Cationic photopolymerization type phosphorus-containing bifunctional oxetane monomer as well as preparation method and application thereof

Abstract

The invention discloses a cationic photopolymerization type phosphorus-containing bifunctional oxetane monomer as well as a preparation method and application thereof, and relates to a compound as shown in a formula (I), and variables R1, R2 and R3 are defined in the specification. The invention further relates to preparation of the compound shown in the formula (I), a photocurable composition containing the compound shown in the formula (I), a photocurable material obtained by photocuring of the photocurable composition and application of the compound shown in the formula (I) in the field of photocurable materials. The compound as shown in the formula (I) has good photopolymerization performance, can endow a material with certain flame retardant property, and can promote the thermal degradation process of the material and promote the material to form carbon. The prepared photocuring material has excellent mechanical properties and surface hydrophobicity. # imgabs0 #

Description

Technical Field

[0001] The present invention is applicable to the field of cationic photocurable materials, and specifically relates to a type of cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer. The present invention also relates to a preparation method of the monomer, a photocurable composition containing the monomer, a photocurable material obtained from the photocurable composition, and the application of the monomer in the field of photocurable materials. Background Art

[0002] In recent years, as people pay more and more attention to energy conservation and environmental protection, photopolymerization technology has been favored in more and more fields. Cationic photopolymerization system has a faster polymerization speed and is not inhibited by oxygen. It has good dimensional stability and strong adhesion. Among the existing cationic photopolymerizable monomers, oxetane cationic photopolymerizable monomers are deeply loved by people because of their low viscosity, low toxicity, low volatility and other characteristics. However, the types of oxetane cationic photopolymerizable monomers reported so far are relatively small. In addition, the polymer materials formed after epoxy monomers are cured are generally easy to burn, so the industry hopes to develop functional monomers with flame retardant effects. Based on this, the development of a series of oxetane monomers that can be cationic photopolymerized and can give materials certain flame retardant properties has important theoretical significance and practical value. Summary of the invention

[0003] The purpose of the present invention is to provide a type of cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer. The inventors have found through research that the cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer provided by the present invention has good photopolymerization performance, can give the material certain flame retardant properties, and can promote the thermal degradation process of the material and promote the carbonization of the material. The prepared photocurable material has excellent mechanical properties and surface hydrophobicity.

[0004] Another object of the present invention is to provide a method for preparing the cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer of the present invention. The preparation method is simple and easy to operate, has mild conditions, and the reaction raw materials are cheap and easy to obtain, and the cost is low.

[0005] Another object of the present invention is to provide a photocurable composition comprising the cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer of the present invention.

[0006] Still another object of the present invention is to provide a photocurable material obtained by photocuring the photocurable composition of the present invention.

[0007] Another object of the present invention is to provide the use of the cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer of the present invention in a photocurable coating composition, a photocurable ink composition or a photoresist composition.

[0008] The technical solution for achieving the above-mentioned purpose of the present invention can be summarized as follows:

[0009] 1. Compounds of the following formula (I):

[0010]

[0011] in

[0012] The R1 group is selected from: C1-C6 alkoxy, C6-C 10 Aryl or C6-C 10 Aryloxy;

[0013] The R2 groups are the same or different and are independently selected from: -(CH2) m -(CO) o -O-(CH2) n -;

[0014] The R3 groups are the same or different and are independently selected from: H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C6-C 10 Aryl or -NH-C1-C6 alkyl;

[0015] m is an integer from 0 to 20;

[0016] n is an integer from 1 to 20; and

[0017] o is an integer of 0 or 1,

[0018] The condition is that when m is 0, o is 0.

[0019] 2. The compound of formula (I) according to item 1, wherein

[0020] The R1 group is a C1-C4 alkoxy group, a C6-C9 aryl group or a C6-C9 aryloxy group; and / or

[0021] The R3 group is H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C6-C9 aryl or -NH-C1-C4 alkyl; and / or

[0022] m is an integer from 0 to 8; and / or

[0023] n is an integer from 1 to 8.

[0024] 3. The compound of formula (I) according to item 1, wherein

[0025] The R1 group is a C1-C2 alkoxy group, a C6-C8 aryl group or a C6-C8 aryloxy group; and / or

[0026] The R3 group is H, halogen, C1-C2 alkyl, C1-C2 haloalkyl, C6-C8 aryl or -NH-C1-C2 alkyl; and / or

[0027] m is an integer from 0 to 5; and / or

[0028] n is an integer from 1 to 5.

[0029] 4. The compound of formula (I) according to item 1, wherein

[0030] The R1 group is a C1-C2 alkoxy group or a C6-C8 aryloxy group; and / or

[0031] The R3 group is H, C1-C2 alkyl or C1-C2 haloalkyl; and / or

[0032] m is an integer from 0 to 3; and / or

[0033] n is an integer from 1 to 3.

[0034] 5. The compound of formula (I) according to item 1, which is one or more compounds selected from the following group:

[0035]

[0036] 6. A method for preparing a compound of formula (I) according to any one of items 1 to 5, comprising making a compound of formula (II):

[0037]

[0038] wherein R1, m and o are as defined in any one of items 1 to 5, and X is OH or halogen,

[0039] Reaction with a compound of formula (III):

[0040]

[0041] wherein R3 and n are as defined in any one of items 1 to 5,

[0042] The compound of formula (I) is obtained.

[0043] 7. The method according to item 6, wherein

[0044] The reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a basic catalyst, and the basic catalyst is preferably sodium hydroxide, potassium hydroxide, triethylamine, 4-dimethylaminopyridine (DMAP), potassium carbonate or any mixture thereof, and more preferably, the molar ratio of the compound of formula (II) to the basic catalyst is 5:1-1:1, more preferably 4:1-1.1:1; and / or

[0045] The molar ratio of the compound of formula (II) to the compound of formula (III) is 1:2-1:3, preferably 1:2.1-1:2.5; and / or

[0046] The reaction between the compound of formula (II) and the compound of formula (III) is carried out at -5°C to 10°C, preferably 0-5°C; and / or,

[0047] The reaction between the compound of formula (II) and the compound of formula (III) is carried out for 2 to 36 hours, preferably 10 to 30 hours.

[0048] 8. The method according to item 6 or 7, wherein the reaction is carried out in the presence of an acid binding agent, the acid binding agent being selected from triethylamine, aniline, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or any mixture thereof, wherein the molar ratio of the compound of formula (II) to the acid binding agent is preferably 1:1-1:2, more preferably 1:1.05-1:1.5.

[0049] 9. The method according to any one of items 6 to 8, wherein the reaction is carried out in the presence of an organic solvent selected from ethyl acetate, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, toluene, xylene, preferably dichloromethane and tetrahydrofuran.

[0050] 10. A photocurable composition comprising the compound of formula (I) according to any one of items 1 to 5 as a polymerizable monomer.

[0051] 11. The photocurable composition according to item 10, which comprises a compound of formula (I), another cationically photopolymerizable reactive monomer or reactive resin, a cationically polymerizable reactive diluent monomer, a cationic photoinitiator and a photosensitizer, and the molar ratio thereof is preferably 2-30:70-90:10-30:1-5:1-5, more preferably 5-25:75-85:15-25:1.5-3:1.5-3.

[0052] 12. The photocurable composition according to item 11, wherein the cationically photopolymerizable reactive monomer or reactive resin is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221) or 4-vinylepoxycyclohexane (VOH); the cationically polymerizable reactive diluent monomer is diethylene glycol divinyl ether (DVE-2); the cationic photoinitiator is diphenyliodonium hexafluorophosphate (810); and the photosensitizer is 2-isopropylthioxanthone (ITX).

[0053] 13. The photocurable composition according to any one of items 10 to 12, which is a photocurable coating composition, a photocurable ink composition or a photoresist composition.

[0054] 14. A photocurable material obtained by photocuring the photocurable composition according to any one of items 10 to 13.

[0055] 15. Use of the compound of formula (I) according to any one of items 1 to 5 in a photocurable coating composition, a photocurable ink composition or a photoresist composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 3 is a graph showing the change in conversion rate of alicyclic epoxy groups in a system containing compound EO prepared in Example 1 as a function of irradiation time.

[0057] Figure 2 3 is a graph showing the change in the conversion rate of oxetane groups in the system containing the compound EO prepared in Example 1 as a function of irradiation time.

[0058] Figure 3 3 is a graph showing the change in conversion rate of alicyclic epoxy groups in a system containing compound PO prepared in Example 2 as a function of irradiation time.

[0059] Figure 4 3 is a graph showing the change in the conversion rate of oxetane groups in the system containing the compound PO prepared in Example 2 as a function of irradiation time.

[0060] Figure 5 Graph showing the water contact angle of the photocured film of the system using the compound EO prepared in Example 1.

[0061] Figure 6 The water contact angle of the photocured film of the system using the compound PO prepared in Example 2 is shown in FIG.

[0062] Figure 7 Graph showing tensile properties of a photocured film of a system using the compound EO prepared in Example 1.

[0063] Figure 8 Graph showing tensile properties of a photocured film of a system using compound PO prepared in Example 2.

[0064] Fig. 9 3 is a TGA curve chart of the photocured film of the system using the compound EO prepared in Example 1.

[0065] Fig.10 3 is a DTG curve of a photocured film of a system using the compound EO prepared in Example 1.

[0066] Fig.11 3 is a TGA curve chart of the photocured film of the system using the compound PO prepared in Example 2.

[0067] Fig.12 3 is a DTG curve of a photocured film of a system using compound PO prepared in Example 2.

[0068] Fig.13 : is a DSC curve chart of the photocured film of the system using the compound EO prepared in Example 1.

[0069] Fig.14 3 is a DSC curve chart of the photocured film of the system using the compound PO prepared in Example 2. DETAILED DESCRIPTION

[0070] According to one aspect of the present invention, there is provided a compound of the following formula (I):

[0071]

[0072] in

[0073] The R1 group is selected from: C1-C6 alkoxy, C6-C 10 Aryl or C6-C 10 Aryloxy;

[0074] The R2 groups are the same or different and are independently selected from: -(CH2) m -(CO) o -O-(CH2) n -;

[0075] The R3 groups are the same or different and are independently selected from: H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C6-C 10 Aryl or -NH-C1-C6 alkyl;

[0076] m is an integer from 0 to 20;

[0077] n is an integer from 1 to 20; and

[0078] o is an integer of 0 or 1,

[0079] The condition is that when m is 0, o is 0.

[0080] In the present invention, the compound of formula (I) has good photopolymerization performance, can give the material certain flame retardant properties, and can promote the thermal degradation process of the material and promote the carbonization of the material, and the prepared photocurable material has excellent mechanical properties such as tensile properties and surface hydrophobicity.

[0081] 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.

[0082] "Halogen" refers to fluorine, chlorine, bromine and iodine. In the present invention, preferably, the halogen includes fluorine, chlorine or a combination thereof.

[0083] The term "C n -C m The term "alkyl" refers to a branched or unbranched saturated hydrocarbon radical having n, preferably 1 to 6, particularly preferably 1 to 4 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers thereof, in particular methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2 The C1-C6 alkyl radical may be methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers thereof, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc. The C1-C4 alkyl radical may be methyl, ethyl, propyl, butyl and isomers thereof, in particular methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.

[0084] The term "C6-C m "Aryl" refers to a monocyclic, bicyclic or higher ring aromatic hydrocarbon group containing 6-m carbon atoms, for example 6-10 carbon atoms. m As examples of the aryl group, there may be mentioned phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methylethylphenyl, diethylphenyl, methylpropylphenyl and naphthyl, etc.; preferably phenyl or naphthyl, especially phenyl.

[0085] 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 mAlkyl, preferably C1-C6 alkoxy, more preferably C1-C4 alkoxy. C1-C6 alkoxy can be methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and isomers thereof, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, etc. C1-C4 alkoxy can be methoxy, ethoxy, propoxy, butoxy and isomers thereof, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert-butoxy.

[0086] The term "C n -C m "Haloalkyl" refers to a C n -C m Alkyl, preferably C1-C6 haloalkyl, more preferably C1-C4 haloalkyl. n -C m As examples of haloalkyl, there may be mentioned monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, dichloromethylethyl, monochlorobutyl, dichloromethylpropyl, trichloromethylpropyl, monochloropentyl, dichloromethylbutyl, monochlorohexyl and isomers thereof, in particular 1-chloromethylethyl, 1,1-dichloromethylethyl, 1-chloromethylpropyl, 2-chloromethylpropyl, 1,1-dichloromethylpropyl, 1,2-dichloromethylpropyl, 2,2-dichloromethylpropyl, 1,1,2-trichloromethylpropyl, 1,2,2-trichloromethylpropyl. Methylpropyl, 1-chloromethylbutyl, 2-chloromethylbutyl, 3-chloromethylbutyl, 1-chloroethylpropyl, 1,1-dichloromethylbutyl, 1,2-dichloromethylbutyl, 1,3-dichloromethylbutyl, 2,2-dichloromethylbutyl, 2,3-dichloromethylbutyl, 3,3-dichloromethylbutyl, 1-chloromethylpentyl, 2-chloromethylpentyl, 3-chloromethylpentyl, 4-chloromethylpentyl, 1-chloroethylbutyl, 2-chloroethylbutyl, 1-chloroethyl-1-methylpropyl, 1-ethyl-2-chloromethylpropyl, etc.

[0087] The term "-NH-C1-C6 alkyl" as used herein refers to n -C m Alkyl corresponding to the open chain C n -C m The terminal carbon atom of an alkane has a -NH bonded to it. n -C m Alkyl, preferably -NH-C1-C4 alkyl, for example aminomethyl, aminoethyl, aminopropyl, aminobutyl, aminopentyl, aminohexyl and isomers thereof, in particular aminomethyl, aminoethyl, amino-n-propyl, aminoisopropyl, amino-n-butyl, amino-sec-butyl, amino-tert-butyl, amino-n-pentyl, amino-n-hexyl and the like.

[0088] In a preferred embodiment of the present invention, the R1 group is a C1-C4 alkoxy group, a C6-C9 aryl group or a C6-C9 aryloxy group; and / or the R3 group is H, halogen, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C6-C9 aryl group or a -NH-C1-C4 alkyl group; and / or m is an integer from 0 to 8; and / or n is an integer from 1 to 8.

[0089] In another preferred embodiment of the present invention, the R1 group is a C1-C2 alkoxy group, a C6-C8 aryl group or a C6-C8 aryloxy group; and / or the R3 group is H, halogen, a C1-C2 alkyl group, a C1-C2 haloalkyl group, a C6-C8 aryl group or a -NH-C1-C2 alkyl group; and / or m is an integer from 0 to 5; and / or n is an integer from 1 to 5.

[0090] In another preferred embodiment of the present invention, the R1 group is a C1-C2 alkoxy group or a C6-C8 aryloxy group; and / or the R3 group is H, a C1-C2 alkyl group or a C1-C2 haloalkyl group; and / or m is an integer from 0 to 3; and / or n is an integer from 1 to 3.

[0091] In another preferred embodiment of the present invention, the R1 group is a C1-C2 alkoxy group or a C6-C8 aryloxy group; and / or the R3 group is H or a C1-C2 alkyl group; and / or m is 0, 1 or 2; and / or n is 1 or 2.

[0092] In another preferred embodiment of the present invention, the compound of formula (I) is one or more compounds selected from the group consisting of:

[0093]

[0094] According to a second aspect of the present invention, there is provided a method for preparing a compound of formula (I) of the present invention, comprising making a compound of formula (II):

[0095]

[0096] wherein R1, m and o are as defined for the compound of formula (I), and X is OH or halogen,

[0097] Reaction with a compound of formula (III):

[0098]

[0099] wherein R3 and n are as defined for the compound of formula (I),

[0100] The compound of formula (I) is obtained.

[0101] The reaction of the compound of formula (II) with the compound of formula (III) can be carried out in the presence of a basic catalyst, and the basic catalyst is preferably sodium hydroxide, potassium hydroxide, triethylamine, 4-dimethylaminopyridine, potassium carbonate or any mixture thereof. More preferably, the molar ratio of the compound of formula (II) to the basic catalyst is 5:1-1:1, more preferably 4:1-1.1:1.

[0102] The molar ratio of the compound of formula (II) to the compound of formula (III) can be 1:2-1:3, preferably 1:2.1-1:2.5.

[0103] The reaction between the compound of formula (II) and the compound of formula (III) can be carried out at -5°C to 10°C, preferably 0-5°C.

[0104] The reaction between the compound of formula (II) and the compound of formula (III) can be carried out for 2 to 36 hours, preferably 10 to 30 hours.

[0105] The reaction between the compound of formula (II) and the compound of formula (III) can be carried out in the presence of an acid binding agent, wherein the acid binding agent is selected from triethylamine, aniline, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or any mixture thereof, wherein the molar ratio of the compound of formula (II) to the acid binding agent is preferably 1:1-1:2, more preferably 1:1.05-1:1.5.

[0106] The reaction between the compound of formula (II) and the compound of formula (III) can be carried out in the presence of an organic solvent selected from ethyl acetate, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, toluene, xylene, preferably dichloromethane and tetrahydrofuran.

[0107] In a preferred embodiment for preparing the compound of formula (I), the compound of formula (III) and triethylamine are dissolved in an organic solvent to obtain a mixture 1, the compound of formula (II) is dissolved in an organic solvent to obtain a mixture 2, and the mixture 2 is added to a constant pressure dropping funnel; in an ice-water bath at 0°C, the mixture 2 is slowly added dropwise to the mixture 1, and then the reaction is stirred at room temperature for 24 hours; after the reaction is completed, the reaction solution is first filtered, and then extracted three times with a saturated NaHCO3 aqueous solution, extracted three times with water, dried over anhydrous Na2SO4, and after rotary evaporation, separated and purified by column chromatography.

[0108] The compound of formula (II) and the compound of formula (III) can be synthesized according to conventional methods or can be obtained from commercial sources.

[0109] The compound of formula (I) of the present invention as a cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer has good photopolymerization performance under high-pressure mercury lamps, 365nm and 385nm wavelength LED light sources. The monomer can give the material certain flame retardant properties and can promote the thermal degradation process of the material and promote the carbonization of the material. It can also improve the mechanical properties and surface hydrophobicity of the photocured film.

[0110] Therefore, according to the third aspect of the present invention, a photocurable composition is provided, which comprises the compound of formula (I) of the present invention as a polymerizable monomer. In addition to the compound of formula (I) of the present invention, the photocurable composition may also comprise additional cationic photopolymerizable active monomers or active resins, cationic polymerizable active diluent monomers, cationic photoinitiators and photosensitizers. In a preferred embodiment of the present invention, the photocurable composition comprises the compound of formula (I), additional cationic photopolymerizable active monomers or active resins, cationic polymerizable active diluent monomers, cationic photoinitiators and photosensitizers, and the molar ratio thereof is preferably 2-30:70-90:10-30:1-5:1-5, more preferably 5-25:75-85:15-25:1.5-3:1.5-3.

[0111] The cationic photopolymerizable active monomer or active resin is a monomer or oligomer containing cationic photocurable groups such as vinyl ether double bonds, alicyclic epoxy groups or oxacycloalkyl groups, preferably 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221) or 4-vinyl epoxycyclohexane (VOH).

[0112] The cationic polymerizable active diluent monomer may be an alkenyl ether compound. As specific examples, one or a combination of two or more of triethylene glycol divinyl ether, isobutyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether (BVE), hydroxyethyl vinyl ether, diethylene glycol divinyl ether (DVE-2), triethylene glycol divinyl ether (TEGDVE), vinyl n-octyl ether, divinyl-1,4-butanediol ether, 2-ethylhexyl vinyl ether, 1,4-cyclohexyl dimethanol divinyl ether, 4-hydroxybutyl vinyl ether (HBVE), triethylene glycol divinyl ether (DVE-3), glycerol carbonate vinyl ether, dodecyl vinyl ether, etc. may be mentioned, preferably diethylene glycol divinyl ether.

[0113] As cationic photoinitiators, iodonium salts and sulfonium salts are commonly used. Advantageously, the iodonium salt photoinitiator and sulfonium salt photoinitiator have the following general formulas (A) and (B), respectively:

[0114]

[0115] in

[0116] R a , R b , R c , R d and R e Each independently is an unsubstituted C6-C 10 aryl, or a C6-C6 substituted group selected from halogen, nitro, carbonyl, C1-C6 alkyl, C1-C6 alkoxy, phenylthio, phenyl and substituted phenyl 10 Aryl, preferably phenyl or naphthyl, or phenyl or naphthyl substituted by substituents selected from halogen, nitro, C1-C6 alkyl and substituted phenyl, wherein the substituted phenyl comprises one or more substituents selected from halogen, nitro, C1-C6 alkyl and C1-C6 alkoxy; and

[0117] Y and Z are non-nucleophilic anions such as triflate, toluenesulfonate, C1-C6 carboxylate, BF4 - 、ClO4 - PF6 - 、AsF6 - or SbF6 - .

[0118] For example, as the photoinitiator, one or more selected from the group consisting of 4-(phenylthio)phenyl·diphenylsulfonium hexafluorophosphate, 4-(phenylthio)phenyl·diphenylsulfonium hexafluoroantimonate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexafluoroantimonate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfonium Hexafluoroantimonate, diphenyliodonium hexafluorophosphate (810), 4-octyloxydiphenyliodonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 4-isobutylphenyl·4'-methylphenyliodonium hexafluorophosphate, 4-isobutylphenyl·4'-methylphenyliodonium hexafluoroantimonate, bis(4-dodecylbenzene)iodonium hexafluoroantimonate, bis(4-dodecylbenzene)iodonium hexafluorophosphate, bis(4-tert-butylbenzene)iodonium hexafluorophosphate or bis(4-tert-butylbenzene)iodonium hexafluoroantimonate.

[0119] As photosensitizers, for example, benzophenone and its derivatives such as 4-(4-methylphenylthio)benzophenone or 4,4′-bis(diethylamino)benzophenone, thioxanthone and its derivatives such as 2-isopropylthioxanthone (ITX), anthraquinone and its derivatives such as 2-ethylanthraquinone, coumarin derivatives such as 5,7-dimethoxy-3-(4-dodecylbenzoyl)coumarin, camphorquinone, phenothiazine and its derivatives, 3-(aroylmethylene)thiazoline, rhodanine and its derivatives, eosin, rhodamine, acridine, anthocyanin, merocyanine dyes may be mentioned; preferably benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, coumarin and its derivatives, and particularly preferably 2-isopropylthioxanthone.

[0120] According to a fourth aspect of the present invention, there is provided a photocurable material obtained by photocuring the photocurable composition of the present invention. The photocuring conditions are not particularly limited as long as the photocurable composition of the present invention can be photocured. The prepared photocurable material has excellent mechanical properties such as tensile properties and surface hydrophobicity.

[0121] According to the last aspect of the present invention, there is provided use of the compound of formula (I) of the present invention in a photocurable coating composition, a photocurable ink composition or a photoresist composition.

[0122] In the following description of the present invention, unless otherwise explicitly stated, the numerical values ​​in the present application can be regarded as modified by the word "about". However, the inventor has reported the numerical values ​​in the examples as accurately as possible, although these numerical values ​​inevitably include certain errors.

[0123] In the present application, unless explicitly excluded, the specific or preferred embodiments of the present invention can be combined. In addition, each element of the embodiment of the present application is a specific preferred selection of the corresponding higher-level technical features. If the higher-level technical features can be combined with other higher-level features, the elements of the embodiment, i.e. the specific preferred selection, can also be combined with the other higher-level features. These combinations should be regarded as a part of the original recorded content of the present application.

[0124] Example

[0125] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0126] The materials and reagents used in the following examples are listed in Table 1. Other materials and reagents can be obtained from commercial sources.

[0127] Table 1: Experimental materials and reagents

[0128]

[0129] Example 1 - Preparation of Cationic Photopolymerizable Phosphorus-Containing Bifunctional Oxetane Monomer EO The synthetic route of EO is as follows:

[0130]

[0131] In a 500mL three-necked flask, weigh 11.24g (110mmol) of 3-methyl-3-hydroxymethyloxetane, 11.13g (110mmol) of triethylamine and 350mL of anhydrous tetrahydrofuran in turn; then add 8.15g (50mmol) of ethyl dichlorophosphate and 90mL of anhydrous tetrahydrofuran to a 100mL constant pressure dropping funnel. Then, under the condition of a 0℃ ice water bath, slowly add the ethyl dichlorophosphate in the constant pressure dropping funnel to the three-necked flask, stir and react for 2 hours; then change to a heating reflux device, heat and reflux at 55℃ for 8 hours to end the reaction. The reaction solution was cooled to room temperature and filtered, and then rotary evaporated at 50°C and -0.09MPa to -0.10MPa. It was then purified and separated by column chromatography with silica gel as the stationary phase and PE:EA=4:1 (v / v) as the eluent to obtain 8.28g of product EO (yield: 56.3%).

[0132] The H-NMR spectrum data of EO is: 1 H NMR (400 MHz, CHLOROFORM-d) δ 4.24 (d, J = 6.1 Hz, 4H), 4.09 (d, J = 6.1 Hz, 4H), 3.90 (q, J = 7.2 Hz, 2H), 3.85 (d, J = 5.6 Hz, 4H), 1.10 (t, J = 7.2 Hz, 3H), 1.07 (s, 6H).

[0133] The NMR carbon spectrum data of EO is: 13 C NMR (101 MHz, chloroform-d) δ 78.5, 71.5 (d, J = 6.0 Hz), 63.9 (d, J = 6.0 Hz), 39.6 (d, J = 7.2 Hz), 20.3, 15.9 (d, J = 7.2 Hz).

[0134] The nuclear magnetic phosphorus spectrum data of EO is: 31 P NMR (162 MHz, chloroform-d) δ -1.07.

[0135] The infrared data of EO is: FTIR (KBr, cm -1 )2962,2875,1732,1460,1390,1264,1018,975,884,837,763,540.

[0136] Example 2 - Preparation of Cationic Photopolymerizable Phosphorus-Containing Bifunctional Oxetane Monomer PO The synthetic route of PO is as follows:

[0137]

[0138] In a 500mL three-necked flask, 11.24g (110mmol) of 3-methyl-3-hydroxymethyloxetane, 11.13g (110mmol) of triethylamine and 400mL of anhydrous tetrahydrofuran were added in sequence; 10.55g (50mmol) of phenyl dichlorophosphate and 50mL of anhydrous tetrahydrofuran were placed in a 50mL constant pressure dropping funnel. Under a 0℃ ice-water bath, the solution in the dropping funnel was slowly added dropwise to the reaction system. Then mechanical stirring was used to react at room temperature for 24 hours. After the reaction was completed, the reaction solution was first filtered, and after rotary evaporation at 50℃ and -0.09MPa to -0.10MPa, it was purified and separated by column chromatography, with the stationary phase being: silica gel, and the eluent being: PE:EA=7:1 (v / v), to obtain the product PO 11.23g (yield: 65.6%).

[0139] The H-NMR spectrum data of PO is: 1 H NMR (400MHz, chloroform-d) δ7.20(t,J=7.9Hz,2H),7.10(d,J=7.9Hz,2H),7.04(t,J=7.9Hz,1H),4.345(d,J=6.1Hz,2H),4.341( d, J=6.1Hz, 2H), 4.21 (d, J=6.1Hz, 2H), 4.20 (d, J=6.1Hz, 2H), 4.10 (d, J=5.6Hz, 2H), 4.09 (d, J=5.6Hz, 2H), 1.17 (s, 6H).

[0140] The NMR carbon spectrum data of PO is: 13 C NMR (101 MHz, chloroform-d) δ 150.4 (d, J = 7.1 Hz), 129.7, 125.3, 119.9 (d, J = 4.8 Hz), 78.6 (d, J = 5.2 Hz), 72.5, 39.8 (d, J = 7.9 Hz), 20.4.

[0141] The nuclear magnetic phosphorus spectrum data of PO is: 31 P NMR (162 MHz, chloroform-d) δ -6.30.

[0142] The infrared data of PO is: FTIR (KBr, cm -1 )2958,2874,1591,1489,1384,1282,1210,1018,939,832,766,688,586,532.

[0143] Example 3

[0144] The purpose of this example is to illustrate the photopolymerization performance of the compound of the present invention. The photocurable composition comprises a cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer, commercial monomers E4221 and DVE-2, a commercial cationic photoinitiator 810 and a photosensitizer ITX, and the molar percentage of each component is: cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer (X): E4221: DVE-2: 810: ITX = X: 80: 20: 2: 2. The photocurable compositions used in the examples are prepared according to this ratio.

[0145] The photopolymerization kinetics in the presence of EO and PO were tested by real-time infrared method (real-time infrared spectrometer: Nicolet 5700, Thermo Electron, USA), and the effects of different contents of EO and PO on the photopolymerization performance of E4221 / DVE-2 system were investigated. The vibration absorption peak of the COC of the three-membered oxygen heterocycle of the monomer E4221 used is located at 750 cm -1 The vibration absorption peak of the COC of the four-membered oxygen heterocycle in the compounds EO and PO as polymerization monomers is located at 980 cm -1 Use a 0.5mm glass spot tube to evenly apply a small amount of photocurable liquid composed of monomers and photoinitiators on the potassium bromide salt sheet, and then use a 365nm ultraviolet point light source to irradiate the sample for 15 minutes. The light source is about 5cm away from the test sample, and the irradiation intensity is 50mW cm -2 . By measuring at 750cm -1 and 980cm -1 The change in the COC bond peak area at the bottom characterizes the real-time conversion rate of different epoxy groups, that is, the monomer.

[0146] The results for the photocurable compositions comprising compounds EO and PO are as follows: Figure 1-4 As shown in Table 2-3 (in the figure and the following table, EO-5% is taken as an example, which means that X in the formula is 5 mol%). The results show that the addition of compounds EO and PO can significantly improve the conversion rate of the monomers in the E4221 / DVE-2 system. In addition, only a small amount of 10 mol% of compounds EO and PO can significantly improve the conversion rate of alicyclic epoxy, and the maximum conversion rate reaches more than 78%. And when 15 mol% of compounds EO and PO are added, the conversion rates of the two themselves are both above 60%. Therefore, the compounds of the present invention can improve the photopolymerization performance of the monomers in the E4221 / DVE-2 system and the compounds of the present invention themselves have good photopolymerization activity.

[0147] Table 2: Monomer conversion at 800 s for photocurable compositions using compound EO

[0148]

[0149] Table 3: Monomer conversion at 800 s for photocurable compositions using compound PO

[0150]

[0151] Example 4

[0152] The purpose of this embodiment is to illustrate that the compounds of the present invention can improve the surface hydrophobicity of the photocurable film. The photocurable composition comprises a cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer, commercial monomers E4221 and DVE-2, a commercial cationic photoinitiator 810, and a photosensitizer ITX, and the molar percentage of each component is: cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer (X): E4221: DVE-2: 810: ITX = X: 80: 20: 2: 2. The photocurable compositions used in the embodiments are prepared according to this ratio. The prepared photocurable composition photosensitive liquid is added to a 30mm×10mm×2mm polytetrafluoroethylene mold, and then placed in an ultraviolet UV light curing machine (model: RX1K300, mercury lamp, main wavelength 365nm, light intensity: 70mW cm -2 ) for 15 to 20 minutes, and then the photocured film was taken out. In order to accelerate the post-curing process of the photocured film, the photocured film was placed in a constant temperature oven at 60° C. for 3 to 4 hours, and then the subsequent performance test was carried out.

[0153] At 20°C, the water contact angle of the UV-cured film was tested using a DSA 25 water contact angle tester. Each sample was measured three times and the average value was taken. The E4221 / DVE-2 system (EO-0% or PO-0%) was used as the blank control group. The test results are shown in Figure 5-6 and Table 4-5.

[0154] from Figure 5-6 As can be seen from Tables 4-5, the water contact angle of the photocured film of the blank E4221 / DVE-2 system without adding the compounds EO and PO is 64.2°, while after adding any one of the compounds EO and PO, the water contact angle of the photocured film is significantly increased, reaching a maximum of 83.8° when EO is added and 83.5° when PO is added. Therefore, the compounds of the present invention can significantly improve the surface hydrophobicity of the photocured film.

[0155] Table 4: Water contact angles of photocured films obtained from photocurable compositions using compound EO

[0156] Photocurable composition EO content X (mol%) Water contact angle (°) E4221 / DVE-2 0 64.2 EO-5% 5 73.0 EO-10% 10 82.3 EO-15% 15 83.7 EO-20% 20 83.8

[0157] Table 5: Water contact angles of photocured films obtained using the photocurable composition of compound PO

[0158] Photocurable composition PO content X (mol%) Water contact angle (°) E4221 / DVE-2 0 64.2 PO-5% 5 76.4 PO-10% 10 80.4 PO-15% 15 81.5 PO-20% 20 83.5

[0159] Example 5

[0160] The purpose of this example is to illustrate that the compounds of the present invention can improve the tensile properties of photocured films.

[0161] Photocured films in the presence of EO and PO were prepared in exactly the same manner as in Example 4. The tensile properties of the photocured films were tested on an electronic universal testing machine (MetS Industries (China) Co., Ltd., E44.304) at a test speed of 2 mm min -1 . Record the corresponding elongation at break and tensile strength in the test software, repeat the test 3 times for each sample and calculate the average value. The test process complies with the requirements of the national standard GB / T 1040.2-2006. The E4221 / DVE-2 system (EO-0% or PO-0%) is the blank control group. The test results are shown in Figure 7-8 and Tables 6-7.

[0162] Depend on Figure 7 As shown in Table 6, after adding compound EO, the tensile strength of the system increases first, then decreases, and then stabilizes, but is higher than the 5.33MPa of the blank E4221 / DVE-2 system. When 5mol% EO is added, the tensile strength of the system is the highest, which is 7.73MPa, and the elongation at break of the system decreases first and then increases. Figure 8 As can be seen from Table 7, after the addition of compound PO, the tensile strength of the system also shows a trend of first increasing and then decreasing, but it is higher than the 5.33MPa of the blank E4221 / DVE-2 system. When 15mol% PO is added, the tensile strength of the system is the highest, which is 9.11MPa, and the elongation at break first decreases from 10.28% of PO-0% to 6.71% of PO-5%, and then increases to 11.33% of PO-20%.

[0163] Table 6: Tensile properties of photocured films obtained from photocurable compositions using compound EO

[0164]

[0165] Table 7: Tensile properties of photocured films obtained from photocurable compositions using compound PO

[0166]

[0167] Example 6

[0168] The photocured films of EO and PO were prepared in the presence of the compounds according to the same method as described in Example 4. The photocured films were then subjected to thermogravimetric analysis using a DTG-60AH (China) differential thermal-thermogravimetric analyzer. 8 to 10 mg of the sample was placed in an alumina crucible and heated at a flow rate of 50 mL min -1 In a nitrogen atmosphere, the temperature was heated from 30°C to 800°C at a rate of 10°C min -1 , the holding time is 10min. E4221 / DVE-2 system (EO-0% or PO-0%) is the blank control group. The test results are shown in Figure 9-12 and Tables 8-9.

[0169] Depend on Figure 9-12 As shown in Tables 8-9, the initial decomposition temperature (T 5％ ) and maximum thermal weight loss temperature (T max ) were significantly reduced, but the residual carbon content at 700℃ increased. The synthesized monomers were helpful for the thermal degradation of the photocurable film and promoted the carbonization of the system.

[0170] Table 8: Thermogravimetric data of photocured films obtained from photocurable compositions using compound EO

[0171]

[0172] Table 9: Thermogravimetric data of photocured films obtained from photocurable compositions using compound PO

[0173]

[0174] Example 7

[0175] Photocured films in the presence of EO and PO were prepared in exactly the same manner as described in Example 4. Then, the glass transition temperature (T g ) was measured, the temperature was increased from 30℃ to 400℃, and the heating rate was set to 10℃min -1 , nitrogen flow rate: 50mL min -1 The E4221 / DVE-2 system (EO-0% or PO-0%) was used as the blank control group. Figure 13-14 and Tables 10-11.

[0176] Depend on Figure 13-14 As shown in Tables 10-11, the glass transition temperature (T g ) were significantly reduced, which shows that the synthesized monomer has a certain plasticizing effect.

[0177] Table 10: Glass transition temperature of photocured films obtained from photocurable compositions using compound EO

[0178]

[0179]

[0180] Table 11: Glass transition temperature of photocured films obtained using the photocurable composition of compound PO

[0181] Photocurable composition PO content X (mol%) <![CDATA[T g (℃)]]> E4221 / DVE-2 0 211.7 PO-5% 5 200.3 PO-10% 10 193.8 PO-15% 15 186.2 PO-20% 20 176.0

[0182] Example 8

[0183] The purpose of this example is to illustrate that the compound of the present invention can improve the flame retardant properties of the photocured film to a certain extent.

[0184] According to the same method as described in Example 4, photocured films in the presence of compounds EO and PO were prepared respectively. Then, according to the relevant content of ASTM D2863, the limiting oxygen index of the photocured film was tested using a 5801 digital oxygen index instrument. The size of the photocured film was 100mm×6.5mm×3mm. Then, according to the relevant requirements of the national standard GB / T 2408-1996, a horizontal combustion test was carried out on the photocured film to study its flame retardant properties. The size of the photocured film used was 125mm×13mm×3mm. E4221 / DVE-2 system (EO-0% or PO-0%) was a blank control group. The test results are shown in Tables 12-13.

[0185] It can be seen from Tables 12-13 that the limiting oxygen index and horizontal combustion test level of the photocured film increased after adding compounds EO and PO, which shows that the synthesized monomer has a certain flame retardant effect.

[0186] Table 12: Flame retardant properties of photocured films obtained from photocurable compositions using compound EO

[0187]

[0188]

[0189] Table 13: Flame retardant properties of photocured films obtained from photocurable compositions using compound PO

[0190]

Claims

1. Compounds of the following formula (I): in The R1 group is selected from: C1-C6 alkoxy, C6-C 10 Aryl or C6-C 10 Aryloxy; The R2 groups are the same or different and are independently selected from: -(CH2) m -(CO) o -O-(CH2) n -; The R3 groups are the same or different and are independently selected from: H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C6-C 10 Aryl or -NH-C1-C6 alkyl; m is an integer from 0 to 20; n is an integer from 1 to 20; and o is an integer of 0 or 1, The condition is that when m is 0, o is 0.

2. The compound of formula (I) according to claim 1, wherein The R1 group is a C1-C4 alkoxy group, a C6-C9 aryl group or a C6-C9 aryloxy group; and / or The R3 group is H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C6-C9 aryl or -NH-C1-C4 alkyl; and / or m is an integer from 0 to 8; and / or n is an integer from 1 to 8.

3. The compound of formula (I) according to claim 1, wherein The R1 group is a C1-C2 alkoxy group, a C6-C8 aryl group or a C6-C8 aryloxy group; and / or The R3 group is H, halogen, C1-C2 alkyl, C1-C2 haloalkyl, C6-C8 aryl or -NH-C1-C2 alkyl; and / or m is an integer from 0 to 5; and / or n is an integer from 1 to 5.

4. The compound of formula (I) according to claim 1, wherein The R1 group is a C1-C2 alkoxy group or a C6-C8 aryloxy group; and / or The R3 group is H, C1-C2 alkyl or C1-C2 haloalkyl; and / or m is an integer from 0 to 3; and / or n is an integer from 1 to 3.

5. The compound of formula (I) according to claim 1, which is one or more compounds selected from the group consisting of:

6. A method for preparing a compound of formula (I) according to any one of claims 1 to 5, comprising making a compound of formula (II): wherein R1, m and o are as defined in any one of claims 1 to 5, and X is OH or halogen, Reaction with a compound of formula (III): wherein R3 and n are as defined in any one of claims 1 to 5, The compound of formula (I) is obtained.

7. The method according to claim 6, wherein The reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a basic catalyst, and the basic catalyst is preferably sodium hydroxide, potassium hydroxide, triethylamine, 4-dimethylaminopyridine (DMAP), potassium carbonate or any mixture thereof, and more preferably, the molar ratio of the compound of formula (II) to the basic catalyst is 5:1-1:1, more preferably 4:1-1.1:1; and / or The molar ratio of the compound of formula (II) to the compound of formula (III) is 1:2-1:3, preferably 1:2.1-1:2.5; and / or The reaction between the compound of formula (II) and the compound of formula (III) is carried out at -5°C to 10°C, preferably 0-5°C; and / or, The reaction between the compound of formula (II) and the compound of formula (III) is carried out for 2 to 36 hours, preferably 10 to 30 hours.

8. The method according to claim 6 or 7, wherein the reaction is carried out in the presence of an acid binding agent, the acid binding agent being selected from triethylamine, aniline, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or any mixture thereof, wherein the preferred molar ratio of the compound of formula (II) to the acid binding agent is 1:1-1:2, more preferably 1:1.05-1:1.

5.

9. The method according to any one of claims 6 to 8, wherein the reaction is carried out in the presence of an organic solvent selected from ethyl acetate, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, toluene, xylene, preferably dichloromethane and tetrahydrofuran.

10. A photocurable composition comprising the compound of formula (I) according to any one of claims 1 to 5 as a polymerizable monomer.

11. The photocurable composition according to claim 10, comprising a compound of formula (I), another cationically photopolymerizable reactive monomer or reactive resin, a cationically polymerizable reactive diluent monomer, a cationic photoinitiator and a photosensitizer, preferably in a molar ratio of 2-30:70-90:10-30:1-5:1-5, more preferably 5-25:75-85:15-25:1.5-3:1.5-3.

12. The photocurable composition according to claim 11, wherein the cationically photopolymerizable active monomer or active resin is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221) or 4-vinyl epoxycyclohexane (VOH); the cationically polymerizable active diluent monomer is diethylene glycol divinyl ether (DVE-2); the cationic photoinitiator is diphenyliodonium hexafluorophosphate (810); and the photosensitizer is 2-isopropylthioxanthone (ITX).

13. The photocurable composition according to any one of claims 10 to 12, which is a photocurable coating composition, a photocurable ink composition or a photoresist composition.

14. A photocurable material obtained by photocuring the photocurable composition according to any one of claims 10 to 13.

15. Use of the compound of formula (I) according to any one of claims 1 to 5 in a photocurable coating composition, a photocurable ink composition or a photoresist composition.

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