Organosilicon compatible macromolecular photoinitiator for LED photopolymerization, and preparation and use thereof

Abstract

The present invention relates to an organosilicon compatible macromolecular photoinitiator. This photoinitiator not only has an absorption wavelength suitable for LED light source polymerization, which can particularly effectively initiate a photopolymerization reaction of an organic silicon resin, but also has good compatibility with an organic silicon resin, and also reduces the migration and volatilization of photolytic fragments during a photopolymerization process. The present invention further relates to a method for preparing the organosilicon compatible macromolecular photoinitiator of the present invention, and the use thereof in LED photopolymerization.

Description

Organosilicon-compatible macromolecular photoinitiators for LED photopolymerization, their preparation and application Technical Field

[0001] This invention belongs to the field of photosensitive polymer materials, specifically relating to an organosilicon-compatible macromolecular photoinitiator, particularly suitable for the LED photopolymerization of organosilicon resins. This invention also relates to the preparation and application of this organosilicon-compatible macromolecular photoinitiator. Background Technology

[0002] Organosilicon materials, with their excellent chemical stability, weather resistance, flexibility, insulation, and low surface energy and tension, have demonstrated significant application value in various fields such as building materials, electronics, communication semiconductors, daily chemical textiles, and new energy. The main preparation methods for organosilicon materials include: sol-gel method, hydrothermal method, solvothermal method, plasma chemical vapor deposition, condensation polymerization, and polymerization method. Polymerization methods can be further divided into catalytic polymerization, emulsion polymerization, thermal polymerization, and photopolymerization. Among these, photopolymerization offers numerous advantages such as high efficiency, energy saving, environmental friendliness, and economy in the preparation of organosilicon materials, and photoinitiators play a crucial role in this process.

[0003] Meanwhile, with the continuous development of LED photopolymerization technology, numerous research teams are dedicated to developing photoinitiators suitable for LED photopolymerization to meet its wide application needs. While some such photoinitiators already exist in the existing technology, currently reported photoinitiators suitable for LED photopolymerization are mainly small-molecule structures. For example, CN104817653A discloses a coumarin compound suitable for UV-LED curing, and CN102492059A discloses a substituted diphenyl sulfide ketone photoinitiator. These photoinitiators and their photolysis fragments are prone to migration and volatilization, leading to product aging, yellowing, unpleasant odors, and toxicity. Furthermore, most existing photoinitiators exhibit poor compatibility in silicone resin systems. These problems significantly limit the development of photoinitiators suitable for silicone materials. Therefore, developing silicone-compatible macromolecular photoinitiators suitable for LED photopolymerization is of great significance. Summary of the Invention

[0004] To promote the development of LED photopolymerization technology, the inventors have been dedicated to the research and application of organosilicon-compatible macromolecules, particularly in the continuous research and development of more organosilicon-compatible macromolecular photoinitiators suitable for LED photopolymerization. Furthermore, given the existing problems in the technology, the inventors have conducted extensive and in-depth research on organosilicon-compatible macromolecular photoinitiators suitable for LED photopolymerization, aiming to find a novel organosilicon-compatible macromolecular photoinitiator that can effectively initiate the photopolymerization reaction of organosilicon resins, is highly compatible with organosilicon resins, and reduces the migration and volatilization of photodegradation debris during the photopolymerization process.

[0005] The inventors have surprisingly discovered that by introducing organosilicon segments into the molecular structure of benzoyl carbamate derivatives, a novel organosilicon-compatible macromolecular photoinitiator with excellent compatibility with organosilicon resins has been successfully prepared. The photoinitiator prepared in this invention not only effectively improves the compatibility between the photoinitiator and organosilicon resin, achieving good blending effects, but also reduces the migration and volatilization of photodegradation debris during photopolymerization, providing a new approach and method for preparing organosilicon materials via photopolymerization. Furthermore, the photoinitiator prepared in this invention exhibits excellent matching with LED light sources at wavelengths of 365-410 nm, especially 385 nm, 395 nm, and 405 nm, demonstrating good photoinitiation capabilities and ensuring a high photopolymerization rate under LED light sources. In addition, the synthesis process of this invention is simple and has significant advantages in preparation. The resulting organosilicon-compatible macromolecular photoinitiator is more environmentally friendly in application, expanding its application scope and promoting the development of LED photopolymerization technology in the field of organosilicon materials.

[0006] The objective of this invention is achieved based on the aforementioned findings.

[0007] Therefore, one object of the present invention is to provide a novel organosilicon-compatible macromolecular photoinitiator. The absorption wavelength of this type of photoinitiator can not only effectively initiate the photopolymerization reaction of organosilicon resin under LED light source, but also has good compatibility with organosilicon resin, while reducing the migration and volatilization of photodegradation 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 organosilicon-compatible macromolecular photoinitiator of the present invention as a photoinitiator in LED photopolymerization.

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

[0011] 1. Organosilicon-compatible macromolecular photoinitiators of formula (I):

[0012] in:

[0013] M is a hydroxyl group, an acrylate group, or a methacrylate group;

[0014] R1 and R2 may be the same or different, and are independently selected from C1-C2. 12 Alkyl groups, C1-C heteroatoms substituted with N, O, or S atoms 12 Alkyl, C1-C 12 alkoxy groups, or combinations thereof;

[0015] R3 and R4 may be the same or different, and are independently selected from C3-C. 12 Alkylene, C1-C 10 alkeneoxy groups, or combinations thereof;

[0016] R5 is independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, or combinations thereof;

[0017] n = 2 - 50;

[0018] p = integers between 0 and 5.

[0019] 2. According to item 1, the organosilicon-compatible macromolecular photoinitiator, wherein M is an acrylate group or a methacrylate group.

[0020] 3. According to item 1 or 2, the organosilicon-compatible macromolecular photoinitiator, wherein:

[0021] R1 and R2 may be the same or different, and are each independently selected from C1-C6 alkyl, N, O, S heteroatom-substituted C1-C6 alkyl, C1-C6 alkoxy, or combinations thereof; preferably, R1 and R2 may be the same or different, and are each independently selected from C1-C4 alkyl, N, O, S heteroatom-substituted C1-C4 alkyl, C1-C4 alkoxy, or combinations thereof; more preferably, R1 and R2 may be the same or different, and are each independently methyl or ethyl, or combinations thereof; most preferably, R1 and R2 are both methyl; and / or

[0022] R3 and R4 may be the same or different, and each is independently selected from C. 3-8 Alkylene, C 1-8 Alkyloxy group, or a combination thereof; preferably R3 and R4 are the same or different, and are independently selected from C3-C6 alkylene, C1-C6 alkene, or a combination thereof; more preferably R3 and R4 are the same or different, and are independently selected from C3-C4 alkylene, C1-C4 alkene, or a combination thereof; most preferably R3 and R4 are both -CH2-CH2-CH2-O-CH2-; and / or

[0023] R5 is independently selected from C1-C6 alkyl, C1-C6 alkoxy, fluorine, chlorine, bromine, or combinations thereof; preferably, R5 is independently selected from C1-C4 alkyl, C1-C4 alkoxy, fluorine, chlorine, bromine, or combinations thereof; more preferably, R5 is independently selected from C1-C2 alkyl, C1-C2 alkoxy, fluorine, chlorine, or combinations thereof; most preferably, R5 is methyl, methoxy, fluorine, or chlorine.

[0024] 4. An organosilicon-compatible macromolecular photoinitiator according to any one of items 1-3, wherein: n = 2-40, preferably n = 2-30, more preferably n = 2-25; and / or

[0025] p = an integer between 0 and 3, preferably p = 0 or 1.

[0026] 5. Organosilicon-compatible macromolecular photoinitiators according to any one of items 1-4, 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

[0027] p=1, R1 and R2 are both methyl groups, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is a methoxy group; or

[0028] p=1, R1 and R2 are both methyl groups, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is fluorine; or

[0029] p=1, R1 and R2 are both methyl groups, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is chlorine.

[0030] 6. A method for preparing an organosilicon-compatible macromolecular photoinitiator according to any one of claims 1-5, comprising the following process steps:

[0031] The parameters in the above formulas are defined as described in any one of claims 1-5.

[0032] 7. The method according to item 6, wherein the phase transfer catalyst in step (1) is selected from one or more of the group consisting of: benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride, preferably benzyltriethylammonium chloride or tetrabutylammonium bromide.

[0033] 8. The method according to item 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.

[0034] 9. The method according to any one of items 6-8, wherein the acid-binding agent in step (2) is one or more selected from pyridine, 3-methylpyridine, 2-methylpyridine, 4-dimethylaminopyridine, triethylamine, and diethylamine, preferably pyridine or triethylamine; and the acyl chloride is acryloyl chloride or methacryloyl chloride.

[0035] 10. The method according to any one of items 6-9, 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.

[0036] 11. Use of an organosilicon-compatible macromolecular photoinitiator obtained according to any one of items 1-5 or any one of items 6-10 as a photoinitiator in LED photopolymerization, particularly in LED photopolymerization with radiation wavelengths of 365-410 nm, especially 385 nm, 395 nm and 405 nm.

[0037] 12. A photopolymerizable composition comprising:

[0038] (a) at least one silicone resin, and

[0039] (b) at least one method according to any one of items 1-5 or any one of items 6-10

[0040] The obtained organosilicon-compatible macromolecular photoinitiator.

[0041] 13. The photopolymerizable composition according to item 12, wherein (a) the content of at least one organosilicon resin is 95-98.5%, and (b) the content of at least one organosilicon-compatible macromolecular photoinitiator is 1-4%, based on the total weight of the photopolymerizable composition.

[0042] 14. A photopolymerizable material that can be obtained from the photopolymerizable composition of item 12 or 13.

[0043] 15. A method for preparing a photopolymerizable material, comprising irradiating the photopolymerizable composition of claim 12 or 13 with an LED light source having a radiation wavelength of 365-410 nm, particularly 385 nm, 395 nm and 405 nm. Attached image description:

[0044] Figure 1 shows the infrared spectra of the organosilicon macromolecular photoinitiator and the raw material epoxy polysiloxane prepared in Example 2;

[0045] Figure 2 shows the UV-Vis absorption spectra of the organosilicon macromolecular photoinitiators prepared in Examples 2, 4, 6, 8, and 10.

[0046] Figure 3 shows the degradation 1H NMR spectrum of the organosilicon macromolecular photoinitiator prepared in Example 2;

[0047] Figure 4 shows the degradation UV spectrum of the organosilicon macromolecular photoinitiator prepared in Example 1;

[0048] Figure 5 shows the photopolymerization kinetics curves of the organosilicon macromolecular photoinitiators prepared in Examples 4 and 10;

[0049] Figure 6 shows the electron paramagnetic resonance (EPR) spectrum of the organosilicon macromolecular photoinitiator prepared in Example 2;

[0050] Figure 7 is a schematic diagram showing the compatibility between the organosilicon macromolecular photoinitiator prepared in Examples 6 and 8 and the methacrylate organosilicon resin. Detailed Implementation

[0051] According to one aspect of the present invention, an organosilicon-compatible macromolecular photoinitiator of general formula (I) is provided:

[0052] in:

[0053] M is a hydroxyl group, an acrylate group, or a methacrylate group;

[0054] R1 and R2 may be the same or different, and are independently selected from C1-C2. 12 Alkyl groups, C1-C heteroatoms substituted with N, O, or S atoms 12 Alkyl, C1-C 12 alkoxy groups, or combinations thereof;

[0055] R3 and R4 may be the same or different, and are independently selected from C3-C. 12 Alkylene, C1-C 10 alkeneoxy groups, or combinations thereof;

[0056] R5 is independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, or combinations thereof;

[0057] n = 2 - 50;

[0058] p = integers between 0 and 5.

[0059] In this invention, the prefix "C" n -C m "In each case, it indicates that the number of carbon atoms contained in the group is nm."

[0060] "Halogen" refers to fluorine, chlorine, bromine, and iodine. In this invention, it is preferred that the halogen includes fluorine, chlorine, or a combination thereof.

[0061] The term "C" used in this article n -C m "Alkyl" refers to a branched or unbranched saturated hydrocarbon group having 1-12, preferably 1-6, and more preferably 1-4 carbon atoms. For example, C1-C6 alkyl groups can be methyl, ethyl, propyl, butyl, pentyl, hexyl, and their isomers, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and n-hexyl. C1-C4 alkyl groups can be methyl, ethyl, propyl, butyl, and their isomers, especially methyl or ethyl.

[0062] The term "C" used in this article n -C m "Alkoxy" refers to the compound formed by the carbon atom in C2O2. n -C m alkyl corresponding to open chain C n -C m In alkanes, an oxygen atom is bonded to any carbon atom as a linking group. n -C m Alkyl groups, such as C1-C 12 Alkoxy groups, preferably C1-C6 alkoxy groups, more preferably C1-C4 alkoxy groups. For example, C1-C6 alkoxy groups can be methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and their isomers, particularly methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, n-pentoxy, isopentoxy, and n-hexoxy. C1-C4 alkoxy groups can be methoxy, ethoxy, propoxy, butoxy, and their isomers, particularly methoxy or ethoxy.

[0063] The term "C" used in this article n -C m "Alkylene" refers to a branched or unbranched saturated alkylene group having 3-12, preferably 3-8, more preferably 3-6, and especially 3-4 carbon atoms. For example, C3-C8 alkylene groups can be propylene, butylene, pentylene, hexylene, heptylene, octylene, and their isomers, especially propylene, butylene, pentylene, and hexylene. C3-C6 alkylene groups can be propylene, butylene, pentylene, hexylene, and their isomers, especially propylene or butylene.

[0064] The term "C" used in this article n -C m "Alkyloxy" refers to the carbonyl group at C10 ... n -C m An oxygen atom is bonded to any carbon atom of an alkyl group as an additional linking group. n -Cm Alkyl groups such as C1-C 10 The alkene oxide is preferably C1-C6, and more preferably C1-C4. For example, C1-C6 alkene oxides can be methyleneoxy, ethoxy, propoxy, butoxy, pentyleoxy, hexyloxy, and their isomers, particularly methyleneoxy, ethoxy, propoxy, butoxy, pentyleoxy, and hexyloxy. C1-C4 alkene oxides can be methyleneoxy, ethoxy, propoxy, butoxy, and their isomers, particularly methyleneoxy, ethoxy, propoxy, or butoxy.

[0065] In a preferred embodiment of the present invention, M is an acrylate group or a methacrylate group.

[0066] In some embodiments of the present invention, R1 and R2 may be the same or different, and are each independently selected from C1-C6 alkyl, N, O, S heteroatom-substituted C1-C6 alkyl, C1-C6 alkoxy, or combinations thereof; preferably, R1 and R2 may be the same or different, and are each independently selected from C1-C4 alkyl, N, O, S heteroatom-substituted C1-C4 alkyl, C1-C4 alkoxy, or combinations thereof; more preferably, R1 and R2 may be the same or different, and are each independently methyl or ethyl, or combinations thereof; most preferably, R1 and R2 are both methyl.

[0067] In some embodiments of the present invention, R3 and R4 may be the same or different, and are each independently selected from C3-C8 alkylene, C1-C8 alkene, or combinations thereof; preferably, R3 and R4 may be the same or different, and are each independently selected from C3-C6 alkylene, C1-C6 alkene, or combinations thereof; more preferably, R3 and R4 may be the same or different, and are each independently selected from C3-C4 alkylene, C1-C4 alkene, or combinations thereof; most preferably, R3 and R4 are both -CH2-CH2-CH2-O-CH2-.

[0068] In some embodiments of the present invention, R5 is independently selected from C1-C6 alkyl, C1-C6 alkoxy, fluorine, chlorine, bromine, or combinations thereof; preferably, R5 is independently selected from C1-C4 alkyl, C1-C4 alkoxy, fluorine, chlorine, bromine, or combinations thereof; more preferably, R5 is independently selected from C1-C2 alkyl, C1-C2 alkoxy, fluorine, chlorine, or combinations thereof; most preferably, R5 is methyl, methoxy, fluorine, or chlorine.

[0069] In some embodiments of the present invention, n = 2-40, preferably n = 2-30, and more preferably n = 2-25.

[0070] In some embodiments of the present invention, p = an integer from 0 to 3, preferably p = 0 or 1.

[0071] In a preferred embodiment of the present invention, p = 0, R1 and R2 are both methyl groups, and R3 and R4 are both -CH2-CH2-CH2-O-CH2-.

[0072] In a preferred embodiment of the present invention, p = 1, R1 and R2 are both methyl groups, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is a methyl group.

[0073] 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.

[0074] In a preferred embodiment of the present invention, p = 1, R1 and R2 are both methyl groups, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is fluorine.

[0075] In a preferred embodiment of the present invention, p = 1, R1 and R2 are both methyl groups, R3 and R4 are both -CH2-CH2-CH2-O-CH2-, and R5 is chlorine.

[0076] A second aspect of the present invention relates to a method for preparing an organosilicon-compatible macromolecular photoinitiator of general formula (I) of the present invention, comprising the following process steps:

[0077] R1, R2, R3, R4, R5, and p are defined above.

[0078] 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.

[0079] In a preferred embodiment of the present invention, the phase transfer catalyst in step (1) of the method of the present invention is benzyltriethylammonium chloride or tetrabutylammonium bromide.

[0080] In step (1) of the method of the present invention, the molar ratio of epoxy polysiloxane of formula (III), phase transfer catalyst and benzoylformic acid of formula (II) is 1:0.1-1:2-6, preferably 1:0.3-1:2-3.

[0081] Step (1) of the method of the present invention is generally carried out in a solvent, preferably an organic solvent. There are no particular restrictions on the type of solvent, as long as it can dissolve the reactants and is chemically inert to the reaction, i.e., does not participate in the reaction. Examples of solvents commonly used are dichloromethane, ethyl acetate, tetrahydrofuran, and N,N-dimethylformamide (DMF). Preferably, the reaction in step (1) is carried out in DMF or tetrahydrofuran. The amount of solvent used is conventional and can be determined by common knowledge in the art or by several routine preliminary experiments.

[0082] More specifically, in step (1) of the method of the present invention, the epoxy polysiloxane of formula (III), the phase transfer catalyst, and the solvent are placed in a reaction vessel. Under nitrogen protection, the mixture is stirred at 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 the 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. It is then washed twice each with saturated sodium carbonate aqueous solution, deionized water, and saturated sodium chloride solution. The crude product is then purified by column chromatography to obtain intermediate product A, namely, a hydroxyl-containing organosilicon macromolecular photoinitiator.

[0083] 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. A suitable acid-binding agent is one or more selected from pyridine, 3-methylpyridine, 2-methylpyridine, 4-dimethylaminopyridine, triethylamine, and diethylamine, preferably pyridine or triethylamine. The acyl chloride is acryloyl chloride or methacryloyl chloride.

[0084] In step (2) of the method of the present invention, 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.

[0085] Step (2) of the method of the present invention is typically carried out in a solvent, preferably an organic solvent. There are no particular restrictions on the type of solvent, as long as it can dissolve the reactants and is chemically inert to the reaction, i.e., does not participate in the reaction. Examples of solvents commonly used are dimethyl sulfoxide, dichloromethane, ethyl acetate, tetrahydrofuran, and N,N-dimethylformamide. Preferably, the reaction is carried out in dichloromethane or tetrahydrofuran. The amount of solvent used is conventional and can be determined by common knowledge in the art or by several routine preliminary experiments.

[0086] More specifically, in step (2) of the method of the present invention, intermediate product A is mixed with an acid-binding agent in an anhydrous solvent. Under nitrogen protection at -10°C to 0°C, an aqueous solution of acyl chloride is slowly added dropwise, and the reaction is carried out for 1-4 hours, preferably 2-3 hours. Subsequently, the temperature is 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 the organosilicon-compatible macromolecule of general formula (I).

[0087] The organosilicon-compatible macromolecular photoinitiator of general formula (I) of this invention is suitable for use as a photoinitiator for LED photopolymerization. It exhibits excellent compatibility with LED light sources with wavelengths of 365-410 nm, especially 385 nm, 395 nm, and 405 nm, demonstrating good photoinitiation capabilities and ensuring a high photopolymerization rate under LED light sources. In particular, the photoinitiator of this invention can effectively initiate the photopolymerization reaction of organosilicon resins and has good compatibility with organosilicon resins, while reducing the migration and volatilization of photodegradation debris during photopolymerization.

[0088] Therefore, in another aspect of the invention, the use of the organosilicon-compatible macromolecular photoinitiator of general formula (I) of the invention as a photoinitiator in LED photopolymerization is provided.

[0089] Furthermore, the present invention provides a photopolymerizable composition comprising:

[0090] (a) at least one silicone resin, and

[0091] (b) at least one organosilicon-compatible macromolecular photoinitiator of the present invention.

[0092] In the photopolymerizable composition of the present invention, (a) the content of at least one organosilicon resin is 95-98.5%, and (b) the content of at least one organosilicon-compatible macromolecular photoinitiator is 1-4%, based on the total weight of the photopolymerizable composition.

[0093] More specifically, the photopolymerizable composition is a free radical photopolymerizable composition comprising 1-4% of the present invention’s organosilicon-compatible macromolecular photoinitiator, 0.5-1% of a hydrogen donor and 95-98.5% of an organosilicon resin, based on the total weight of the photopolymerizable composition.

[0094] Furthermore, the silicone resin may 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 may be selected from one or more 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 their salts.

[0095] Besides photoinitiators and hydrogen donors, photopolymerizable compositions may contain a variety of additives. Examples include thermal inhibitors designed to prevent premature polymerization, such as 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxo radicals and their derivatives; antistatic agents; flow improvers and thickeners; chain transfer agents; photosensitizers used to modify or broaden spectral sensitivity, such as aromatic carbonyl compounds like benzophenone derivatives and thioxanthone derivatives; fillers; or pigments.

[0096] The photopolymerizable compositions of the present invention can be used for various purposes, such as as printing inks (e.g., screen printing inks, offset or flexographic printing inks, inkjet inks, sheet-fed printing inks, electrophotographic inks, gravure inks), as transparent coatings, white coatings, or colored coatings, for photographic reproduction methods, for holographic recording materials, for image recording methods or for producing printing plates that can be developed using organic solvents or aqueous alkaline media, for producing screen printing masks, as dental filling compounds, as adhesives, as pressure-sensitive adhesives, as laminating resins, as etching resists or permanent resists, as photostructured dielectrics and as soldering masks for electronic circuits, as resists for producing color filters for any type of display screen or for generating structures during the manufacture of plasma displays and electroluminescent displays, for producing optical switches and gratings, for manufacturing three-dimensional articles by bulk polymerization or according to stereolithography, for manufacturing composite materials of gel coatings and thick-layer compositions, for coating or sealing electronic components, or as coatings for optical fibers. The composition is also suitable for producing optical lenses (e.g., contact lenses or Fresnel lenses) and for manufacturing medical devices, auxiliaries, or implants.

[0097] Therefore, in another aspect of the invention, a photopolymerizable material is provided that can be obtained from a photopolymerizable composition comprising the organosilicon-compatible macromolecular photoinitiator of the present invention, which is obtained by irradiating the photopolymerizable composition comprising the organosilicon-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.

[0098] The beneficial effects of this invention are as follows:

[0099] (1) The organosilicon macromolecular photoinitiator prepared in this invention has excellent matching with LED light sources with wavelengths of 365-410nm, especially 385nm, 395nm and 405nm, and exhibits good photoinitiation ability, ensuring a high-efficiency photopolymerization rate under LED light source.

[0100] (2) The organosilicon-compatible macromolecular photoinitiator prepared by the present invention not only effectively improves the compatibility between the photoinitiator and the organosilicon resin and achieves a good blending effect, but also reduces the migration and volatilization of photodecomposition fragments during photopolymerization, providing a new approach and method for preparing organosilicon materials by photopolymerization.

[0101] (3) The synthesis process of this invention is simple and has significant advantages in preparation. The resulting organosilicon-compatible macromolecular photoinitiator is more environmentally friendly in application, expands the application scope, and promotes the development of LED photopolymerization technology in the field of organosilicon materials.

[0102] Example

[0103] The present invention will be explained below with reference to embodiments. Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature or product specifications in the art.

[0104] The materials and reagents used in the following examples are listed in Table A, and the experimental instruments are shown in Table B. Other materials and reagents are commercially available.

[0105] Table A - Experimental Materials and Reagents

[0106] Table B - Experimental Instruments

[0107] Examples 1-2:

[0108] Example 1 is the synthesis of a hydroxyl organosilicon macromolecular photoinitiator.

[0109] 20 g (0.01 mol, M = 2000 g / mol) X-22-163A, 2.27 g benzyltriethylammonium chloride (0.01 mol), and 100 mL DMF were placed in a 500 mL three-necked flask. The mixture was stirred at 90 °C for 30 minutes under nitrogen protection. Subsequently, 50 mL of DMF solution containing 4.5 g (0.03 mol) benzoylformic acid was added, and the reaction mixture was maintained at 110 °C for 24 hours. After removing the solvent by rotary evaporation, the product was dissolved in 100 mL of ethyl acetate and washed twice each with 50 mL of saturated sodium carbonate aqueous solution, 50 mL of deionized water, and 50 mL of saturated sodium chloride solution. The crude product was then purified by column chromatography (EA:PE = 1:5 v / v) to obtain 18.1 g of a pale yellow liquid intermediate, PASi-1, a hydroxyl organosilicon macromolecular photoinitiator, with a yield of 78.7%.

[0110] 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).

[0111] Example 2 is the synthesis of a polymerizable organosilicon macromolecular photoinitiator.

[0112] 11.5 g (5 mmol) of PASi-1 and 1.1 g (10 mmol) of triethylamine were mixed in 50 mL of anhydrous dichloromethane. Under nitrogen protection at 0 °C, a solution of 0.9 g (10 mmol) of acryloyl chloride in 20 mL of anhydrous dichloromethane was slowly added dropwise, and the reaction was allowed to proceed for 2 hours. The temperature was then 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 100 mL of ethyl acetate. The product was washed three times with 50 mL of deionized water, and the organic phase was collected to give 11.2 g of a yellow liquid product, PASi-2, which can polymerize organosilicon macromolecular photoinitiators with a yield of 93.0%.

[0113] 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).

[0114] Examples 3-4:

[0115] Example 3 is the synthesis of a fluorine-containing hydroxyl organosilicon macromolecular photoinitiator.

[0116] 20 g (0.01 mol, M = 2000 g / mol) X-22-163A, 3.22 g tetrabutylammonium bromide (0.01 mol), and 100 mL DMF were placed in a 500 mL three-necked flask. The mixture was stirred at 90 °C for 30 minutes under nitrogen protection. Then, 50 mL of DMF solution containing 5.0 g (0.03 mol) p-fluorobenzoylcarboxylic acid was added, and the reaction mixture was maintained at 110 °C for 24 hours. After removing the solvent by rotary evaporation, the product was dissolved in 100 mL of ethyl acetate and washed twice each with 50 mL of saturated sodium carbonate aqueous solution, 50 mL of deionized water, and 50 mL of saturated sodium chloride solution. The crude product was then purified by column chromatography (EA:PE = 1:5 v / v) to obtain 18.4 g of a pale yellow liquid intermediate, PASi-3, a fluorinated hydroxyl organosilicon macromolecular photoinitiator, with a yield of 78.8%.

[0117] 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).

[0118] Example 4 describes the synthesis of a fluorine-containing polymerizable organosilicon macromolecular photoinitiator.

[0119] 11.7 g (5 mmol) of PASi-3 and 1.1 g (10 mmol) of triethylamine were mixed in 50 mL of anhydrous dichloromethane. Under nitrogen protection at 0 °C, a solution of 0.9 g (10 mmol) of acryloyl chloride in 20 mL of anhydrous dichloromethane was slowly added dropwise, and the reaction was allowed to proceed for 2 hours. The temperature was then 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 100 mL of ethyl acetate. The product was washed three times with 50 mL of deionized water, and the organic phase was collected to give 11.4 g of the yellow liquid product PASi-4, a fluorinated polymerizable organosilicon macromolecular photoinitiator, in 93.1% yield.

[0120] 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).

[0121] Examples 5-6:

[0122] Example 5 describes the synthesis of a chlorine-containing hydroxyl organosilicon macromolecular photoinitiator.

[0123] 20 g (0.01 mol, M = 2000 g / mol) X-22-163A, 3.22 g tetrabutylammonium bromide (0.01 mol), and 100 mL DMF were placed in a 500 mL three-necked flask. The mixture was stirred at 90 °C for 30 minutes under nitrogen protection. Then, 50 mL of DMF solution containing 5.5 g (0.03 mol) p-chlorobenzoylformic acid was added, and the reaction mixture was maintained at 110 °C for 24 hours. After removing the solvent by rotary evaporation, the product was dissolved in 100 mL of ethyl acetate and washed twice each with 50 mL of saturated sodium carbonate aqueous solution, 50 mL of deionized water, and 50 mL of saturated sodium chloride solution. The crude product was then purified by column chromatography (EA:PE = 1:5 v / v) to obtain 18.9 g of a pale yellow liquid intermediate, PASi-5, a chlorinated hydroxyl organosilicon macromolecular photoinitiator, with a yield of 79.8%.

[0124] 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).

[0125] Example 6 describes the synthesis of a chlorine-containing polymerizable organosilicon macromolecular photoinitiator.

[0126] 11.8 g (5 mmol) of PASi-5 and 0.79 g (10 mmol) of pyridine were mixed in 50 mL of anhydrous dichloromethane. Under nitrogen protection at 0 °C, a solution of 0.9 g (10 mmol) of acryloyl chloride in 20 mL of anhydrous dichloromethane was slowly added dropwise, and the reaction was allowed to proceed for 2 hours. The temperature was then 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 100 mL of ethyl acetate. The product was washed three times with 50 mL of deionized water, and the organic phase was collected to give 11.2 g of the yellow liquid product PASi-6, a chlorine-containing polymerizable organosilicon macromolecular photoinitiator, in 90.8% yield.

[0127] 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).

[0128] Examples 7-8:

[0129] Example 7 is the synthesis of a methyl-containing hydroxyl organosilicon macromolecular photoinitiator.

[0130] 20 g (0.01 mol, M = 2000 g / mol) X-22-163A, 3.22 g tetrabutylammonium bromide (0.01 mol), and 100 mL DMF were placed in a 500 mL three-necked flask. The mixture was stirred at 90 °C for 30 minutes under nitrogen protection. Then, 50 mL of DMF solution containing 4.9 g (0.03 mol) p-methylbenzoylformic acid was added, and the reaction mixture was maintained at 110 °C for 24 hours. After removing the solvent by rotary evaporation, the product was dissolved in 100 mL of ethyl acetate and washed twice each with 50 mL of saturated sodium carbonate aqueous solution, 50 mL of deionized water, and 50 mL of saturated sodium chloride solution. The crude product was then purified by column chromatography (EA:PE = 1:5 v / v) to obtain 18.6 g of a pale yellow liquid intermediate, PASi-7, a methyl-containing hydroxyl organosilicon macromolecular photoinitiator, with a yield of 79.9%.

[0131] 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).

[0132] Example 8 describes the synthesis of a methyl-containing polymerizable organosilicon macromolecular photoinitiator.

[0133] 11.6 g (5 mmol) of PASi-7 and 0.79 g (10 mmol) of pyridine were mixed in 50 mL of anhydrous tetrahydrofuran. Under nitrogen protection at 0 °C, 20 mL of anhydrous tetrahydrofuran solution containing 0.9 g (10 mmol) of acryloyl chloride was slowly added dropwise, and the reaction was allowed to proceed for 2 hours. The temperature was then 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 100 mL of ethyl acetate. The product was washed three times with 50 mL of deionized water, and the organic phase was collected to give 11.3 g of the yellow liquid product PASi-8, a methyl-containing polymerizable organosilicon macromolecular photoinitiator, in 93.1% yield.

[0134] 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).

[0135] Examples 9-10:

[0136] Example 9 describes the synthesis of a methoxyl-containing hydroxyl organosilicon macromolecular photoinitiator.

[0137] 20 g (0.01 mol, M = 2000 g / mol) X-22-163A, 3.22 g tetrabutylammonium bromide (0.01 mol), and 100 mL DMF were placed in a 500 mL three-necked flask. The mixture was stirred at 90 °C for 30 minutes under nitrogen protection. Then, 50 mL of DMF solution containing 5.4 g (0.03 mol) p-methoxybenzoylformic acid was added, and the reaction mixture was maintained at 110 °C for 24 hours. After removing the solvent by rotary evaporation, the product was dissolved in 100 mL of ethyl acetate and washed twice each with 50 mL of saturated sodium carbonate aqueous solution, 50 mL of deionized water, and 50 mL of saturated sodium chloride solution. The crude product was then purified by column chromatography (EA:PE = 1:5 v / v) to obtain 18.8 g of a pale yellow liquid intermediate, PASi-9, a methoxylated hydroxyl organosilicon macromolecular photoinitiator, with a yield of 79.7%.

[0138] 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).

[0139] Example 10 describes the synthesis of a methoxyl-containing polymerizable organosilicon macromolecular photoinitiator.

[0140] 11.8 g (5 mmol) of PASi-9 and 0.79 g (10 mmol) of pyridine were mixed in 50 mL of anhydrous tetrahydrofuran. Under nitrogen protection at 0 °C, a 20 mL solution of anhydrous tetrahydrofuran containing 1.04 g (10 mmol) of methacryloyl chloride was slowly added dropwise, and the reaction was allowed to proceed for 2 hours. The temperature was then 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 100 mL of ethyl acetate. The product was washed three times with 50 mL of deionized water, and the organic phase was collected to give 11.4 g of the yellow liquid product PASi-10, a methoxylated polymerizable organosilicon macromolecular photoinitiator, in 92.4% yield.

[0141] 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).

[0142] Test Example 1:

[0143] The purpose of Test Example 1 is to demonstrate the successful preparation of the photoinitiator PASi-2 prepared in Example 2.

[0144] The functional group changes of PASi-2 compared with the raw material epoxy polysiloxane X-22-163A were determined by Fourier transform infrared spectroscopy, and its infrared spectrum is shown in Figure 1. The results show that, compared with X-22-163A, the carbonyl absorption peaks of benzoyl ester and acrylate in PASi-2 are at 1732 cm⁻¹, respectively. - 1 and 1689cm -1 Appears on the left and right. At 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 sides, respectively, indicating that the epoxy ring of X-22-163A was successfully opened and connected with benzoyl carboxylate and acrylate, that is, the photoinitiator PASi-2 was successfully prepared.

[0145] Test Example 2:

[0146] The purpose of Test Example 2 is to demonstrate 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.

[0147] Prepare PASi-2, PASi-4, PASi-6, PASi-8, and PASi-10 at concentrations of 1×10⁻⁶. -4 A mol / L acetonitrile solution was used. The UV-Vis absorption spectra of five different solutions in the wavelength range of 200-500 nm were measured using a UV-Vis spectrophotometer, and the results are shown in Figure 2. The results show that the maximum absorption wavelength of all five photoinitiators is below 350 nm, but they all have a certain absorption capacity at around 400 nm. This weak absorption capacity can endow the initiators with the initiation ability at the LED emission wavelength.

[0148] Test Example 3:

[0149] The purpose of Test Example 3 is to demonstrate that the photoinitiator PASi-2 prepared in Example 2 undergoes photodegradation under 405nm LED light irradiation.

[0150] Dissolve 0.012 g of PASi-2 and 0.0005 g of triethylamine in 50 mL of CDCl3 to prepare a solution of 10 -4 A mol / L CDCl3 solution was used. The solution was irradiated with 405 nm LED light for 0 s, 120 s, 240 s, and 480 s, respectively, and the 1H NMR spectra were measured using a nuclear magnetic resonance spectrometer. The results are shown in Figure 3. The results show that as the irradiation time with 405 nm LED light increased, two new peaks gradually formed in the 7.0-7.3 ppm range of the 1H NMR spectrum. This indicates that PASi-2 undergoes photodegradation under LED light irradiation, and the carbonyl group connected to the benzene ring may have undergone a hydrogen abstraction reaction to generate alkyl radicals. This leads to an increase in the electron cloud density of the benzene ring and a shift of the chemical shift to a higher field.

[0151] Test Example 4:

[0152] The purpose of Test Example 4 is to demonstrate that the photoinitiator PASi-1 prepared in Example 1 undergoes a photochemical reaction under 405nm LED light irradiation.

[0153] Dissolve 0.0115 g of PASi-1 and 0.001 g of the hydrogen donor ethyl p-dimethylaminobenzoate (EDB) in 50 mL of acetonitrile to prepare a solution of 10 -4 A mol / L acetonitrile solution was used. After irradiation with a 405 nm LED lamp for different times, UV-Vis absorption measurements were performed, and the degradation UV spectrum is shown in Figure 4. The results show that with the extension of the 405 nm LED lamp irradiation time, the absorbance of both PASi-1 and EDB acetonitrile solutions gradually decreased at 250 nm and 307 nm. This indicates that PASi-1 and EDB undergo a photochemical reaction under 405 nm LED lamp irradiation.

[0154] Test Example 5:

[0155] The purpose of Test Example 5 is to demonstrate that the photoinitiators PASi-4 and PASi-10 prepared in Examples 4 and 10 can effectively initiate the polymerization of organosilicon resins under 385nm LED light irradiation.

[0156] 1. Preparation of organosilicon resin composition

[0157] Two photosensitive resin compositions were prepared using methacrylate silicone resin X-22-164A (Mn = 1720) in the following proportions:

[0158] X-22-164A (95 parts by weight), PASi-4 (4 parts by weight), EDB (1 part by weight);

[0159] X-22-164A (95 parts by weight), PASi-10 (4 parts by weight), EDB (1 part by weight).

[0160] 2. Polymerization performance test

[0161] The photopolymerization kinetics of the prepared photosensitive resin composition are shown in Figure 5. The results indicate that the photoinitiators PASi-4 and PASi-10 prepared in this invention exhibit photopolymerization kinetics at an emission wavelength of 385 nm (light intensity 100 mW / cm²). 2 Under the illumination of an LED light source, the photopolymerization reaction of methacrylate silicone resin X-22-164A can be successfully initiated, with double bond conversion rates reaching 50.7% and 63.3%, respectively. This indicates that the photoinitiator of the present invention can effectively initiate the polymerization of silicone resin.

[0162] Test Example 6:

[0163] The purpose of Test Example 6 is to demonstrate that the photoinitiator PASi-2 prepared in Example 2 can generate free radicals under 405nm LED light irradiation.

[0164] 0.012 g of PASi-2, 0.001 g of EDB, and 0.0028 g of 5,5-dimethyl-1-pyrrolline-N-oxide (DMPO) were dissolved in 50 mL of tert-butylbenzene. The EPR spectrum of the PASi-2 and EDB mixture after irradiation with a 405 nm LED light source, and the simulated EPR spectrum, were measured using electron paramagnetic resonance (EPR) spectroscopy. The results show that fitting the EPR spectrum of the PASi-2 and EDB mixture using the hyperfine splitting constant and comparing it with the measured EPR spectrum indicates that the free radicals captured by DMPO after irradiation of the PASi-2 and EDB mixture are aminoalkyl free radicals.

[0165] Test Example 7:

[0166] The purpose of Test Example 7 is to demonstrate that the photoinitiators PASi-6 and PASi-8 prepared in Examples 6 and 8 have good compatibility with organosilicon resins.

[0167] 1. Preparation of organosilicon resin composition

[0168] Two compositions were prepared using methacrylate silicone resins X-22-164A (Mn = 1720) and X-22-164B (Mn = 3260) in the following proportions:

[0169] X-22-164A (95 parts by weight), PASi-6 (5 parts by weight);

[0170] X-22-164B (95 parts by weight), PASi-8 (5 parts by weight).

[0171] 2. Compatibility testing

[0172] After stirring the above composition thoroughly, it was allowed to stand in the dark for 24 hours, and the separation of the composition was observed. The results are shown in Figure 7. The results show that no separation phenomenon occurred in either composition, indicating that the two photoinitiators PASi-6 and PASi-8 have good compatibility with organosilicon resin.

[0173] Test Example 8:

[0174] The purpose of Test Example 8 is to demonstrate that the photoinitiator PASi-10 of Example 10 has a low mobility.

[0175] 1. Preparation of organosilicon resin composition

[0176] Two compositions were prepared using methacrylate silicone resin X-22-164A (Mn=1720), photoinitiator PASi-10, and commercially available 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) in the following proportions:

[0177] X-22-164A (95 parts by weight), PASi-10 (4 parts by weight), EDB (1 part by weight);

[0178] X-22-164A (96 parts by weight), 1173 (4 parts by weight).

[0179] 2. Migration Rate Testing

[0180] After mixing the two compositions thoroughly, use 100mW / cm 2The film was photocured by irradiating it with a 365nm UV lamp for 15 minutes, and the unreacted monomers and initiators on the film surface were rinsed with ethanol. A suitable amount of the film was immersed in ethanol, and the change in absorbance was monitored. The monitoring wavelength for PASi-10 was 251nm, and for 1173 it was 254nm. The results are shown in Table 1. The results show that at 1 h, the migration rate of PASi-10 was 5.10% of that of 1173; at 48 h, the migration rate of PASi-10 was 11.12% of that of 1173. Therefore, the PASi-10 photoinitiator of Example 10 has a low migration rate.

[0181] Table 1. Relative mobility of photoinitiators PASi-10 and 1173 in Example 10

[0182] The above results demonstrate that the organosilicon macromolecular photoinitiator provided by this invention can effectively initiate the photopolymerization reaction of organosilicon resin under LED light source, and has good compatibility with organosilicon resin, while reducing the migration and volatilization of photodegradation fragments during photopolymerization.

Claims

1. Organosilicon-compatible macromolecular photoinitiators of formula (I): in: M is a hydroxyl group, an acrylate group, or a methacrylate group; R1 and R2 may be the same or different, and are independently selected from C1-C2. 12 Alkyl groups, C1-C heteroatoms substituted with N, O, or S atoms 12 Alkyl, C1-C 12 alkoxy groups, or combinations thereof; R3 and R4 may be the same or different, and are independently selected from C3-C. 12 Alkylene, C1-C 10 alkeneoxy groups, or combinations thereof; R5 is independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, or combinations thereof; n＝2-50； p = integers between 0 and 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 may be the same or different, and are each independently selected from C1-C6 alkyl, N, O, S heteroatom-substituted C1-C6 alkyl, C1-C6 alkoxy, or combinations thereof. Preferably, R1 and R2 may be the same or different, and are each independently selected from C1-C4 alkyl, N, O, S heteroatom-substituted C1-C4 alkyl, C1-C4 alkoxy, or combinations thereof. More preferably, R1 and R2 may be the same or different, and are each independently methyl or ethyl, or combinations thereof. Most preferably, R1 and R2 are both methyl. And / or R3 and R4 may be the same or different, and are each independently selected from C3-C8 alkylene, C1-C8 alkene, or combinations thereof; preferably, R3 and R4 may be the same or different, and are each independently selected from C3-C6 alkylene, C1-C6 alkene, or combinations thereof; more preferably, R3 and R4 may be the same or different, and are each independently selected from C3-C4 alkylene, C1-C6 alkene, or combinations thereof. 1-4 alkeneoxy groups, or combinations 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 combinations thereof; preferably, R5 is independently selected from C1-C4 alkyl, C1-C4 alkoxy, fluorine, chlorine, bromine, or combinations thereof; more preferably, R5 is independently selected from C1-C2 alkyl, C1-C2 alkoxy, fluorine, chlorine, or combinations thereof; most preferably, R5 is methyl, methoxy, fluorine, or chlorine.

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

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

6. A method for preparing an organosilicon-compatible macromolecular photoinitiator according to any one of claims 1-5, comprising the following process steps: The parameters in the above formulas are defined as described in any one of claims 1-5.

7. The method according to claim 6, wherein the phase transfer catalyst in step (1) is selected from one or more of the group consisting of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride, preferably benzyltriethylammonium chloride or tetrabutylammonium bromide.

8. The method according to 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 6-8, wherein the acid-binding agent in step (2) is one or more selected from pyridine, 3-methylpyridine, 2-methylpyridine, 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 6-9, 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. The use of the organosilicon-compatible macromolecular photoinitiator obtained by the method of any one of claims 1-5 or any one of claims 6-10 as a photoinitiator in LED photopolymerization, particularly in LED photopolymerization with radiation wavelengths of 365-410 nm, especially 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 macromolecular photoinitiator obtained by the method of any one of claims 1-5 or any one of claims 6-10.

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

14. A photopolymerizable material that can be obtained from the photopolymerizable composition of claim 12 or 13.

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

Images