Organosilicon compatible macromolecular photoinitiator for LED (light-emitting diode) photopolymerization as well as preparation and application of organosilicon compatible macromolecular photoinitiator

Abstract

The invention relates to an organic silicon compatible macromolecular photoinitiator, the absorption wavelength of the initiator is not only suitable for LED light source polymerization, especially can effectively initiate the photopolymerization reaction of organic silicon resin, but also has good compatibility with the organic silicon resin, and simultaneously reduces the migration and volatilization of photolysis fragments in the photopolymerization process. The invention further relates to a method for preparing the organic silicon compatible macromolecular photoinitiator and application of the organic silicon compatible macromolecular photoinitiator in LED photopolymerization.

Description

Technical Field

[0001] The invention belongs to the field of photosensitive polymer materials, and specifically relates to an organosilicon compatible macromolecular photoinitiator, which is particularly suitable for LED photopolymerization of organosilicon resins. The invention also relates to the preparation and application of the organosilicon compatible macromolecular photoinitiator. Background Art

[0002] With its excellent chemical stability, weather resistance, flexibility, insulation, low surface energy and low surface tension, silicone materials have shown important application value in many fields such as building materials, electronics and electrical, communications semiconductors, daily chemical textiles and new energy. The preparation methods of silicone materials mainly include: sol-gel method, hydrothermal method, solvent thermal method, plasma chemical vapor deposition method, polycondensation method and polymerization method. The polymerization method can be divided into catalytic polymerization, emulsion polymerization, thermal polymerization and photopolymerization. Among them, the preparation of silicone materials by photopolymerization has many advantages such as high efficiency, energy saving, environmental protection and economy, and photoinitiator plays a very important role in the preparation of silicone materials by photopolymerization.

[0003] At the same time, with the continuous development of LED photopolymerization technology, in order to meet the wide application needs of LED photopolymerization technology, many scientific research teams are committed to the development of photoinitiators suitable for LED photopolymerization. There are already some such photoinitiators in the prior art, but the currently reported photoinitiators that can be used for LED photopolymerization are mainly small molecule structures. For example, CN104817653A discloses a coumarin compound suitable for UV-LED light source curing, and CN102492059A discloses substituted diphenyl sulfide ether ketone photoinitiators, etc. This type of photoinitiator and its photolysis fragments are easy to migrate and volatilize, resulting in product aging and yellowing, unpleasant odor and toxicity. In addition, most of the photoinitiators in the prior art have poor compatibility in silicone resin systems. These problems greatly limit the development of photoinitiators suitable for silicone materials. Therefore, it is of great significance to develop silicone-compatible macromolecular photoinitiators suitable for LED photopolymerization. Summary of the invention

[0004] In order to promote the development of LED photopolymerization technology, the inventors have been committed to the promotion and application research of organosilicon compatible macromolecules, especially continuously researching and developing more organosilicon compatible macromolecular photoinitiators suitable for LED photopolymerization. At the same time, especially in view of the problems existing in the prior art, the inventors have conducted extensive and in-depth research on organosilicon compatible macromolecular photoinitiators suitable for LED photopolymerization, in order to find a new organosilicon compatible macromolecular photoinitiator that can effectively initiate the photopolymerization reaction of organosilicon resin, is well compatible with organosilicon resin, and can reduce the migration and volatilization of photolytic fragments during the photopolymerization process.

[0005] The inventors were surprised to find that by introducing organosilicon segments into the molecular structure of benzoylformate derivatives, a novel organosilicon compatible macromolecular photoinitiator with good compatibility with organosilicon resin was successfully prepared. The photoinitiator prepared by the present invention not only effectively improves the compatibility between the photoinitiator and the organosilicon resin, achieves a good blending effect, and simultaneously reduces the migration and volatilization of photolysis fragments during the photopolymerization process, providing a new approach and method for preparing organosilicon materials by photopolymerization. In addition, the photoinitiator prepared by the present invention has excellent matching with LED light sources of 365-410nm wavelength, especially 385nm, 395nm and 405nm wavelength, showing good light initiation ability, and ensuring efficient photopolymerization rate under LED light source. In addition, the synthesis process of the present invention is simple, and has significant advantages in preparation, and the obtained organosilicon compatible macromolecular photoinitiator is more environmentally friendly in application, expands the scope of application, and promotes the development of LED photopolymerization technology in the field of organosilicon materials.

[0006] The object of the present invention is achieved based on the above-mentioned discovery.

[0007] Therefore, an object of the present invention is to provide a novel silicone-compatible macromolecular photoinitiator, the absorption wavelength of which can not only effectively initiate the photopolymerization reaction of silicone resin under LED light source, but also has good compatibility with silicone resin, while reducing the migration and volatilization of photolytic fragments during photopolymerization.

[0008] Another object of the present invention is to provide a method for preparing the organosilicon-compatible macromolecular photoinitiator of the present invention.

[0009] Another object of the present invention is to provide the use of the silicone-compatible macromolecular photoinitiator of the present invention as a photoinitiator in LED photopolymerization.

[0010] The technical solution for achieving the above-mentioned purpose of the present invention can be summarized as follows:

[0011] 1. Silicone-compatible macromolecular photoinitiator of formula (I):

[0012]

[0013] in:

[0014] M is a hydroxyl group, an acrylate group or a methacrylate group;

[0015] R1 and R2 are the same or different and are independently selected from C1-C 12 Alkyl, C1-C substituted with N, O, S heteroatom 12 Alkyl, C1-C 12 Alkoxy, or a combination thereof;

[0016] R3 and R4 are the same or different and are independently selected from C3-C 12 Alkylene, C1-C 10 Alkyleneoxy,

[0017] or a combination thereof;

[0018] R5 are each independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, or a combination thereof;

[0019] n = 2-50;

[0020] p=an integer from 0 to 5.

[0021] 2. The organosilicon-compatible macromolecular photoinitiator according to item 1, wherein M is an acrylate group or a methacrylate group.

[0022] 3. The organosilicon-compatible macromolecular photoinitiator according to item 1 or 2, wherein:

[0023] R1 and R2 are the same or different and are independently selected from C1-C6 alkyl, C1-C6 alkyl substituted with N, O, S heteroatom, C1-C6 alkoxy, or a combination thereof; preferably R1 and R2 are the same or different and are independently selected from C1-C4 alkyl, C1-C4 alkyl substituted with N, O, S heteroatom, C1-C

[0024] C4 alkoxy, or a combination thereof; more preferably R1 and R2 are the same or different and are independently methyl or ethyl, or a combination thereof; most preferably R1 and R2 are both methyl; and / or

[0025] R3 and R4 are the same or different and are independently selected from C 3-8 Alkylene, C 1-8 Preferably R3 and R4 are the same or different and are independently selected from C3-C6 alkylene,

[0026] C1-C6 alkyleneoxy, or a combination thereof; more preferably, R3 and R4 are the same or different and are independently selected from C3-C4 alkylene, C1-C4 alkyleneoxy, or a combination thereof; most preferably, R3 and R4 are both

[0027] -CH2-CH2-CH2-O-CH2-; and / or

[0028] R5 is independently selected from C1-C6 alkyl, C1-C6 alkoxy, fluorine, chlorine, bromine, or a combination thereof; preferably, R5 is independently selected from C1-C4 alkyl, C1-C4 alkoxy, fluorine, chlorine, bromine, or a combination thereof; more preferably, R5 is independently selected from C1-C2 alkyl, C1-C2 alkoxy, fluorine, chlorine, or a combination thereof; most preferably, R5 is methyl, methoxy, fluorine or chlorine.

[0029] 4. The organosilicon-compatible macromolecular photoinitiator according to any one of items 1 to 3, wherein: n=2-40, preferably n=2-30, more preferably n=2-25; and / or

[0030] p=an integer of 0-3, preferably p=0 or 1.

[0031] 5. The organosilicon-compatible macromolecular photoinitiator according to any one of items 1 to 4, wherein: p=0, R1 and R2 are both methyl, R3 and R4 are both -CH2-CH2-CH2-O-CH2-; or p=1, R1 and R2 are both methyl, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is methyl; or

[0032] p=1, R1 and R2 are both methyl, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is methoxy; or

[0033] p=1, R1 and R2 are both methyl, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is fluorine; or

[0034] p=1, R1 and R2 are both methyl, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is chlorine.

[0035] 6. A method for preparing a silicone-compatible macromolecular photoinitiator according to any one of items 1 to 5, comprising the following process steps:

[0036]

[0037] The parameters in the above formulae are defined as in any one of claims 1 to 5.

[0038] 7. According to the method of item 6, the phase transfer catalyst of step (1) is selected from one or more of the following groups: benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride, preferably benzyltriethylammonium chloride or tetrabutylammonium bromide.

[0039] 8. The method according to item 6 or 7, wherein in step (1), the molar ratio of the epoxypolysiloxane of formula (III), the phase transfer catalyst and the benzoylformic acid of formula (II) is 1:0.1-1:2-6, preferably 1:0.3-1:2-3.

[0040] 9. The method according to any one of items 6 to 8, wherein the acid-binding agent in step (2) is one or more selected from pyridine, 3-picoline, 2-picoline, 4-dimethylaminopyridine, triethylamine, and diethylamine, preferably pyridine or triethylamine; and the acyl chloride is acryloyl chloride or methacryloyl chloride.

[0041] 10. The method according to any one of items 6 to 9, wherein in step (2), the molar ratio of the intermediate product A, the acyl chloride and the acid binding agent is 1:2-6:2-6, preferably 1:2-3:2-3.

[0042] 11. Use of the silicone-compatible macromolecular photoinitiator obtained according to any one of items 1 to 5 or according to any one of items 6 to 10 as a photoinitiator in LED photopolymerization, especially in LED photopolymerization with a radiation wavelength of 365-410 nm, especially 385 nm, 395 nm and 405 nm.

[0043] 12. A photopolymerizable composition comprising:

[0044] (a) at least one silicone resin, and

[0045] (b) at least one method according to any one of items 1 to 5 or according to any one of items 6 to 10

[0046] The obtained silicone-compatible macromolecular photoinitiator.

[0047] 13. The photopolymerizable composition according to item 12, wherein the content of (a) at least one silicone resin is 95-98.5%, and the content of (b) at least one silicone-compatible macromolecular photoinitiator is 1-4%, based on the total weight of the photopolymerizable composition.

[0048] 14. A photopolymerizable material obtainable from the photopolymerizable composition of item 12 or 13.

[0049] 15. A method for preparing a photopolymerizable material, which comprises irradiating the photopolymerizable composition of item 12 or 13 with an LED light source having a radiation wavelength of 365-410 nm, especially 385 nm, 395 nm and 405 nm. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 This is the infrared spectrum of the organosilicon macromolecular photoinitiator prepared in Example 2 and the raw material epoxy polysiloxane;

[0051] Figure 2 The UV-visible absorption spectra of the organosilicon macromolecular photoinitiators prepared in Examples 2, 4, 6, 8, and 10;

[0052] Figure 3 This is the degradation H-NMR spectrum of the organosilicon macromolecular photoinitiator prepared in Example 2;

[0053] Figure 4 This is the degradation UV spectrum of the organosilicon macromolecular photoinitiator prepared in Example 1;

[0054] Figure 5 The photopolymerization kinetic curves of the organosilicon macromolecular photoinitiators prepared in Examples 4 and 10;

[0055] Figure 6 This is the electron paramagnetic resonance spectrum (EPR) of the organosilicon macromolecular photoinitiator prepared in Example 2;

[0056] Figure 7 Schematic diagram of the compatibility between the organosilicon macromolecular photoinitiator prepared in Examples 6 and 8 and the methacrylate silicone resin. DETAILED DESCRIPTION

[0057] According to one aspect of the present invention, there is provided a silicone-compatible macromolecular photoinitiator of general formula (I):

[0058]

[0059] in:

[0060] M is a hydroxyl group, an acrylate group or a methacrylate group;

[0061] R1 and R2 are the same or different and are independently selected from C1-C 12 Alkyl, C1-C substituted with N, O, S heteroatom 12 Alkyl, C1-C 12 Alkoxy, or a combination thereof;

[0062] R3 and R4 are the same or different and are independently selected from C3-C 12 Alkylene, C1-C 10 Alkyleneoxy,

[0063] or a combination thereof;

[0064] R5 are each independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, or a combination thereof;

[0065] n = 2-50;

[0066] p=an integer from 0 to 5.

[0067] In the present invention, the prefix "C n -C m " in each case means that the number of carbon atoms contained in the group is nm.

[0068] "Halogen" refers to fluorine, chlorine, bromine and iodine. In the present invention, preferably, the halogen includes fluorine, chlorine or a combination thereof.

[0069] The term "C n -C m "Alkyl" means a branched or unbranched saturated hydrocarbon radical having nm, such as 1 to 12, preferably 1 to 6, more preferably 1 to 4 carbon atoms. For example, C1-C6 alkyl can be methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers thereof, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl. C1-C4 alkyl can be methyl, ethyl, propyl, butyl and isomers thereof, in particular methyl or ethyl.

[0070] The term "C n -C m "Alkoxy" refers to n -C m Alkyl corresponding to the open chain C n -C m Any carbon atom of an alkane is bonded with an oxygen atom as a linker. n -C m Alkyl, such as C1-C 12 Alkoxy, preferably C1-C6 alkoxy, more preferably C1-C4 alkoxy. For example, C1-C6 alkoxy can be methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy and isomers thereof, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, n-pentoxy, isopentoxy and n-hexoxy. C1-C4 alkoxy can be methoxy, ethoxy, propoxy, butoxy and isomers thereof, in particular methoxy or ethoxy.

[0071] The term "C n -C m "Alkylene" means a branched or unbranched saturated hydrocarbon radical having nm, such as 3-12, preferably 3-8, more preferably 3-6, and especially 3-4 carbon atoms. For example, C3-C8 alkylene can be propylene, butylene, pentylene, hexylene, heptylene, octylene and isomers thereof, in particular propylene, butylene, pentylene, hexylene. C3-C6 alkylene can be propylene, butylene, pentylene, hexylene and isomers thereof, in particular propylene or butylene.

[0072] The term "C n -C m "Alkyleneoxy" refers to n -C m Any carbon atom of the alkyl group is bonded with an oxygen atom as the C of another connecting group.n -C m Alkyl such as C1-C 10 Alkyleneoxy, preferably C1-C6 alkyleneoxy, more preferably C1-C4 alkyleneoxy. For example, C1-C6 alkyleneoxy can be methyleneoxy, ethyleneoxy, propyleneoxy, butyleneoxy, pentyloxy, hexyleneoxy and isomers thereof, in particular methyleneoxy, ethyleneoxy, propyleneoxy, butyleneoxy, pentyloxy and hexyleneoxy. C1-C4 alkyleneoxy can be methyleneoxy, ethyleneoxy, propyleneoxy, butyleneoxy and isomers thereof, in particular methyleneoxy, ethyleneoxy, propyleneoxy or butyleneoxy.

[0073] In a preferred embodiment of the present invention, M is an acrylate group or a methacrylate group.

[0074] In some embodiments of the present invention, R1 and R2 are the same or different and are independently selected from C1-C6 alkyl, C1-C6 alkyl substituted by N, O, S heteroatoms, C1-C6 alkoxy, or a combination thereof; preferably, R1 and R2 are the same or different and are independently selected from C1-C4 alkyl, C1-C4 alkyl substituted by N, O, S heteroatoms, C1-C4 alkoxy, or a combination thereof; more preferably, R1 and R2 are the same or different and are independently methyl or ethyl, or a combination thereof; most preferably, R1 and R2 are both methyl.

[0075] In some embodiments of the present invention, R3 and R4 are the same or different and are independently selected from C3-C8 alkylene, C1-C8 alkyleneoxy, or a combination thereof; preferably, R3 and R4 are the same or different and are independently selected from C3-C6 alkylene, C1-C6 alkyleneoxy, or a combination thereof; more preferably, R3 and R4 are the same or different and are independently selected from C3-C4 alkylene, C1-C4 alkyleneoxy, or a combination thereof; most preferably, R3 and R4 are both -CH2-CH2-CH2-O-CH2-.

[0076] In some embodiments of the present invention, R5 is independently selected from C1-C6 alkyl, C1-C6 alkoxy, fluorine, chlorine, bromine, or a combination thereof; preferably, R5 is independently selected from C1-C4 alkyl, C1-C4 alkoxy, fluorine, chlorine, bromine, or a combination thereof; more preferably, R5 is independently selected from C1-C2 alkyl, C1-C2 alkoxy, fluorine, chlorine, or a combination thereof; most preferably, R5 is methyl, methoxy, fluorine or chlorine.

[0077] In some embodiments of the present invention, n=2-40, preferably n=2-30, more preferably n=2-25.

[0078] In some embodiments of the present invention, p=an integer from 0 to 3, preferably p=0 or 1.

[0079] In a preferred embodiment of the present invention, p=0, R1 and R2 are both methyl, and R3 and R4 are both -CH2-CH2-CH2-O-CH2-.

[0080] In a preferred embodiment of the present invention, p=1, R1 and R2 are both methyl, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is methyl.

[0081] In a preferred embodiment of the present invention, p=1, R1 and R2 are both methyl, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is methoxy.

[0082] In a preferred embodiment of the present invention, p=1, R1 and R2 are both methyl, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is fluorine.

[0083] In a preferred embodiment of the present invention, p=1, R1 and R2 are both methyl, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is chlorine.

[0084] The second aspect of the present invention relates to a method for preparing the organosilicon-compatible macromolecular photoinitiator of the general formula (I) of the present invention, comprising the following process steps:

[0085]

[0086] wherein R1, R2, R3, R4, R5 and p are as defined above.

[0087] The step (1) of the method of the present invention is carried out in a solvent in the presence of a phase transfer catalyst. Suitable phase transfer catalysts are, for example, one or more selected from the group consisting of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride.

[0088] In a preferred embodiment of the present invention, the phase transfer catalyst in step (1) of the process of the present invention is benzyltriethylammonium chloride or tetrabutylammonium bromide.

[0089] In step (1) of the method of the present invention, the molar ratio of the epoxy polysiloxane of formula (III), the phase transfer catalyst and the benzoylformic acid of formula (II) is 1:0.1-1:2-6, preferably 1:0.3-1:2-3.

[0090] The step (1) of the method of the present invention is usually carried out in a solvent, preferably in an organic solvent. There is no particular restriction on the choice of solvent type, as long as it can dissolve the reactants and is chemically inert to the reaction, that is, it does not participate in the reaction. As examples of solvents, dichloromethane, ethyl acetate, tetrahydrofuran, N,N-dimethylformamide (DMF) are usually used. Preferably, the reaction of step (1) is carried out in DMF or tetrahydrofuran. The amount of solvent used is conventional and can be determined by common sense in the art, or by several routine preliminary experiments.

[0091] More specifically, in step (1) of the method of the present invention, the epoxy polysiloxane of formula (III), a phase transfer catalyst and a solvent are placed in a reaction vessel. Under nitrogen protection, the mixture is stirred at a temperature of 80-100° C., preferably about 90° C. for 20-50 minutes, preferably 20-30 minutes. Subsequently, a solution of benzoylformic acid of formula (II) in a solvent is added, and the reaction system is maintained at 100-130° C., preferably about 110° C. for 10-30 hours, preferably 18-24 hours. After the reaction is completed, the solvent is removed by rotary evaporation, and the product is dissolved in ethyl acetate, washed twice with saturated sodium carbonate aqueous solution, deionized water and saturated sodium chloride solution, and then the crude product is purified by column chromatography to obtain an intermediate product A, i.e., a hydroxyl-containing organosilicon macromolecular photoinitiator.

[0092] Step (2) of the method of the present invention is carried out in a solvent in the presence of an acid binding agent and an acyl chloride. Suitable acid binding agents are selected from one or more of pyridine, 3-picoline, 2-picoline, 4-dimethylaminopyridine, triethylamine, and diethylamine, preferably pyridine or triethylamine. The acyl chloride is acryloyl chloride or methacryloyl chloride.

[0093] In step (2) of the method of the present invention, the molar ratio of the intermediate product A, the acyl chloride and the acid binding agent is 1:2-6:2-6, preferably 1:2-3:2-3.

[0094] Step (2) of the method of the present invention is usually carried out in a solvent, preferably an organic solvent. There is no particular restriction on the choice of solvent type, as long as it can dissolve the reactants and is chemically inert to the reaction, i.e., does not participate in the reaction. As examples of solvents, dimethyl sulfoxide, dichloromethane, ethyl acetate, tetrahydrofuran, N,N-dimethylformamide are usually used. Preferably, the reaction is carried out in dichloromethane or tetrahydrofuran. The amount of solvent used is conventional and can be determined by common sense in the art, or by several routine preliminary experiments.

[0095] More specifically, in step (2) of the method of the present invention, the intermediate product A is mixed with an acid binding agent in an anhydrous solvent. Under nitrogen protection at -10°C to 0°C, an anhydrous solution of acyl chloride is slowly added dropwise, and the reaction is carried out for 1-4 hours, preferably 2-3 hours. The temperature is then raised to 20-40°C, preferably about 30°C, and the reaction is continued for 10-24 hours, preferably 12-18 hours. After the reaction is completed, the solvent is removed by rotary evaporation, and the product is dissolved in ethyl acetate. The product is washed three times with deionized water, and the organic phase is collected to obtain a silicone-compatible macromolecule of the product general formula (I).

[0096] The organosilicon-compatible macromolecular photoinitiator of the general formula (I) of the present invention is suitable for use as a photoinitiator for LED photopolymerization, and has excellent compatibility with LED light sources with wavelengths of 365-410 nm, especially 385 nm, 395 nm and 405 nm, exhibits good photoinitiating ability, and ensures efficient photopolymerization rate under LED light sources. In particular, the photoinitiator of the present invention can effectively initiate the photopolymerization reaction of the organosilicon resin, and has good compatibility with the organosilicon resin, while reducing the migration and volatilization of photolytic fragments during the photopolymerization process.

[0097] Therefore, in another aspect of the present invention, there is provided use of the organosilicon-compatible macromolecular photoinitiator of the general formula (I) of the present invention as a photoinitiator in LED photopolymerization.

[0098] Furthermore, the present invention provides a photopolymerizable composition comprising:

[0099] (a) at least one silicone resin, and

[0100] (b) at least one silicone-compatible macromolecular photoinitiator of the present invention.

[0101] In the photopolymerizable composition of the present invention, (a) at least one silicone resin is present in an amount of 95-98.5%, and (b) at least one silicone-compatible macromolecular photoinitiator is present in an amount of 1-4%, based on the total weight of the photopolymerizable composition.

[0102] More specifically, the photopolymerizable composition is a free radical photopolymerizable composition comprising 1-4% of the silicone-compatible macromolecular photoinitiator of the present invention, 0.5-1% of a hydrogen donor, and 95-98.5% of a silicone resin, based on the total weight of the photopolymerizable composition.

[0103] Further, the silicone resin can be selected from one or more of epoxy (meth) acrylate silicone resin, polyurethane (meth) acrylate silicone resin, polyester (meth) acrylate silicone resin, polyether (meth) acrylate silicone resin, and (meth) acrylate silicone resin; the hydrogen donor is selected from one or more of tertiary amine compounds, such as triethylamine, tributylamine, triethanolamine, ethyl p-dimethylaminobenzoate (EDB), N-methyldiethanolamine, N,N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine, diazabicyclooctane (triethylenediamine), 18-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and salts thereof.

[0104] In addition to the photoinitiator and the hydrogen donor, the photopolymerizable composition may contain various additives. Examples thereof are thermal inhibitors intended to prevent premature polymerization, such as 2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl radical and its derivatives; antistatic agents; flow improvers and adhesion promoters; chain transfer agents; photosensitizers for changing or broadening the spectral sensitivity, such as aromatic carbonyl compounds such as benzophenone derivatives, thioxanthone derivatives; fillers; or pigments.

[0105] The photopolymerizable compositions according to the invention can be used for various purposes, for example as printing inks (for example screen printing inks, offset or flexographic printing inks, inkjet inks, sheet-fed printing inks, electrophotographic inks, gravure inks), as clear, white or pigmented coatings, for photocopying processes, for holographic recording materials, for image recording processes or for the production of printing plates which can be developed with organic solvents or with aqueous alkaline media, for the production of masks for screen printing, as dental filling compounds, as adhesives, as pressure-sensitive adhesives, as laminating resins, as etch resists or permanent resists, as photostructurable dielectrics and as solder masks for electronic circuits, as resists for the production of color filters for display screens of any type or for the generation of structures during the production of plasma displays and electroluminescent displays, for the production of optical switches, gratings, for the production of three-dimensional articles by bulk polymerization or according to stereolithography, for the production of composite materials of gel coatings and thick-layered compositions, for coating or sealing electronic components or as coatings for optical fibers. The compositions are also suitable for the production of optical lenses, such as contact lenses or Fresnel lenses, and for the manufacture of medical devices, aids or implants.

[0106] Therefore, in another aspect of the present invention, a photopolymerizable material is provided which can be obtained from a photopolymerizable composition comprising the silicone-compatible macromolecular photoinitiator of the present invention, which is obtained by irradiating the photopolymerizable composition comprising the silicone-compatible macromolecular photoinitiator of the present invention with an LED light source having a radiation wavelength of 365-410 nm, especially 385 nm, 395 nm and 405 nm.

[0107] The beneficial effects of the present invention are:

[0108] (1) The organosilicon macromolecular photoinitiator prepared by the present invention has excellent matching with LED light sources with wavelengths of 365-410nm, especially 385nm, 395nm and 405nm, and exhibits good photoinitiation ability, ensuring efficient photopolymerization rate under LED light sources.

[0109] (2) The silicone-compatible macromolecular photoinitiator prepared by the present invention not only effectively improves the compatibility between the photoinitiator and the silicone resin, achieving a good blending effect, but also reduces the migration and volatilization of photolytic fragments during the photopolymerization process, thereby providing a new approach and method for preparing silicone materials by photopolymerization.

[0110] (3) The synthesis process of the present invention is simple and has significant advantages in preparation. The obtained organosilicon-compatible macromolecular photoinitiator is more environmentally friendly in application, expands the scope of application, and promotes the development of LED photopolymerization technology in the field of organosilicon materials.

[0111] Example

[0112] The scheme of the present invention will be explained below in conjunction with embodiments. It will be appreciated by those skilled in the art that the following embodiments are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention. Where specific techniques or conditions are not indicated in the embodiments, the techniques or conditions or product specifications described in the literature in the art are followed.

[0113] The materials and reagents used in the following examples are listed in Table A, the experimental instruments are shown in Table B, and other materials and reagents can be obtained from commercial sources.

[0114] Table A - Experimental Materials and Reagents

[0115]

[0116]

[0117] Table B - Experimental Instruments

[0118] Instrument Name Instrument Model Manufacturer Real-time infrared spectrometer Nicolet 5700 Thermo Electron Nuclear Magnetic Resonance (NMR) Avance 400M Bruker, Germany Electronic balance AR1140 OHAUS Rotary evaporator RE-52 Shanghai Yarong Biochemical Instrument Factory Electron Paramagnetic Resonance Spectrometer (EPR) ELEXSYS II Bruker, Germany UV-Vis Spectrophotometer UV-3600 Shimadzu Corporation Fourier Transform Infrared Spectrometer Nicolet 50XC Nicole Corporation LED light source irradiation machine UVEC-4II Shenzhen Lamprek Company

[0119] Embodiment 1-2:

[0120] Example 1 is the synthesis of a hydroxyl organosilicon macromolecular photoinitiator.

[0121]

[0122] 20g (0.01mol, M = 2000g / mol) X-22-163A, 2.27g benzyltriethylammonium chloride (0.01mol) and 100mL DMF were placed in a 500mL three-necked flask. Stir at 90°C for 30 minutes under nitrogen protection. Subsequently, 50mL DMF solution containing 4.5g (0.03mol) benzoylformic acid was added, and the reaction system was maintained at 110°C for 24 hours. After removing the solvent by rotary evaporation, the product was dissolved in 100mL ethyl acetate, washed twice with 50mL saturated sodium carbonate aqueous solution, 50mL deionized water and 50mL saturated sodium chloride solution, and then purified by column chromatography (EA:PE = 1:5v / v) to obtain 18.1g of light yellow liquid intermediate product PASi-1, hydroxyl organosilicon macromolecular photoinitiator, with a yield of 78.7%.

[0123] 1 H NMR (400MHz, CDCl3, ppm) δ8.07(m,2H),7.67(m,1H),7.56(m,2H),4.82(m,1H),4.46(d,J=8Hz ,1H),4.41(d,J=8Hz,1H),3.67(m,2H),3.47(m,2H),1.63(m,2H),0.55(m,2H),0.08(s,79H).

[0124] Example 2 is the synthesis of a polymerizable organosilicon macromolecular photoinitiator.

[0125] Mix 11.5g (5mmol) PASi-1 and 1.1g (10mmol) triethylamine in 50mL anhydrous dichloromethane. Under nitrogen protection at 0°C, slowly drop 20mL anhydrous dichloromethane solution containing 0.9g (10mmol) acryloyl chloride and react for 2 hours. Then heat to 30°C and continue to react for 12 hours. After removing the solvent by rotary evaporation, the crude product is dissolved in 100mL ethyl acetate. Wash three times with 50mL deionized water, collect the organic phase, and obtain 11.2g yellow liquid product PASi-2, a polymerizable silicone macromolecular photoinitiator, with a yield of 93.0%.

[0126] 1H NMR (400MHz, CDCl3, ppm) δ7.96 (m, 2H), 7.60 (m, 1H), 7.46 (m, 2H), 6.37 (m, 1H), 6.09 (m, 1H), 5.78 (d, J = 8Hz, 1H), 4.7 6(m,1H),4.43(d,J=8Hz,1H),4.33(d,J=8Hz,1H),3.59(m,2H),3.43(m,2H),1.59(m,2H),0.50(m,2H),0.07(s,79H).

[0127] Embodiment 3-4:

[0128] Example 3 is the synthesis of a fluorine-containing hydroxyl organosilicon macromolecular photoinitiator.

[0129] 20g (0.01mol, M = 2000g / mol) X-22-163A, 3.22g tetrabutylammonium bromide (0.01mol) and 100mL DMF were placed in a 500mL three-necked flask. Stirred at 90°C for 30 minutes under nitrogen protection. Subsequently, 50mL DMF solution containing 5.0g (0.03mol) of p-fluorobenzoylformic acid was added, and the reaction system was maintained at 110°C for 24 hours. After removing the solvent by rotary evaporation, the product was dissolved in 100mL ethyl acetate, washed twice with 50mL saturated sodium carbonate aqueous solution, 50mL deionized water and 50mL saturated sodium chloride solution, and then purified by column chromatography (EA: PE = 1: 5v / v) to obtain 18.4g of light yellow liquid intermediate product PASi-3, a fluorinated hydroxyl organosilicon macromolecular photoinitiator, with a yield of 78.8%.

[0130] 1 H NMR (400MHz, CDCl3, ppm) δ7.95 (d, J = 7.3Hz, 2H), 7.48 (d, J = 7.3Hz, 2H), 4.42-4.1 7(m,3H),3.63-3.38(m,2H),3.35(m,2H),1.42(m,2H),0.61(m,2H),0.09(s,79H).

[0131] Example 4 is the synthesis of a fluorine-containing polymerizable organosilicon macromolecular photoinitiator.

[0132] 11.7g (5mmol) PASi-3 and 1.1g (10mmol) triethylamine were mixed in 50mL anhydrous dichloromethane. Under nitrogen protection at 0°C, 20mL anhydrous dichloromethane solution containing 0.9g (10mmol) acryloyl chloride was slowly added dropwise and reacted for 2 hours. Then the temperature was raised to 30°C and the reaction was continued for 12 hours. After removing the solvent by rotary evaporation, the crude product was dissolved in 100mL ethyl acetate. Washed three times with 50mL deionized water, the organic phase was collected, and 11.4g of yellow liquid product PASi-4, a fluorine-containing polymerizable silicone macromolecular photoinitiator, was obtained with a yield of 93.1%.

[0133] 1 H NMR (400MHz, CDCl3, ppm) δ7.83(d,J=7.2Hz,2H),7.44(d,J=7.2Hz,2H),6.41(m,1H),6.12(m,1H),5.83(m,1 H),5.46(m,1H),4.50-4.25(m,2H),3.71-3.46(m,2H),3.35(m,2H),1.42(m,2H),0.61(m,2H),0.09(s,79H).

[0134] Embodiment 5-6:

[0135] Example 5 is the synthesis of a chlorine-containing hydroxyl organosilicon macromolecular photoinitiator.

[0136] 20g (0.01mol, M = 2000g / mol) X-22-163A, 3.22g tetrabutylammonium bromide (0.01mol) and 100mL DMF were placed in a 500mL three-necked flask. Stirred at 90°C for 30 minutes under nitrogen protection. Subsequently, 50mL DMF solution containing 5.5g (0.03mol) p-chlorobenzoylformic acid was added, and the reaction system was maintained at 110°C for 24 hours. After removing the solvent by rotary evaporation, the product was dissolved in 100mL ethyl acetate, washed twice with 50mL saturated sodium carbonate aqueous solution, 50mL deionized water and 50mL saturated sodium chloride solution, and then purified by column chromatography (EA:PE = 1:5v / v) to obtain 18.9g of light yellow liquid intermediate product PASi-5, a chlorine-containing hydroxyl organosilicon macromolecular photoinitiator, with a yield of 79.8%.

[0137] 1H NMR (400MHz, CDCl3, ppm) δ7.86 (d, J = 7.3Hz, 2H), 7.51 (d, J = 7.3Hz, 2H), 4.40-4.1 5(m,3H),3.59-3.40(m,2H),3.33(m,2H),1.45(m,2H),0.60(m,2H),0.08(s,79H).

[0138] Example 6 is the synthesis of a chlorine-containing polymerizable silicone macromolecular photoinitiator.

[0139] 11.8g (5mmol) PASi-5 and 0.79g (10mmol) pyridine were mixed in 50mL anhydrous dichloromethane. Under nitrogen protection at 0°C, 20mL anhydrous dichloromethane solution containing 0.9g (10mmol) acryloyl chloride was slowly added dropwise and reacted for 2 hours. Then the temperature was raised to 30°C and the reaction was continued for 12 hours. After removing the solvent by rotary evaporation, the crude product was dissolved in 100mL ethyl acetate. Washed three times with 50mL deionized water, the organic phase was collected, and 11.2g of yellow liquid product PASi-6, a chlorine-containing polymerizable silicone macromolecular photoinitiator, was obtained with a yield of 90.8%.

[0140] 1 H NMR (400MHz, CDCl3, ppm) δ7.85(d,J=7.3Hz,2H),7.50(d,J=7.3Hz,2H),6.40(m,1H),6.14(m,1H),5.85(m,1 H),5.44(m,1H),4.55-4.21(m,2H),3.59-3.41(m,2H),3.33(m,2H),1.45(m,2H),0.60(m,2H),0.09(s,79H).

[0141] Embodiment 7-8:

[0142] Example 7 is the synthesis of a methyl-containing hydroxyl organosilicon macromolecular photoinitiator.

[0143] 20g (0.01mol, M = 2000g / mol) X-22-163A, 3.22g tetrabutylammonium bromide (0.01mol) and 100mL DMF were placed in a 500mL three-necked flask. Stirred at 90°C for 30 minutes under nitrogen protection. Subsequently, 50mL DMF solution containing 4.9g (0.03mol) p-methylbenzoylformic acid was added, and the reaction system was maintained at 110°C for 24 hours. After removing the solvent by rotary evaporation, the product was dissolved in 100mL ethyl acetate, washed twice with 50mL saturated sodium carbonate aqueous solution, 50mL deionized water and 50mL saturated sodium chloride solution, and then purified by column chromatography (EA: PE = 1: 5v / v) to obtain 18.6g of light yellow liquid intermediate product PASi-7, a methyl-containing hydroxyl organosilicon macromolecular photoinitiator, with a yield of 79.9%.

[0144] 1 H NMR (400MHz, CDCl3, ppm) δ7.97(d,J=7.3Hz,2H),7.38(d,J=7.3Hz,2H),4.45-4.13(m,3H ),3.60-3.35(m,2H),3.33(m,2H),2.41(s,3H),1.48(m,2H),0.65(m,2H),0.08(s,79H).

[0145] Example 8 is the synthesis of a methyl-containing polymerizable organosilicon macromolecular photoinitiator.

[0146] 11.6g (5mmol) PASi-7 and 0.79g (10mmol) pyridine were mixed in 50mL anhydrous tetrahydrofuran. Under nitrogen protection at 0°C, 20mL anhydrous tetrahydrofuran solution containing 0.9g (10mmol) acryloyl chloride was slowly added dropwise and reacted for 2 hours. Then the temperature was raised to 30°C and the reaction was continued for 12 hours. After filtration, the solvent was removed by rotary evaporation and the crude product was dissolved in 100mL ethyl acetate. Washed three times with 50mL deionized water, the organic phase was collected, and 11.3g of yellow liquid product PASi-8, a methyl-containing polymerizable silicone macromolecular photoinitiator, was obtained with a yield of 93.1%.

[0147] 1H NMR (400MHz, CDCl3, ppm) δ7.80(d,J=7.3Hz,2H),7.39(d,J=7.3Hz,2H),6.41(m,1H),6.13(m,1H),5.84(m,1H),5.4 3(m,1H),4.45-4.13(m,2H),3.60-3.36(m,2H),3.33(m,2H),2.41(s,3H),1.48(m,2H),0.65(m,2H),0.08(s,79H).

[0148] Embodiment 9-10:

[0149] Example 9 is the synthesis of a methoxy-containing hydroxyl organosilicon macromolecular photoinitiator.

[0150] 20g (0.01mol, M = 2000g / mol) X-22-163A, 3.22g tetrabutylammonium bromide (0.01mol) and 100mL DMF were placed in a 500mL three-necked flask. Under nitrogen protection, the mixture was stirred at 90°C for 30 minutes. Subsequently, 50mL DMF solution containing 5.4g (0.03mol) p-methoxybenzoylformic acid was added, and the reaction system was maintained at 110°C for 24 hours. After the solvent was removed by rotary evaporation, the product was dissolved in 100mL ethyl acetate, washed twice with 50mL saturated sodium carbonate aqueous solution, 50mL deionized water and 50mL saturated sodium chloride solution, and then purified by column chromatography (EA:PE = 1:5v / v) to obtain 18.8g of light yellow liquid intermediate product PASi-9, a methoxy-containing hydroxyl organosilicon macromolecular photoinitiator, with a yield of 79.7%.

[0151] 1 H NMR (400MHz, CDCl3, ppm) δ8.22(d,J=7.3Hz,2H),7.12(d,J=7.3Hz,2H),4.44-4.12(m,3H ),3.81(s,3H),3.65-3.35(m,2H),3.33(m,2H),1.43(m,2H),0.62(m,2H),0.08(s,79H).

[0152] Example 10 is the synthesis of a methoxy-containing polymerizable silicone macromolecular photoinitiator.

[0153] 11.8g (5mmol) PASi-9 and 0.79g (10mmol) pyridine were mixed in 50mL anhydrous tetrahydrofuran. Under nitrogen protection at 0°C, 20mL anhydrous tetrahydrofuran solution containing 1.04g (10mmol) methacryloyl chloride was slowly added dropwise and reacted for 2 hours. Then the temperature was raised to 30°C and the reaction was continued for 12 hours. After filtration, the solvent was removed by rotary evaporation and the crude product was dissolved in 100mL ethyl acetate. Washed three times with 50mL deionized water, the organic phase was collected, and 11.4g of yellow liquid product PASi-10, a methoxy-containing polymerizable silicone macromolecular photoinitiator, was obtained with a yield of 92.4%.

[0154] 1 H NMR (400MHz, CDCl3, ppm) δ8.09(d,J=7.3Hz,2H),7.11(d,J=7.3Hz,2H),6.48(m,1H),6.40(m,1H),5.49(m,1H),4.5 1-4.20(m,2H),3.81(s,3H),3.65-3.35(m,2H),3.33(m,2H),2.01(s,3H),1.43(m,2H),0.62(m,2H),0.08(s,79H).

[0155] Test Example 1:

[0156] The purpose of Test Example 1 is to illustrate the successful preparation of the photoinitiator PASi-2 prepared in Example 2.

[0157] The changes of the functional groups of PASi-2 compared with the raw material epoxy polysiloxane X-22-163A were measured by Fourier transform infrared spectrometer. The infrared spectrum is as follows Figure 1 The results show that compared with X-22-163A, the carbonyl absorption peaks of benzoyl formate and acrylate in PASi-2 are at 1732 cm -1 and 1689cm -1 Appears around 1633, 1595, 1451, 1057 and 798cm -1 The characteristic absorption peaks of C=C, -Ar, Si-O-Si and Si-CH3 appeared on the left and right, respectively, indicating that the epoxy ring of X-22-163A was opened and successfully connected with benzoylformate and acrylate, that is, the preparation of photoinitiator PASi-2 was successful.

[0158] Test Example 2:

[0159] The purpose of Test Example 2 is to illustrate that the photoinitiators PASi-2, PASi-4, PASi-6, PASi-8, and PASi-10 prepared in Examples 2, 4, 6, 8, and 10 have absorption at the LED emission wavelength.

[0160] PASi-2, PASi-4, PASi-6, PASi-8, and PASi-10 were prepared at a concentration of 1×10 -4 mol / L acetonitrile solution. The UV-visible absorption spectra of five different solutions in the wavelength range of 200-500nm were tested using a UV-visible spectrophotometer. The results are as follows: Figure 2 The results show that the maximum absorption wavelengths of the five photoinitiators are all below 350nm, but they all have certain absorption capabilities at wavelengths around 400nm, and this weak absorption capability can give the initiators the initiation ability at the LED emission wavelength.

[0161] Test Example 3:

[0162] The purpose of Test Example 3 is to illustrate that the photoinitiator PASi-2 prepared in Example 2 undergoes photodegradation under 405 nm LED light irradiation.

[0163] Take 0.012g of PASi-2 and 0.0005g of triethylamine and dissolve them in 50mL of CDCl3 to prepare 10 -4 mol / L CDCl3 solution. After irradiation with 405nm LED light for 0s, 120s, 240s and 480s, the nuclear magnetic resonance hydrogen spectrum was tested by nuclear magnetic resonance spectrometer. The results are as follows Figure 3 The results show that as the 405nm LED light irradiation time increases, two new peaks gradually form in the H NMR spectrum at 7.0-7.3ppm. This indicates that PASi-2 undergoes photodegradation under LED light irradiation, and the carbonyl group connected to the benzene ring may undergo a hydrogen abstraction reaction to generate an alkyl radical, which leads to an increase in the electron cloud density of the benzene ring and a shift of the chemical shift to the high field.

[0164] Test Example 4:

[0165] The purpose of Test Example 4 is to illustrate that the photoinitiator PASi-1 prepared in Example 1 undergoes a photochemical reaction under 405 nm LED light irradiation.

[0166] Take 0.0115g of PASi-1 and 0.001g of hydrogen donor ethyl p-dimethylaminobenzoate (EDB) and dissolve them in 50mL of acetonitrile to prepare 10 -4 mol / L acetonitrile solution. After irradiation under 405nm LED light for different time periods, UV-visible absorption measurement was performed. The degradation UV graph is shown in Figure 4 The results show that as the irradiation time of 405nm LED light increases, the absorbance of acetonitrile solutions of PASi-1 and EDB at 250nm and 307nm gradually decreases. This indicates that PASi-1 and EDB will undergo a photochemical reaction under the irradiation of 405nm LED light.

[0167] Test Example 5:

[0168] The purpose of Test Example 5 is to illustrate that the photoinitiators PASi-4 and PASi-10 prepared in Examples 4 and 10 can effectively initiate polymerization of silicone resin under 385 nm LED light irradiation.

[0169] 1. Preparation of silicone resin composition

[0170] Methacrylate silicone resin X-22-164A (Mn=1720) was selected to prepare two photosensitive resin compositions according to the following ratios:

[0171] X-22-164A (95 parts by mass), PASi-4 (4 parts by mass), EDB (1 part by mass);

[0172] X-22-164A (95 parts by mass), PASi-10 (4 parts by mass), EDB (1 part by mass).

[0173] 2. Aggregation performance test

[0174] The test results of the photopolymerization kinetics of the prepared photosensitive resin composition are as follows: Figure 5 The results show that the photoinitiators PASi-4 and PASi-10 prepared by the present invention have an emission wavelength of 385nm (light intensity 100mW / cm 2 ) under the irradiation of LED light source, the methacrylate silicone resin X-22-164A can be successfully initiated to undergo photopolymerization, and the double bond conversion rates can reach 50.7% and 63.3%, respectively, which indicates that the photoinitiator of the present invention can effectively initiate the polymerization of silicone resin.

[0175] Test Example 6:

[0176] The purpose of Test Example 6 is to illustrate that the photoinitiator PASi-2 prepared in Example 2 can generate free radicals under 405 nm LED light irradiation.

[0177] 0.012g of PASi-2, 0.001g of EDB and 0.0028g of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) were dissolved in 50mL of tert-butylbenzene. The mixture of PASi-2 and EDB was tested by electron paramagnetic resonance spectrometer (EPR) after irradiation with 405nm LED light source. The EPR spectrum captured by DMPO and the simulated EPR spectrum are shown in Figure 2. Figure 6The results show that the EPR spectrum of the PASi-2 and EDB mixture is fitted using the hyperfine splitting constant and then compared with the measured EPR spectrum, indicating that the free radicals captured by DMPO in the PASi-2 and EDB mixture after illumination are aminoalkyl radicals.

[0178] Test Example 7:

[0179] The purpose of Test Example 7 is to illustrate that the photoinitiators PASi-6 and PASi-8 prepared in Examples 6 and 8 have good compatibility with silicone resin.

[0180] 1. Preparation of silicone resin composition

[0181] Methacrylate silicone resins X-22-164A (Mn=1720) and X-22-164B (Mn=3260) were selected and two compositions were prepared according to the following proportions:

[0182] X-22-164A (95 parts by mass), PASi-6 (5 parts by mass);

[0183] X-22-164B (95 parts by mass), PASi-8 (5 parts by mass).

[0184] 2. Compatibility test

[0185] After the above composition is stirred evenly, it is kept away from light for 24 hours, and the stratification of the composition is observed. The results are as follows: Figure 7 The results show that there is no delamination in the two compositions, indicating that the two photoinitiators PASi-6 and PASi-8 have good compatibility with the silicone resin.

[0186] Test Example 8:

[0187] The purpose of Test Example 8 is to illustrate that the photoinitiator PASi-10 of Example 10 has a lower mobility.

[0188] 1. Preparation of silicone resin composition

[0189] Methacrylate silicone resin X-22-164A (Mn=1720), photoinitiator PASi-10 and commercial 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) were selected to prepare two compositions according to the following proportions:

[0190] X-22-164A (95 parts by mass), PASi-10 (4 parts by mass), EDB (1 part by mass);

[0191] X-22-164A (96 parts by mass), 1173 (4 parts by mass).

[0192] 2. Mobility test

[0193] After the above two compositions were stirred evenly, 100 mW / cm 2 The film was irradiated with 365nm ultraviolet light for 15 minutes for photocuring, and the unreacted monomers and initiators on the film surface were washed with ethanol. An appropriate amount of film was soaked in ethanol, and the absorbance value of the solution was monitored. The monitoring wavelength of PASi-10 was 251nm, and the monitoring wavelength of 1173 was 254nm. The results are shown in Table 1. The results show that at 1 hour, the mobility of PASi-10 was 5.10% of that of 1173; at 48 hours, the mobility of PASi-10 was 11.12% of that of 1173. It can be seen that the PASi-10 photoinitiator of Example 10 has a lower mobility.

[0194] Table 1. Relative mobility of photoinitiators PASi-10 and 1173 of Example 10

[0195] Time (h) PASi-10(%) 1173(％) 1 5.10 100 24 8.17 100 48 11.12 100

[0196] The above results indicate that the organosilicon macromolecular photoinitiator provided by the present invention can effectively initiate the photopolymerization reaction of the organosilicon resin under the LED light source, and has good compatibility with the organosilicon resin, while reducing the migration and volatilization of photolytic fragments during the photopolymerization process.

Claims

1. Silicone-compatible macromolecular photoinitiator of formula (I): in: M is a hydroxyl group, an acrylate group or a methacrylate group; R1 and R2 are the same or different and are independently selected from C1-C 12 Alkyl, C1-C substituted with N, O, S heteroatom 12 Alkyl, C1-C 12 Alkoxy, or a combination thereof; R3 and R4 are the same or different and are independently selected from C3-C 12 Alkylene, C1-C 10 Alkyleneoxy, or a combination thereof; R5 are each independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, or a combination thereof; n＝2-50； p=an integer from 0 to 5.

2. The organosilicon-compatible macromolecular photoinitiator according to claim 1, wherein M is an acrylate group or a methacrylate group.

3. The organosilicon-compatible macromolecular photoinitiator according to claim 1 or 2, wherein: R1 and R2 are the same or different and are independently selected from C1-C6 alkyl, C1-C6 alkyl substituted by N, O, S heteroatoms, C1-C6 alkoxy, or a combination thereof; preferably, R1 and R2 are the same or different and are independently selected from C1-C4 alkyl, C1-C4 alkyl substituted by N, O, S heteroatoms, C1-C4 alkoxy, or a combination thereof; more preferably, R1 and R2 are the same or different and are independently selected from methyl or ethyl, or a combination thereof; most preferably, R1 and R2 are both methyl; and / or R3 and R4 are the same or different and are independently selected from C3-C8 alkylene, C1-C8 alkyleneoxy, or a combination thereof; preferably, R3 and R4 are the same or different and are independently selected from C3-C6 alkylene, C1-C6 alkyleneoxy, or a combination thereof; more preferably, R3 and R4 are the same or different and are independently selected from C3-C4 alkylene, C 1-4 Alkyleneoxy, or a combination thereof; most preferably R3 and R4 are both -CH2-CH2-CH2-O-CH2-; and / or R5 is independently selected from C1-C6 alkyl, C1-C6 alkoxy, fluorine, chlorine, bromine, or a combination thereof; Preferably, R5 is independently selected from C1-C4 alkyl, C1-C4 alkoxy, fluorine, chlorine, bromine, or a combination thereof; more preferably, R5 is independently selected from C1-C2 alkyl, C1-C2 alkoxy, fluorine, chlorine, or a combination thereof; most preferably, R5 is methyl, methoxy, fluorine or chlorine.

4. The organosilicon-compatible macromolecular photoinitiator according to any one of claims 1 to 3, wherein: n=2-40, preferably n=2-30, more preferably n=2-25; and / or p=an integer of 0-3, preferably p=0 or 1.

5. The organosilicon-compatible macromolecular photoinitiator according to any one of claims 1 to 4, wherein: p=0, R1 and R2 are both methyl, R3 and R4 are both -CH2-CH2-CH2-O-CH2-; or p=1, R1 and R2 are both methyl, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is methyl; or p=1, R1 and R2 are both methyl, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is methoxy; or p=1, R1 and R2 are both methyl, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is fluorine; or p=1, R1 and R2 are both methyl, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is chlorine.

6. A method for preparing a silicone-compatible macromolecular photoinitiator according to any one of claims 1 to 5, comprising the following process steps: (1) (2) The parameters in the above formulae are defined as in any one of claims 1-5.

7. according to the method for claim 6, wherein the phase-transfer catalyst of step (1) is selected from one or more of the following groups: benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride, preferably benzyltriethylammonium chloride or tetrabutylammonium bromide.

8. according to the method for claim 6 or 7, wherein in step (1), the molar ratio of the epoxy polysiloxane of formula (III), the phase transfer catalyst and the benzoylformic acid of formula (II) is 1:0.1-1:2-6, preferably 1:0.3-1:2-3.

9. The method according to any one of claims 6 to 8, wherein the acid binding agent in step (2) is one or more selected from pyridine, 3-picoline, 2-picoline, 4-dimethylaminopyridine, triethylamine, and diethylamine, preferably pyridine or triethylamine; and the acyl chloride is acryloyl chloride or methacryloyl chloride.

10. The method according to any one of claims 6 to 9, wherein in step (2), the molar ratio of intermediate product A, acyl chloride and acid binding agent is 1:2-6:2-6, preferably 1:2-3:2-3.

11. Use of the organosilicon-compatible macromolecular photoinitiator obtained according to any one of claims 1 to 5 or according to any one of claims 6 to 10 as a photoinitiator in LED photopolymerization, in particular in LED photopolymerization with a radiation wavelength of 365 to 410 nm, in particular 385 nm, 395 nm and 405 nm.

12. A photopolymerizable composition comprising: (a) at least one silicone resin, and (b) at least one organosilicon-compatible macrophotoinitiator obtainable according to a process according to any one of claims 1 to 5 or according to any one of claims 6 to 10.

13. The photopolymerizable composition according to claim 12, wherein (a) the at least one silicone resin is present in an amount of 95-98.5%, and (b) the at least one silicone-compatible macro-photoinitiator is present in an amount of 1-4%, based on the total weight of the photopolymerizable composition.

14. A photopolymerizable material obtainable from a photopolymerizable composition according to claim 12 or 13.

15. A method for preparing a photopolymerizable material, which comprises irradiating the photopolymerizable composition of claim 12 or 13 with an LED light source having a radiation wavelength of 365-410 nm, especially 385 nm, 395 nm and 405 nm.

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