.77-2.84(m，1H)，3.76(s，2H)，6.96-6.99(d，1H)，7.08-7.12(m，4H)，7.27-7.29(d，1H)，7.34-7.36(d，1H)。 1 H-NMR (CDCl 3 , 500 MHz): 1.15-1.17 (d, 6H), 2.77-2.84 (m, 1H), 3.76 (s, 2H), 6.96-6.99 (d, 1H), 7.08-7.12 (m, 4H), 7.27-7.29 (d, 1H), 7.34-7.36 (d, 1H).
②2-异丙基-9H-硫杂蒽10-氧化物的合成
②Synthesis of 2-isopropyl-9H-thioxanthene 10-oxide
室温下，在100mL四口烧瓶中加入2-异丙基-9H-硫杂蒽(2.40g)和氯仿 (30mL)，搅拌溶解后，将反应体系降温至10～15℃，然后向其中缓慢滴加含有质量百分含量为85％的间氯过氧苯甲酸(2.1g)的氯仿溶液(30mL)，滴加结束后继续维持此温度搅拌反应2～3h；取样HPLC检测分析中控，待反应结束后(2-异丙基-9H-硫杂蒽含量(面积归一法)＜0.5％)，停止反应，有机相碱洗一次、水洗一次，母液浓缩至干，得到2-异丙基-9H-硫杂蒽10-氧化物(2.3g，收率90％，HPLC 97.4％)。At room temperature, 2-isopropyl-9H-thioxanthene (2.40 g) and chloroform were added to a 100 mL four-necked flask. (30mL), after stirring and dissolving, the reaction system was cooled to 10-15°C, and then a chloroform solution (30mL) containing 85% by mass of meta-chloroperbenzoic acid (2.1g) was slowly added dropwise, and the temperature was maintained and stirred for 2-3h after the addition was completed; sampling was performed for HPLC detection and analysis, and after the reaction was completed (2-isopropyl-9H-thioxanthene content (area normalization method) <0.5%), the reaction was stopped, the organic phase was washed once with alkali and once with water, and the mother liquor was concentrated to dryness to obtain 2-isopropyl-9H-thioxanthene 10-oxide (2.3g, yield 90%, HPLC 97.4%).
(5)亚砜化合物的制备(5) Sulfoxide compounds Preparation
①2-异丙基-9，9-二甲基-9H-硫杂蒽的合成
①Synthesis of 2-isopropyl-9,9-dimethyl-9H-thioxanthine
在250mL三口烧瓶中加入化合物ITX(2.54g)和甲苯(40mL)，搅拌溶解，使用氮气对反应体系中的气体置换三次后，冰水浴降温至～0℃，向反应体系中滴加2.5M三甲基铝甲苯溶液(22mL)，滴加结束后保持～0℃继续搅拌1h，之后自然升至室温继续搅拌24h，TLC(EA∶Hex＝1∶20)和HPLC同步跟踪反应，待反应结束后，将体系降至～0℃，滴加饱和食盐水(25mL)，滴加结束后继续搅拌30min，分液，用饱和食盐水洗涤上层有机相两次(25mL×2)，有机相减压浓缩除去溶剂，得淡黄色油状产物2-异丙基-9，9-二甲基-9H-硫杂蒽(2.5g，收率93.2％，HPLC 92.98％)，其核磁氢谱如下：Compound ITX (2.54 g) and toluene (40 mL) were added to a 250 mL three-necked flask, stirred and dissolved, and the gas in the reaction system was replaced three times with nitrogen. The reaction system was cooled to ~0°C in an ice-water bath, and 2.5 M trimethylaluminum toluene solution (22 mL) was added dropwise to the reaction system. After the addition was completed, the mixture was kept at ~0°C and stirred for 1 h. The mixture was then naturally warmed to room temperature and stirred for 24 h. The reaction was tracked by TLC (EA: Hex = 1: 20) and HPLC. After the reaction was completed, the system was cooled to ~0°C and saturated brine (25 mL) was added dropwise. After the addition was completed, the mixture was stirred for 30 min. The upper organic phase was washed twice with saturated brine (25 mL × 2). The organic phase was concentrated under reduced pressure to remove the solvent to obtain a light yellow oily product, 2-isopropyl-9,9-dimethyl-9H-thioxanthine (2.5 g, yield 93.2%, HPLC 92.98%), and its H NMR spectrum was as follows:
1H-NMR(CDCl3，500MHz)：1.14-1.15(d，6H)，1.58(s，6H)，2.76-2.83(m，1H)，6.94-6.96(dd，1H)，7.04-7.06(dd，2H)，7.12-7.13(dd，1H)，7.24-7.26(d，1H)，7.30-7.32(dd，1H)，7.38-7.40(dd，1H)。 1 H-NMR (CDCl 3 , 500 MHz): 1.14-1.15 (d, 6H), 1.58 (s, 6H), 2.76-2.83 (m, 1H), 6.94-6.96 (dd, 1H), 7.04-7.06 (dd, 2H), 7.12-7.13 (dd, 1H), 7.24-7.26 (d, 1H), 7.30-7.32 (dd, 1H), 7.38-7.40 (dd, 1H).
②2-异丙基-9，9-二甲基-9H-硫杂蒽-10-氧化物的合成
②Synthesis of 2-isopropyl-9,9-dimethyl-9H-thioxanthine-10-oxide
室温下，在100mL四口烧瓶中加入2-异丙基-9，9-二甲基-9H-硫杂蒽(2.68g)和氯仿(30mL)，搅拌溶解后，体系开始降温至10～15℃，然后向其中缓慢滴加含有质量百分含量为85％的间氯过氧苯甲酸(2.1g)的氯仿溶液(30mL)，滴加结束后继续维持此温度搅拌反应2～3h；取样HPLC检测分析中控，待反应结束后(2-异丙基-9，9-二甲基-9H-硫杂蒽含量(面积归一法)＜0.5％)，停止反应，有机相碱洗一次、水洗一次，母液浓缩至干，得到2-异丙基-9，9-二甲基-9H-硫杂蒽-10-氧化物(2.64g，收率93％，HPLC 96.8％)。At room temperature, 2-isopropyl-9,9-dimethyl-9H-thioxanthene (2.68 g) and chloroform (30 mL) were added to a 100 mL four-necked flask. After stirring and dissolving, the system began to cool down to 10-15°C, and then a chloroform solution (30 mL) containing 85% by mass of m-chloroperbenzoic acid (2.1 g) was slowly added dropwise. After the addition was completed, the temperature was maintained and stirred for 2-3 h. Sampling was performed for HPLC detection and analysis. After the reaction was completed (the content of 2-isopropyl-9,9-dimethyl-9H-thioxanthene (area normalization method) was <0.5%), the reaction was stopped, the organic phase was washed once with alkali and once with water, and the mother liquor was concentrated to dryness to obtain 2-isopropyl-9,9-dimethyl-9H-thioxanthene-10-oxide (2.64 g, yield 93%, HPLC 96.8%).
(6)亚砜化合物的制备(6) Sulfoxide compounds Preparation
室温下，在干燥的100mL四口烧瓶中加入9-(烯丙基)-9H-噻吨2.38g和二氯甲烷50g，搅拌溶清，保持内温0-5℃，滴加m-CPBA的二氯甲烷溶液(2.2g/50gDCM)，滴加完毕，自然升至温室反应2-3h，HPLC跟踪反应，反应结束，反应液先加入10％片碱溶液洗两次(30mL×2)，再水洗两次后有机相减压浓缩干，得到产品2.2g(HPLC 98.5％，收率85.0％)；LC-MS(M+H)+：255.06。At room temperature, 2.38 g of 9-(allyl)-9H-thioxanthine and 50 g of dichloromethane were added to a dry 100 mL four-necked flask. The mixture was stirred to dissolve. The internal temperature was maintained at 0-5°C, and a dichloromethane solution of m-CPBA (2.2 g/50 g DCM) was added dropwise. After the addition was completed, the temperature was naturally raised to room temperature for reaction for 2-3 h. The reaction was tracked by HPLC. After the reaction was completed, the reaction solution was first washed twice with 10% caustic soda solution (30 mL×2), and then washed twice with water. The organic phase was concentrated under reduced pressure to dryness to obtain 2.2 g of the product (HPLC 98.5%, yield 85.0%); LC-MS (M+H) + : 255.06.
(7)亚砜化合物的制备 (7) Sulfoxide compounds Preparation
参考实施例亚砜化合物的合成方法，将其中的反应物9-(烯丙基)-9H-噻吨替换为9-环己基-9H-噻吨即可，其它反应条件不变。Reference Example Sulfoxide Compound The synthetic method is to replace the reactant 9-(allyl)-9H-thioxanthine with 9-cyclohexyl-9H-thioxanthine, and the other reaction conditions remain unchanged.
LC-MS(M+H)+：297.3。 LC-MS (M+H) + : 297.3.
应用例1-10以及对比应用例1Application Examples 1-10 and Comparative Application Example 1
应用例1-10和对比应用例1分别提供一种光固化组合物，所述光固化组合物的具体组成详见表2，需要说明的是，表2中的各组分的用量均为质量份数。Application Examples 1-10 and Comparative Application Example 1 respectively provide a photocurable composition. The specific composition of the photocurable composition is shown in Table 2. It should be noted that the amount of each component in Table 2 is in parts by mass.
所述光固化组合物的制备方法如下：The preparation method of the photocurable composition is as follows:
首先将相应的光引发剂溶解在溶剂碳酸丙烯酯中，然后与其他组分(A1、A2、A3)混合均匀，配制得到光固化组合物。Firstly, the corresponding photoinitiator is dissolved in the solvent propylene carbonate, and then evenly mixed with other components (A1, A2, A3) to prepare a photocurable composition.
表2

Table 2

其中，溶剂为碳酸丙烯酯；Wherein, the solvent is propylene carbonate;
A1：3，4-环氧环己烯甲基-3，4-环氧环己烯酸酯；A1: 3,4-epoxycyclohexenemethyl-3,4-epoxycyclohexene ester;
A2：3-羟甲基-3-乙基氧杂环丁烷；A2: 3-hydroxymethyl-3-ethyloxetane;
A3：1，4-环己基二甲醇二乙烯基醚；A3: 1,4-cyclohexyl dimethanol divinyl ether;
光引发剂1-10依次为上述实施例1-10提供的噻吨硫鎓盐光引发剂；Photoinitiators 1-10 are the thioxanthenolsulfonium salt photoinitiators provided in Examples 1-10 above;
光引发剂A为： Photoinitiator A is:
对应用例1-10和对比应用例1-2提供的光固化组合物的性能进行测试，具体测试方法如下：The performance of the photocurable composition provided in Example 1-10 and Comparative Example 1-2 was tested, and the specific test method was as follows:
迁移性评价：将上述应用例和对比应用例提供的光固化组合物分别在黄光灯下搅拌，取料于PET模板上滚涂成膜，在90℃下干燥5min除去溶剂，形成膜厚约2μm的涂膜；将形成有涂膜的基板冷却至室温，用高压汞灯(曝光机型号RW-UV70201，波长200～500nm，光强100mW/cm2)照射，对涂膜进行曝光，曝光时间5s，分别得到所需的固化膜；接着，以10mL甲醇为模拟液，将固化后的膜放于模拟液中，室温放置24h，用HPLC分析析出光引发剂的量(岛津LC-MS2020，流动相甲醇/水＝55/45，0.5％磷酸二氢盐)，以液相中出峰的百分含量进行比较，液相中相对引发剂含量越低，越不易迁移。Migration evaluation: The photocurable compositions provided in the above application examples and comparative application examples were stirred under a yellow light lamp, and the materials were roll-coated on a PET template to form a film, and dried at 90°C for 5 minutes to remove the solvent to form a coating film with a thickness of about 2 μm; the substrate with the coating film was cooled to room temperature, and irradiated with a high-pressure mercury lamp (exposure machine model RW-UV70201, wavelength 200-500nm, light intensity 100mW/ cm2 ) to expose the coating film for an exposure time of 5 seconds to obtain the desired cured films; then, 10 mL of methanol was used as a simulated liquid, and the cured film was placed in the simulated liquid and placed at room temperature for 24 hours. The amount of precipitated photoinitiator was analyzed by HPLC (Shimadzu LC-MS2020, mobile phase methanol/water = 55/45, 0.5% dihydrogen phosphate), and the percentage of the peak in the liquid phase was compared. The lower the relative initiator content in the liquid phase, the less likely it is to migrate.
气味评价：将上述应用例和对比应用例提供的光固化组合物分别在黄光灯 下搅拌，取料于PET模板上滚涂成膜，在90℃下干燥5min除去溶剂，形成膜厚约2μm的涂膜；将形成有涂膜的基板冷却至室温，用高压汞灯(曝光机型号RW-UV70201，波长200～500nm，光强100mW/cm2)照射，对涂膜进行曝光，曝光时间5s，分别得到所需的固化膜；立即将涂有固化膜的基材放入密封袋中密封1小时，然后打开密封袋对残余气味进行测试，评估的标准以数字标示如下：Odor evaluation: The photocurable compositions provided in the above application examples and comparative application examples were placed under yellow light. Stirring under low temperature, the material was rolled onto a PET template to form a film, and dried at 90°C for 5 minutes to remove the solvent, forming a coating film with a thickness of about 2 μm; the substrate with the coating film was cooled to room temperature, and irradiated with a high-pressure mercury lamp (exposure machine model RW-UV70201, wavelength 200-500nm, light intensity 100mW/ cm2 ) to expose the coating film for 5 seconds to obtain the desired cured films; the substrate coated with the cured film was immediately placed in a sealed bag and sealed for 1 hour, and then the sealed bag was opened to test the residual odor. The evaluation standards are indicated by numbers as follows:
0级：没有气味；1级：非常轻微的气味；2级：轻微的气味；3级：明显的气味；4级：强烈的气味；5级：非常强烈的气味。Level 0: no odor; Level 1: very slight odor; Level 2: slight odor; Level 3: obvious odor; Level 4: strong odor; Level 5: very strong odor.
对上述应用例和对比应用例提供的光固化组合物的性能测试详见下表3：The performance tests of the photocurable compositions provided in the above application examples and comparative application examples are detailed in Table 3 below:
表3
table 3
通过表3的数据可知，本申请中通过对噻吨硫鎓盐光引发剂的结构进行设 计，制备得到的噻吨硫鎓盐光引发剂具有较低的迁移性和气味性，其经迁移性测试后，噻吨硫鎓盐光引发剂析出的含量＜0.009％，具体为0.0063％～0.0088％，且经气味性测试后，没有异味出现，解决了现有的光引发剂释放有毒和难闻的光解产物的问题。From the data in Table 3, it can be seen that in this application, the structure of the thioxanthenol sulfonium salt photoinitiator is designed. The prepared thioxanthene sulfonium salt photoinitiator has lower mobility and odor. After the mobility test, the precipitated thioxanthene sulfonium salt photoinitiator content is less than 0.009%, specifically 0.0063% to 0.0088%, and after the odor test, no odor is present, thus solving the problem of existing photoinitiators releasing toxic and unpleasant photolysis products.
申请人声明，本申请通过上述实施例来详细说明本申请的提供的噻吨硫鎓盐光引发剂的具体结构和制备方法，但本申请并不局限于上述详细说明。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本申请的保护范围和公开范围之内。 The applicant declares that the present application uses the above-mentioned embodiments to explain in detail the specific structure and preparation method of the thioxanthenol sulfonium salt photoinitiator provided by the present application, but the present application is not limited to the above-mentioned detailed description. The technicians in the relevant technical field should understand that any improvement to the present application, the equivalent replacement of the raw materials of the product of the present application, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present application.

Claims (15)

  1. 一种噻吨硫鎓盐光引发剂，其中，所述噻吨硫鎓盐光引发剂具有如下式I所示结构：
    A thioxanthonesulfonium salt photoinitiator, wherein the thioxanthonesulfonium salt photoinitiator has a structure shown in the following formula I:
    其中，M表示硫原子、S＝O；Wherein, M represents a sulfur atom, S＝O;
    R′1、R1、R2、R3、R4、R5各自独立地选自氢、取代或未取代的C1-C30烷基、C1-C20烷氧基、C1-C20烷硫基、C2-C20烯基、C2-C20炔基、C6-C14芳基、C3-C20杂芳基、含有C-R″-C结构的碳原子个数为2～30的取代基；R′ 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C2-C20 alkenyl, C2-C20 alkynyl, C6-C14 aryl, C3-C20 heteroaryl, and a substituent having 2 to 30 carbon atoms and a CR″-C structure;
    所述取代的取代基包括C6-C14芳基；The substituted substituents include C6-C14 aryl;
    所述R″选自O、S、酯基、硫酯基、酰胺基或氨基甲酸酯基；The R″ is selected from O, S, an ester group, a thioester group, an amide group or a carbamate group;
    γ-表示无机阴离子或有机阴离子。γ- represents an inorganic anion or an organic anion.
  2. 根据权利要求1所述的噻吨硫鎓盐光引发剂，其中，所述含有C-R″-C结构的碳原子个数为2～30的取代基选自：含有C-R″-C结构的C2-C20直链或支链烷基、含有C-R″-C结构的C3-C20环烷基、含有C-R″-C结构的被C3～C8环烷基取代的C1-C10的链状烷基、含有C-R″-C结构的被C1-C20链状烷基取代的C3-C8环烷基、含有C-R″-C结构的被C6-C14芳基取代的C1-C10烷基、含有C-R″-C结构的C2-C20链状烯基、含有C-R″-C结构的C2-C20炔基；The thioxanthenol sulfonium salt photoinitiator according to claim 1, wherein the substituent having 2 to 30 carbon atoms and containing a C-R"-C structure is selected from: a C2-C20 straight or branched alkyl group containing a C-R"-C structure, a C3-C20 cycloalkyl group containing a C-R"-C structure, a C1-C10 chain alkyl group substituted with a C3 to C8 cycloalkyl group containing a C-R"-C structure, a C3-C8 cycloalkyl group substituted with a C1-C20 chain alkyl group containing a C-R"-C structure, a C1-C10 alkyl group substituted with a C6-C14 aryl group containing a C-R"-C structure, a C2-C20 chain alkenyl group containing a C-R"-C structure, and a C2-C20 alkynyl group containing a C-R"-C structure;
    其中，R″具有与权利要求1相同的保护范围。Wherein, R″ has the same protection scope as claim 1.
  3. 根据权利要求1或2所述的噻吨硫鎓盐光引发剂，其中，所述R′1、R1、 R2、R3、R4、R5各自独立地选自氢、未取代的C1-C20直链或支链烷基、未取代的C3-C20环烷基、C3～C8环烷基取代的C1-C10的链状烷基、C1-C20链状烷基取代的C3-C8环烷基、C6-C14芳基取代的C1-C10烷基、C1-C15烷氧基、C1-C15烷硫基、C2-C20链状烯基、C5-C20环烯基、C2-C16炔基、C6-C14芳基、C3-C20杂芳基、含有C-R″-C结构的C2-C20直链或支链烷基；The thioxanthenolsulfonium salt photoinitiator according to claim 1 or 2, wherein R′ 1 , R 1 , R2 , R3 , R4 , R5 are each independently selected from hydrogen, unsubstituted C1-C20 straight or branched alkyl, unsubstituted C3-C20 cycloalkyl, C1-C10 chain alkyl substituted with C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted with C1-C20 chain alkyl, C1-C10 alkyl substituted with C6-C14 aryl, C1-C15 alkoxy, C1-C15 alkylthio, C2-C20 chain alkenyl, C5-C20 cycloalkenyl, C2-C16 alkynyl, C6-C14 aryl, C3-C20 heteroaryl, C2-C20 straight or branched alkyl containing CR″-C structure;
    其中，R″具有与权利要求1相同的保护范围。Wherein, R″ has the same protection scope as claim 1.
  4. 根据权利要求2或3所述的噻吨硫鎓盐光引发剂，其中，所述R′1、R1、R2、R3、R4、R5各自独立地选自未取代的C1-C10的直链或支链烷基；The thioxanthenolsulfonium salt photoinitiator according to claim 2 or 3, wherein R' 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from unsubstituted C1-C10 straight or branched alkyl groups;
    可选地，所述C1-C10的直链或支链烷基包括甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、异戊基、新戊基、2-甲基丁基、1-乙基丙基、己基、异己基、庚基、辛基、壬基。Optionally, the C1-C10 straight or branched alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, 2-methylbutyl, 1-ethylpropyl, hexyl, isohexyl, heptyl, octyl, and nonyl.
  5. 根据权利要求2或3所述的噻吨硫鎓盐光引发剂，其中，所述R′1、R1、R2、R3、R4、R5各自独立地选自未取代的C3-C8环烷基；The thioxanthenolsulfonium salt photoinitiator according to claim 2 or 3, wherein R' 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from unsubstituted C3-C8 cycloalkyl groups;
    可选地，所述C3-C8环烷基包括环丙基、环丁基、环戊基、环己基、环庚基、环辛基。Optionally, the C3-C8 cycloalkyl group includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  6. 根据权利要求2或3所述的噻吨硫鎓盐光引发剂，其中，所述R′1、R1、R2、R3、R4、R5各自独立地选自C3-C8环烷基取代的C1-C7链状烷基；The thioxanthenolsulfonium salt photoinitiator according to claim 2 or 3, wherein R' 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from a C1-C7 chain alkyl substituted with a C3-C8 cycloalkyl group;
    可选地，所述C3-C8环烷基取代的C1-C7链状烷基包括环戊基乙基、环戊基甲基、环己基甲基、环己基乙基。Optionally, the C1-C7 chain alkyl substituted by the C3-C8 cycloalkyl group includes cyclopentylethyl, cyclopentylmethyl, cyclohexylmethyl, and cyclohexylethyl.
  7. 根据权利要求2或3所述的噻吨硫鎓盐光引发剂，其中，所述R′1、R1、R2、R3、R4、R5各自独立地选自C1-C10链状烷基取代的C3-C7环烷基；The thioxanthenolsulfonium salt photoinitiator according to claim 2 or 3, wherein R' 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from a C3-C7 cycloalkyl group substituted with a C1-C10 chain alkyl group;
    可选地，所述C1-C10链状烷基取代的C3-C7环烷基包括2-甲基-1-环戊基、3-甲基-1-环戊基、2-甲基-1-环己基、3-甲基-1-环己基、4-甲基-1-环己基。 Optionally, the C3-C7 cycloalkyl substituted by the C1-C10 chain alkyl group includes 2-methyl-1-cyclopentyl, 3-methyl-1-cyclopentyl, 2-methyl-1-cyclohexyl, 3-methyl-1-cyclohexyl, and 4-methyl-1-cyclohexyl.
  8. 根据权利要求2或3所述的噻吨硫鎓盐光引发剂，其中，所述R′1、R1、R2、R3、R4、R5各自独立地选自C6-C10芳基取代的C1-C6烷基；The thioxanthenolsulfonium salt photoinitiator according to claim 2 or 3, wherein R' 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from C1-C6 alkyl substituted with C6-C10 aryl;
    可选地，所述C6-C10芳基取代的C1-C6烷基包括苄基、α-苯基乙基、β-苯基乙基、3-苯基丙基、4-苯基丁基、1-萘基甲基、2-萘基甲基。Optionally, the C1-C6 alkyl substituted by the C6-C10 aryl group includes benzyl, α-phenylethyl, β-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 1-naphthylmethyl, and 2-naphthylmethyl.
  9. 根据权利要求2-8任一项所述的噻吨硫鎓盐光引发剂，其特征在于，所述R′1、R1、R2、R3、R4、R5各自独立地选自C1-C10烷氧基；The thioxanthenolsulfonium salt photoinitiator according to any one of claims 2 to 8, characterized in that R′ 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from C1-C10 alkoxy groups;
    可选地，所述C1-C10烷氧基包括甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、叔丁氧基、戊氧基、异戊氧基、新戊氧基、2-乙基己氧基、4-甲基戊氧基、己氧基、庚氧基、辛氧基、壬氧基；Optionally, the C1-C10 alkoxy group includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, 2-ethylhexyloxy, 4-methylpentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy;
    可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自C1-C10烷硫基；Optionally, said R′ 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from C1-C10 alkylthio;
    可选地，所述C1-C10烷硫基包括甲硫基、乙硫基、丙硫基、异丙硫基、正丁硫基、仲丁硫基、异丁硫基、叔丁硫基。Optionally, the C1-C10 alkylthio group includes methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio and tert-butylthio.
    可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自C2-C10链状烯基；Optionally, said R′ 1 , R 1 , R 2 , R 3 , R 4 , and R5 are each independently selected from C2-C10 chain alkenyl groups;
    可选地，所述C2-C10链状烯基包括乙烯基、1-丙烯基、烯丙基、异丙烯基、甲代烯丙基、丁烯基、戊烯基、己烯基、异己烯基、庚烯基、辛烯基、壬烯基；Optionally, the C2-C10 chain alkenyl group includes vinyl, 1-propenyl, allyl, isopropenyl, methallyl, butenyl, pentenyl, hexenyl, isohexenyl, heptenyl, octenyl, nonenyl;
    可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自C5-C10环烯基；Optionally, said R′ 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from C5-C10 cycloalkenyl;
    可选地，所述C5-C10环烯基包括环戊烯基、环己烯基、环庚烯基、环辛烯基、降冰片烯基；Optionally, the C5-C10 cycloalkenyl group includes cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, norbornene;
    可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自C2-C10炔基；Optionally, said R′ 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from C2-C10 alkynyl;
    可选地，所述C2-C10炔基包括乙炔基、1-丙炔基、异丙炔基、丁炔基、戊炔基、己炔基、庚炔基、辛炔基、壬炔基；Optionally, the C2-C10 alkynyl group includes ethynyl, 1-propynyl, isopropynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl;
    可选地，所述R′1、R1、R2、R3、R4、R5各自独立地选自C6-C10芳基；Optionally, the R′ 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from C6-C10 aryl groups;
    可选地，所述C6-C10芳基包括苯基、1-萘基、2-萘基； Optionally, the C6-C10 aryl group includes phenyl, 1-naphthyl, 2-naphthyl;
    可选地，R’1、R1、R2、R3、R4、R5分别独立地选自C3-C10杂芳基；Optionally, R' 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from C3-C10 heteroaryl;
    可选地，所述C3-C10杂芳基包括噻吩基、噻吩-2-甲基、吡啶基、2-呋喃基、喹啉基、吡喃基、咪唑基、哌啶基、吗啉基、噻吨基、吲哚基；Optionally, the C3-C10 heteroaryl includes thienyl, thien-2-methyl, pyridyl, 2-furyl, quinolyl, pyranyl, imidazolyl, piperidinyl, morpholinyl, thioxanthenyl, indolyl;
    可选地，所述R′1、R1、R2、R3、R4、R5分别独立地选自含有C-R″-C结构的C2-C10直链或支链烷基；Optionally, the R′ 1 , R 1 , R 2 , R 3 , R 4 , and R 5 are independently selected from C2-C10 straight or branched alkyl groups containing a CR″-C structure;
    可选地，所述含有C-R″-C结构的C2-C10直链或支链烷基包括-(CH2CH2O)2CH3、-(CH2CH2O)2CH2CH3、 Optionally, the C2-C10 straight or branched alkyl group containing a CR″-C structure includes -(CH 2 CH 2 O) 2 CH 3 , -(CH 2 CH 2 O) 2 CH 2 CH 3 ,
  10. 根据权利要求1-9任一项所述的噻吨硫鎓盐光引发剂，其中，所述γ-表示X-、ClO4 -、CN-、HSO4 -、CF3COO-、(BX4)-、(SbX6)-、(AsX6)-、(PX6)-、Al[OC(CF3)3]4 -、磺酸根离子、B(C6X5)4 -或[(Rf)bPF6-b]-中的任一种；The thioxanthenolsulfonium salt photoinitiator according to any one of claims 1 to 9, wherein the γ- represents any one of X- , ClO4- , CN- , HSO4- , CF3COO- , ( BX4 ) - , ( SbX6 ) - , ( AsX6 ) - , ( PX6 ) - , Al[OC( CF3 ) 3 ]4- , sulfonate ion, B ( C6X5 ) 4- or [(Rf)bPF6 -b ] - ;
    其中，X选自F或Cl；wherein X is selected from F or Cl;
    Rf表示C1-C6氟代烷基，b表示1～5的整数，且b表示2～5的整数时，Rf基团相同或不相同；Rf represents a C1-C6 fluoroalkyl group, b represents an integer from 1 to 5, and when b represents an integer from 2 to 5, the Rf groups are the same or different;
    可选地，所述γ-选自PF6 -、SbF6 -、AsF6 -、BF4 -、B(C6F5)4 -中的任一种。Optionally, the γ- is selected from any one of PF 6 - , SbF 6 - , AsF 6 - , BF 4 - , and B(C 6 F 5 ) 4 - .
  11. 根据权利要求1-10任一项所述的噻吨硫鎓盐光引发剂，其中，所述噻吨硫鎓盐光引发剂的阳离子部分选自阳离子结构1-12中的任意一种：

    The thioxanthonesulfonium salt photoinitiator according to any one of claims 1 to 10, wherein the cationic portion of the thioxanthonesulfonium salt photoinitiator is selected from any one of cationic structures 1 to 12:

  12. 一种如权利要求1-11任一项所述的噻吨硫鎓盐光引发剂的制备方法，其中，所述制备方法包括如下步骤：A method for preparing the thioxanthenolsulfonium salt photoinitiator according to any one of claims 1 to 11, wherein the preparation method comprises the following steps:
    在催化剂的作用下，化合物1与化合物2进行傅克反应，反应结束后，向其中加入有机盐或无机盐进行阴离子交换反应，得到所述噻吨硫鎓盐光引发剂；Under the action of a catalyst, compound 1 and compound 2 undergo a Friedel-Crafts reaction, and after the reaction is completed, an organic salt or an inorganic salt is added thereto to perform an anion exchange reaction to obtain the thioxanthenolsulfonium salt photoinitiator;
    其中，化合物1为 Among them, compound 1 is
    化合物2为 Compound 2 is
    M、R1’、R1、R2、R3、R4、R5具有与权利要求1相同的保护范围。M, R 1 ', R 1 , R 2 , R 3 , R 4 , and R 5 have the same protection scope as that of claim 1.
  13. 根据权利要求12所述的制备方法，其特征在于，所述催化剂选自硫酸、三氯化铝、三氯化铁、氯化锌、五氧化二磷-甲烷磺酸中的任意一种或至少两种的组合；The preparation method according to claim 12, characterized in that the catalyst is selected from any one of sulfuric acid, aluminum chloride, ferric chloride, zinc chloride, phosphorus pentoxide-methanesulfonic acid or a combination of at least two thereof;
    可选地，所述傅克反应的温度≤25℃，进一步可选为-5～15℃；Optionally, the temperature of the Friedel-Crafts reaction is ≤25°C, and may further be -5 to 15°C;
    可选地，所述傅克反应的时间为1～5h；Optionally, the Friedel-Crafts reaction time is 1 to 5 hours;
    可选地，所述有机盐或无机盐选自六氟磷酸钾、四氟硼酸钾、六氟锑酸钾、四(五氟苯基)硼酸钠、六氟锑酸钠、六氟砷酸钠中的任意一种；Optionally, the organic salt or inorganic salt is selected from any one of potassium hexafluorophosphate, potassium tetrafluoroborate, potassium hexafluoroantimonate, sodium tetrakis(pentafluorophenyl)borate, sodium hexafluoroantimonate, and sodium hexafluoroarsenate;
    可选地，所述阴离子交换反应的温度为20～25℃；Optionally, the temperature of the anion exchange reaction is 20-25°C;
    可选地，所述阴离子交换反应的时间为1～3h。Optionally, the anion exchange reaction time is 1 to 3 hours.
  14. 一种如权利要求1-11任一项所述的噻吨硫鎓盐光引发剂的应用，其中，所述噻吨硫鎓盐光引发剂用于制备涂料、油墨或粘合剂。A use of the thioxanthene sulfonium salt photoinitiator according to any one of claims 1 to 11, wherein the thioxanthene sulfonium salt photoinitiator is used to prepare coatings, inks or adhesives.
  15. 一种光固化组合物，其中，所述光固化组合物包括如权利要求1-11任一项所述的噻吨硫鎓盐光引发剂； A photocurable composition, wherein the photocurable composition comprises the thioxanthenolsulfonium salt photoinitiator according to any one of claims 1 to 11;
    可选地，所述光固化组合物包括如下组分：含环氧乙烷基团的化合物和/或含乙烯基醚基团的化合物、氧杂环丁烷化合物、如权利要求1-11任一项所述的噻吨硫鎓盐光引发剂。 Optionally, the photocurable composition comprises the following components: a compound containing an oxirane group and/or a compound containing a vinyl ether group, an oxetane compound, and a thioxanthenolsulfonium salt photoinitiator as claimed in any one of claims 1 to 11.
PCT/CN2023/136475 2022-12-30 2023-12-05 Thioxanthene sulfonium salt photoinitiator as well as preparation method therefor and use thereof WO2024140063A1 (en)

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