Cationically photopolymerizable phosphorus-containing bifunctional oxetane monomer, preparation method therefor, and use thereof

Abstract

The present invention relates to a compound as shown in formula (I), wherein each variable R1, R2 and R3 is as defined in the description. The present invention further relates to the preparation of the compound as shown in formula (I), a photocurable composition comprising the compound as shown in formula (I), a photocured material obtained by photocuring the photocurable composition, and the use of the compound as shown in formula (I) in the field of photocured materials. The compound as shown in formula (I) has good photopolymerization performance, can impart certain flame retardant performance to the material, can promote the thermal degradation process of the material, and promote the char formation of the material. The photocured material has excellent mechanical properties and surface hydrophobicity.

Description

Cationic photopolymerizable phosphorus-containing bifunctional oxetane monomers, their preparation methods and applications Technical Field

[0001] This invention relates to the field of cationic photocurable materials, specifically to a class of cationic photopolymerizable phosphorus-containing bifunctional oxetane monomers. This invention also relates to methods for preparing such monomers, photocurable compositions containing such monomers, photocurable materials obtained from such photocurable compositions, and the application of such monomers in the field of photocurable materials. Background Technology

[0002] In recent years, with increasing attention to energy conservation and environmental protection, photopolymerization technology has gained popularity in a growing number of fields. Cationic photopolymerization systems offer rapid polymerization speeds, are not inhibited by oxygen, and exhibit good dimensional stability and strong adhesion. Among existing cationic photopolymerizable monomers, oxetane-based cationic photopolymerizable monomers are favored due to their low viscosity, low toxicity, and low volatility. However, the types of oxetane-based cationic photopolymerizable monomers reported so far are relatively few. Furthermore, the polymer materials formed after epoxy monomer curing are generally flammable; therefore, the industry hopes to develop functional monomers with flame-retardant properties. Based on this, developing a series of oxetane monomers that can be cationically photopolymerized and impart certain flame-retardant properties to materials has significant theoretical and practical value. Summary of the Invention

[0003] The purpose of this invention is to provide a class of cationic photopolymerizable phosphorus-containing bifunctional oxetane monomers. Through research, the inventors have discovered that the cationic photopolymerizable phosphorus-containing bifunctional oxetane monomers provided by this invention possess excellent photopolymerization properties, can impart certain flame-retardant properties to the material, and can promote the thermal degradation process and char formation of the material. The prepared photocurable material exhibits 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 oxobutane monomer of the present invention. This preparation method is simple and easy to implement, uses mild conditions, and the reactants are inexpensive and readily available, resulting in low cost.

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

[0006] 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 application of the cationic photopolymerizable phosphorus-containing bifunctional oxoheterocyclic butane monomer of the present invention in photocurable coating compositions, photocurable ink compositions or photoresist compositions.

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

[0009] 1. The following compound (Ⅰ):

[0010] in

[0011] The R1 group is selected from: C1-C6 alkoxy, C6-C 10 Aryl or C6-C 10 aryloxy group;

[0012] The R2 groups may be the same or different and are independently selected from: -(CH2) m -(CO) o -O-(CH2) n -;

[0013] The R3 groups may be 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;

[0014] m is an integer between 0 and 20;

[0015] n is an integer from 1 to 20; and

[0016] o is an integer that is either 0 or 1.

[0017] The condition is that when m is 0, o is 0.

[0018] 2. The compound of formula (Ⅰ) according to item 1, wherein

[0019] R1 group is a C1-C4 alkoxy, C6-C9 aryl, or C6-C9 aryloxy group; and / or

[0020] The R3 group is H, a 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

[0021] m is an integer from 0 to 8; and / or

[0022] n is an integer from 1 to 8.

[0023] 3. The compound of formula (Ⅰ) according to item 1, wherein

[0024] R1 group is a C1-C2 alkoxy, C6-C8 aryl, or C6-C8 aryloxy group; and / or

[0025] The R3 group is H, a 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

[0026] m is an integer between 0 and 5; and / or

[0027] n is an integer between 1 and 5.

[0028] 4. The compound of formula (Ⅰ) according to item 1, wherein

[0029] R1 group is a C1-C2 alkoxy or a C6-C8 aryloxy group; and / or

[0030] R3 is an H, a C1-C2 alkyl group, or a C1-C2 haloalkyl group; and / or

[0031] m is an integer between 0 and 3; and / or

[0032] n is an integer between 1 and 3.

[0033] 5. The compound of formula (I) according to item 1, wherein it is one or more compounds selected from the group consisting of:

[0034] 6. A method for preparing a compound of formula (I) according to any one of claims 1-5, comprising causing a compound of formula (II):

[0035] Where R1, m, and o are defined as in any of items 1-5, and X is OH or a halogen.

[0036] Reaction with compound of formula (III):

[0037] R3 and n are defined as in any of the terms 1-5.

[0038] Compound of formula (I) was obtained.

[0039] 7. The method according to item 6, wherein

[0040] The reaction between compound (II) and compound (III) is carried out in the presence of a basic catalyst, preferably sodium hydroxide, potassium hydroxide, triethylamine, 4-dimethylaminopyridine (DMAP), potassium carbonate, or any mixture thereof; more preferably, the molar ratio of compound (II) to the basic catalyst is 5:1 to 1:1, more preferably 4:1 to 1.1:1; and / or

[0041] The molar ratio of compound (II) to compound (III) is 1:2-1:3, preferably 1:2.1-1:2.5; and / or

[0042] 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,

[0043] The reaction between the compound of formula (II) and the compound of formula (III) is carried out for 2-36 hours, preferably 10-30 hours.

[0044] 8. The method according to claim 6 or 7, wherein the reaction is carried out in the presence of an acid-binding agent 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 to 1:2, more preferably 1:1.05 to 1:1.5.

[0045] 9. The method according to any one of claims 6-8, 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.

[0046] 10. A photocurable composition comprising a compound of formula (I) according to any one of claims 1-5 as a polymerizable monomer.

[0047] 11. The photocurable composition according to claim 10, comprising a compound of formula (I), an additional cationicly photopolymerizable active monomer or active resin, a cationicly polymerizable active diluent monomer, a cationic photoinitiator and a photosensitizer, wherein the molar ratio 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.

[0048] 12. The photocurable composition according to claim 11, wherein the cationic photopolymerizable active monomer or active resin is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate (E4221) or 4-vinylepoxycyclohexane (VOH); the cationic photopolymerizable active diluent monomer is diethylene glycol divinyl ether (DVE-2); the cationic photoinitiator is diphenyliodonium hexafluorophosphate (810); and the photosensitizer is 2-isopropylthioxanthraquinone (ITX).

[0049] 13. The photocurable composition according to any one of claims 10-12, wherein the composition is a photocurable coating composition, a photocurable ink composition, or a photoresist composition.

[0050] 14. A photocurable material obtained by photocuring a photocurable composition according to any one of claims 10-13.

[0051] 15. Use of the compound of formula (I) according to any one of items 1-5 in a photocurable coating composition, a photocurable ink composition or a photoresist composition. Attached Figure Description

[0052] Figure 1 is a graph showing the change in the conversion rate of alicyclic epoxy groups with irradiation time in a system containing the compound EO prepared in Example 1.

[0053] Figure 2 is a graph showing the change in the conversion rate of oxobutyran groups with irradiation time in a system containing the compound EO prepared in Example 1.

[0054] Figure 3 is a graph showing the change in the conversion rate of alicyclic epoxy groups with irradiation time in a system containing compound PO prepared in Example 2.

[0055] Figure 4 is a graph showing the change in the conversion rate of the oxobutyryl group with irradiation time in the system containing compound PO prepared in Example 2.

[0056] Figure 5 is a diagram of the water contact angle of the photocurable film using the compound EO system prepared in Example 1.

[0057] Figure 6 shows the water contact angle of the photocurable film using the compound PO system prepared in Example 2.

[0058] Figure 7 is a graph showing the tensile properties of the photocurable film using the compound EO prepared in Example 1.

[0059] Figure 8 is a tensile property diagram of the photocurable film using the compound PO prepared in Example 2.

[0060] Figure 9 is a TGA curve of the photocurable film of the system using the compound EO prepared in Example 1.

[0061] Figure 10 is a DTG curve of the photocurable film of the system using the compound EO prepared in Example 1.

[0062] Figure 11 is a TGA curve of the photocurable film of the system using compound PO prepared in Example 2.

[0063] Figure 12 is a DTG curve of the photocurable film of the system using compound PO prepared in Example 2.

[0064] Figure 13 is a DSC curve of the photocurable film of the system using the compound EO prepared in Example 1.

[0065] Figure 14 is a DSC curve of the photocurable film of the system using compound PO prepared in Example 2. Detailed Implementation

[0066] According to one aspect of the present invention, a compound of formula (Ⅰ) is provided:

[0067] in

[0068] The R1 group is selected from: C1-C6 alkoxy, C6-C 10 Aryl or C6-C 10 aryloxy group;

[0069] The R2 groups may be the same or different and are independently selected from: -(CH2) m -(CO) o -O-(CH2) n -;

[0070] The R3 groups may be 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;

[0071] m is an integer between 0 and 20;

[0072] n is an integer from 1 to 20; and

[0073] o is an integer that is either 0 or 1.

[0074] The condition is that when m is 0, o is 0.

[0075] In this invention, the compound of formula (I) has good photopolymerization properties, can impart certain flame retardant properties to the material, can promote the thermal degradation process of the material and promote the char formation of the material, and the prepared photocurable material has excellent mechanical properties such as tensile properties and surface hydrophobicity.

[0076] In this invention, the prefix "C" n -C m "In each case, it indicates that the group contains nm of carbon atoms."

[0077] "Halogen" refers to fluorine, chlorine, bromine, and iodine. In this invention, it is preferred that the halogen includes fluorine, chlorine, or a combination thereof.

[0078] The term "C" used in this article n -C m"Alkyl" refers to a branched or unbranched saturated hydrocarbon group having 1-6, particularly 1-4 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl and their isomers, especially 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 -Dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, etc. C1-C6 alkyl groups can be methyl, ethyl, propyl, butyl, pentyl, hexyl, and their isomers, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc. C1-C4 alkyl groups can be methyl, ethyl, propyl, butyl, and their isomers, especially methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, or 1,1-dimethylethyl.

[0079] The term "C6-C" is used in this article. m "Aryl" refers to a monocyclic, bicyclic, or more cyclic aromatic hydrocarbon group containing 6-m carbon atoms, such as 6-10 carbon atoms. As a C6-C... m Examples of aryl groups include phenyl, tolyl, ethylphenyl, propanylphenyl, butylphenyl, xylyl, methyl-ethylphenyl, diethylphenyl, methyl-propylphenyl, and naphthyl; phenyl or naphthyl is preferred, especially phenyl.

[0080] 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 mAlkyl groups, preferably C1-C6 alkoxy groups, more preferably C1-C4 alkoxy groups. 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, n-hexoxy, etc. C1-C4 alkoxy groups can be methoxy, ethoxy, propoxy, butoxy, and their isomers, particularly methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, or tert-butoxy.

[0081] The term "C" used in this article n -C m "Halogenated alkyl" refers to a C-aryl group that has been substituted with one or more identical or different halogen atoms. n -C m Alkyl group, preferably C1-C6 haloalkyl group, more preferably C1-C4 haloalkyl group. As a C n -C m Examples of haloalkyl groups may include monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, dichloromethylethyl, monochlorobutyl, dichloromethylpropyl, trichloromethylpropyl, monochloropentyl, dichloromethylbutyl, monochlorohexyl and their isomers, particularly 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-trichloroethylethyl, and 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.

[0082] The term "-NH-C1-C6 alkyl" as used in this article refers to alkyl groups with a C1-C6 alkyl content. n -C m alkyl corresponding to open chain C n -C m A -NH atom is bonded to the terminal carbon atom of the alkane. n -C m Alkyl groups, preferably -NH-C1-C4 alkyl groups, such as aminomethyl, aminoethyl, aminopropyl, aminobutyl, aminopentyl, aminohexyl and their isomers, especially aminomethyl, aminoethyl, aminon-propyl, aminoisopropyl, aminon-butyl, aminosec-butyl, aminotert-butyl, aminon-pentyl, aminon-hexyl, etc.

[0083] In a preferred embodiment of the present invention, the R1 group is a C1-C4 alkoxy, C6-C9 aryl, or C6-C9 aryloxy; 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.

[0084] In another preferred embodiment of the invention, the R1 group is a C1-C2 alkoxy, C6-C8 aryl, or C6-C8 aryloxy; 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.

[0085] In another preferred embodiment of the present invention, the R1 group is a C1-C2 alkoxy or a C6-C8 aryloxy; and / or the R3 group is H, a C1-C2 alkyl or a C1-C2 haloalkyl; and / or m is an integer from 0 to 3; and / or n is an integer from 1 to 3.

[0086] In another preferred embodiment of the present invention, the R1 group is a C1-C2 alkoxy or a C6-C8 aryloxy; and / or the R3 group is H or a C1-C2 alkyl; and / or m is 0, 1 or 2; and / or n is 1 or 2.

[0087] In another preferred embodiment of the invention, the compound of formula (I) is one or more compounds selected from the group consisting of:

[0088] According to a second aspect of the present invention, a method for preparing the compound of formula (I) of the present invention is provided, comprising making the compound of formula (II):

[0089] Where R1, m, and o are as defined for compounds of formula (Ⅰ), and X is OH or a halogen.

[0090] Reaction with compound of formula (III):

[0091] Where R3 and n are as defined for the compound of formula (Ⅰ),

[0092] Compound of formula (I) was obtained.

[0093] The reaction between compound (II) and compound (III) can be carried out in the presence of a basic catalyst, preferably sodium hydroxide, potassium hydroxide, triethylamine, 4-dimethylaminopyridine, potassium carbonate or any mixture thereof, more preferably, the molar ratio of compound (II) to basic catalyst is 5:1 to 1:1, more preferably 4:1 to 1.1:1.

[0094] The molar ratio of compound (II) to compound (III) can be 1:2-1:3, preferably 1:2.1-1:2.5.

[0095] 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 at 0-5°C.

[0096] The reaction between the compound of formula (II) and the compound of formula (III) can proceed for 2-36 hours, preferably 10-30 hours.

[0097] 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 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 to 1:2, more preferably 1:1.05 to 1:1.5.

[0098] 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.

[0099] In a preferred embodiment for preparing compound (I), compound (III) and triethylamine are dissolved in an organic solvent to obtain mixture 1, and compound (II) is dissolved in an organic solvent to obtain mixture 2. Mixture 2 is added to a constant pressure dropping funnel. Mixture 2 is slowly added dropwise to mixture 1 under 0°C ice-water bath conditions, and then the mixture is stirred at room temperature for 24 hours. After the reaction is completed, the reaction solution is first filtered, then extracted three times with saturated NaHCO3 aqueous solution, then extracted three times with water, dried with anhydrous Na2SO4, and then purified by column chromatography after rotary evaporation.

[0100] Compounds of formula (II) and (III) can be synthesized by conventional methods or are available commercially.

[0101] The compound of formula (I) of this invention, as a cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer, exhibits good photopolymerization performance under high-pressure mercury lamps and LED light sources at wavelengths of 365 nm and 385 nm. This monomer can impart certain flame-retardant properties to the material and promote its thermal degradation and char formation. It can also improve the mechanical properties and surface hydrophobicity of the photocurable film.

[0102] Therefore, according to a third aspect of the invention, a photocurable composition is provided, comprising the compound of formula (I) of the invention as a polymerizable monomer. In addition to comprising the compound of formula (I) of the invention, the photocurable composition may also comprise additional cationic photopolymerizable reactive monomers or reactive resins, cationic photopolymerizable reactive diluent monomers, cationic photoinitiators, and photosensitizers. In a preferred embodiment of the invention, the photocurable composition comprises the compound of formula (I), additional cationic photopolymerizable reactive monomers or reactive resins, cationic photopolymerizable reactive diluent monomers, cationic photoinitiators, and photosensitizers, wherein the molar ratio 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.

[0103] 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 oxocyclic alkyl groups, preferably 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl carboxylate (E4221) or 4-vinylepoxycyclohexane (VOH).

[0104] The cationic polymerizable reactive diluent monomer can be an alkenyl ether compound. Specific examples include one or more of the following: 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-cyclohexyldiethanol divinyl ether, 4-hydroxybutyl vinyl ether (HBVE), triethylene glycol divinyl ether (DVE-3), glycerol carbonate vinyl ether, and dodecyl vinyl ether, preferably diethylene glycol divinyl ether.

[0105] Iodonium salts and thionium salts are commonly used as cationic photoinitiators. Advantageously, the iodonium salt photoinitiator and the thionium salt photoinitiator respectively have the following general formulas (A) and (B):

[0106] in

[0107] R a R b R c R d and R e Each is an unreplaced C6-C. 10 aryl, or C6-C6 substituted with a substituent selected from halogen, nitro, carbonyl, C1-C6 alkyl, C1-C6 alkoxy, phenylthio, phenyl, and substituted phenyl groups. 10 The aryl group, preferably phenyl or naphthyl, or a phenyl or naphthyl group substituted with a substituent selected from halogens, nitro groups, C1-C6 alkyl groups, and substituted phenyl groups, wherein the substituted phenyl group comprises one or more substituents selected from halogens, nitro groups, C1-C6 alkyl groups, and C1-C6 alkoxy groups; and

[0108] Y and Z are non-nucleophilic anions, such as trifluoromethanesulfonate, toluenesulfonate, C1-C6 carboxylate, and BF4. - ClO4 - PF6 - AsF6 - Or SbF6 - .

[0109] For example, one or more selected from the group consisting of 4-(phenylthio)phenyl diphenylthionium hexafluorophosphate, 4-(phenylthio)phenyl diphenylthionium hexafluoroantimonate, bis(4-(diphenylsulfonium)phenyl)sulfide bis(hexafluorophosphate), bis(4-(diphenylsulfonium)phenyl)sulfide bis(hexafluoroantimonate), 10-(4-biphenyl)-2-isopropylthioxanthionone-10-thionium hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthionone-10-thionium Hexafluoroantimonate, diphenyliodonium hexafluorophosphate (810), 4-octoxydiphenyliodonium hexafluorophosphate, 4-octoxydiphenyliodonium 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.

[0110] As photosensitizers, examples include benzophenone and its derivatives such as 4-(4-methylphenylthio)benzophenone or 4,4'-di(diethylamino)benzophenone, thioxanthrone and its derivatives such as 2-isopropylthioxanthrone (ITX), anthraquinone and its derivatives such as 2-ethylanthrone, coumarin derivatives such as 5,7-dimethoxy-3-(4-dodecylbenzoyl)coumarin, camphorquinone, phenothiazine and its derivatives, 3-(aromaticylmethylene)thiazoline, razotanine and its derivatives, eosin, rhodamine, acridine, anthocyanins, and cyanine dyes; preferably benzophenone and its derivatives, thioxanthrone and its derivatives, anthraquinone and its derivatives, and coumarin and its derivatives, especially 2-isopropylthioxanthrone.

[0111] According to a fourth aspect of the present invention, a photocurable material is provided, which is obtained by photocuring the photocurable composition of the present invention. The photocuring conditions are not particularly limited, as long as they enable the photocurable composition of the present invention to undergo photocuring. The prepared photocurable material exhibits excellent mechanical properties such as tensile properties and surface hydrophobicity.

[0112] According to a final aspect of the invention, the use of the compound of formula (I) of the invention in a photocurable coating composition, a photocurable ink composition or a photoresist composition is provided.

[0113] In the following description of the invention, unless otherwise expressly stated, all numerical values ​​in this application are to be regarded as being modified by the word "approximately". However, the inventors have reported the numerical values ​​in the embodiments as accurately as possible, although these numerical values ​​inevitably include a certain degree of error.

[0114] In this application, unless explicitly excluded, specific or preferred embodiments of the invention can be combined. Furthermore, each element of the embodiments of this application is a specific preferred choice of its corresponding higher-level technical feature. If a higher-level technical feature can be combined with other higher-level features, then the elements of the embodiments, i.e., the specific preferred choices, can also be combined with those other higher-level features. These combinations should be considered part of the original description of this application.

[0115] Example

[0116] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0117] The materials and reagents used in the following examples are listed in Table 1. Other materials and reagents are commercially available.

[0118] Table 1: Experimental Materials and Reagents

[0119] Example 1 - Preparation of cationic photopolymerizable phosphorus-containing bifunctional oxobutane monomer EO

[0120] The synthetic route for EO is as follows:

[0121] In a 500 mL three-necked flask, 11.24 g (110 mmol) of 3-methyl-3-hydroxymethyloxetane, 11.13 g (110 mmol) of triethylamine, and 350 mL of anhydrous tetrahydrofuran were weighed out sequentially. Then, 8.15 g (50 mmol) of ethyl dichlorophosphate and 90 mL of anhydrous tetrahydrofuran were added to a 100 mL constant-pressure dropping funnel. The ethyl dichlorophosphate in the constant-pressure dropping funnel was then slowly added dropwise to the three-necked flask under 0 °C ice-water bath conditions, and the reaction was stirred for 2 hours. Subsequently, the reaction was refluxed at 55 °C for 8 hours to complete the reaction. After cooling the reaction solution to room temperature, it was filtered and then purified and separated by column chromatography at 50℃ and -0.09MPa to -0.10MPa. The stationary phase was silica gel and the eluent was PE:EA = 4:1 (v / v). 8.28g of product EO was obtained (yield: 56.3%).

[0122] The 1H NMR data of EO are as follows: 1 ¹H NMR (400MHz, chloroform-d) δ 4.24 (d, J = 6.1Hz, 4H), 4.09 (d, J = 6.1Hz, 4H), 3.90 (q, J = 7.2Hz, 2H), 3.85 (d, J = 5.6Hz, 4H), 1.10 (t, J = 7.2Hz, 3H), 1.07 (s, 6H).

[0123] The carbon NMR data of EO are as follows: 13 C NMR (101MHz, chloroform-d) δ 78.5, 71.5 (d, J = 6.0Hz), 63.9 (d, J = 6.0Hz), 39.6 (d, J = 7.2Hz), 20.3, 15.9 (d, J = 7.2Hz).

[0124] The NMR phosphorus spectrum data of EO are as follows: 31 P NMR (162MHz, chloroform-d) δ-1.07.

[0125] The infrared data for EO are: FTIR (KBr, cm -1 )2962,2875,1732,1460,1390,1264,1018,975,884,837,763,540.

[0126] Example 2 - Preparation of cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer PO

[0127] The synthetic route for PO is as follows:

[0128] In a 500 mL three-necked flask, 11.24 g (110 mmol) of 3-methyl-3-hydroxymethyloxetane, 11.13 g (110 mmol) of triethylamine, and 400 mL of anhydrous tetrahydrofuran were added sequentially. 10.55 g (50 mmol) of phenyl dichlorophosphate and 50 mL of anhydrous tetrahydrofuran were placed in a 50 mL constant-pressure dropping funnel. The solution in the dropping funnel was slowly added dropwise to the reaction system under 0 °C ice-water bath conditions. The reaction was then mechanically stirred and allowed to proceed at room temperature for 24 hours. After the reaction was complete, the reaction solution was first filtered, then rotary evaporated at 50 °C and -0.09 MPa to -0.10 MPa, followed by purification and separation by column chromatography. The stationary phase was silica gel, and the eluent was PE:EA = 7:1 (v / v), yielding 11.23 g of product PO (yield: 65.6%).

[0129] The 1H NMR spectrum data of PO are as follows: 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).

[0130] The carbon NMR data of PO are as follows: 13 C NMR (101MHz, chloroform-d) δ 150.4 (d, J = 7.1Hz), 129.7, 125.3, 119.9 (d, J = 4.8Hz), 78.6 (d, J = 5.2Hz), 72.5, 39.8 (d, J = 7.9Hz), 20.4.

[0131] The NMR phosphorus spectrum data of PO are as follows: 31 P NMR (162MHz, chloroform-d) δ -6.30.

[0132] The infrared data for PO is: FTIR (KBr, cm -1 )2958,2874,1591,1489,1384,1282,1210,1018,939,832,766,688,586,532.

[0133] Example 3

[0134] The purpose of this embodiment is to illustrate the photopolymerization properties of the compounds of the present invention. The photocurable composition comprises a cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer, commercial monomers E4221 and DVE-2, as well as a commercial cationic photoinitiator 810 and a photosensitizer ITX, with the molar percentages of each component being: cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer (X):E4221:DVE-2:810:ITX = X:80:20:2:2. All photocurable compositions used in the embodiments were prepared according to this ratio.

[0135] The photopolymerization kinetics in the presence of compounds EO and PO were tested using real-time infrared spectroscopy (Nicolet 5700, Thermo Electron, USA), and the effects of their respective contents on the photopolymerization performance of the E4221 / DVE-2 system were investigated. The vibrational absorption peak of the COC of the three-membered oxygen heterocycle of the monomer E4221 was located at 750 cm⁻¹. -1 Around 980 cm⁻¹, the vibrational absorption peak of the COC of the four-membered oxygen heterocycle in the monomers EO and PO is located at 980 cm⁻¹. -1 Approximately 50 mW / cm². A small amount of photocurable liquid, consisting of monomer and photoinitiator, was evenly coated onto a potassium bromide salt sheet using a 0.5 mm glass spotting tube. The sample was then irradiated for 15 minutes using a 365 nm UV spot light source, approximately 5 cm from the sample, with an irradiance of 50 mW / cm². -2 Measurements were taken at 750cm. -1 and 980cm -1 The change in the peak area of ​​the COC bond indicates the real-time conversion rate of different epoxy groups, i.e., monomers.

[0136] The results for the photocurable compositions containing compounds EO and PO are shown in Figures 1-4 and Tables 2-3, respectively (in the figures and tables below, EO-5% is used as an example, indicating that X in the formulation is 5 mol%). The results show that the addition of compounds EO and PO can significantly improve the conversion rate of monomers in the E4221 / DVE-2 system. Furthermore, only a small amount (10 mol%) of compounds EO and PO is needed to significantly improve the conversion rate of alicyclic epoxides, with maximum conversion rates exceeding 78%. Moreover, when 15 mol% of compounds EO and PO are added, the conversion rates of both are above 60%. Therefore, the compounds of this invention can improve the photopolymerization performance of monomers in the E4221 / DVE-2 system, and the compounds themselves possess good photopolymerization activity.

[0137] Table 2: Monomer conversion rate of photocurable compositions using compound EO at 800 s

[0138] Table 3: Monomer conversion rate at 800s for photocurable compositions using compound PO

[0139] Example 4

[0140] The purpose of this embodiment is to illustrate that the compound of the present invention can improve the surface hydrophobicity of photocurable films. The photocurable composition comprises a cationic photopolymerizable phosphorus-containing bifunctional oxetane monomer (X): E4221:DVE-2:810:ITX = X:80:20:2:2. The photocurable compositions used in this embodiment were prepared according to this ratio. The prepared photocurable composition photosensitive liquid was added to a 30mm × 10mm × 2mm polytetrafluoroethylene mold, and then cured in a UV curing machine (model: RX1K300, mercury lamp, main wavelength 365nm, light intensity: 70mW cm⁻¹). -2 After irradiating for 15-20 minutes, the photocured film was removed. To accelerate the post-curing process of the photocured film, it was placed in a constant temperature oven at 60°C for 3-4 hours before subsequent performance testing.

[0141] The water contact angle of the UV-cured film was tested at 20℃ using a DSA 25 water contact angle meter. Each sample was measured three times, and the average value was taken. The E4221 / DVE-2 system (EO-0% or PO-0%) served as a blank control group. The test results are shown in Figure 5-6 and Table 4-5.

[0142] As shown in Figures 5-6 and Tables 4-5, the water contact angle of the photocurable film of the blank E4221 / DVE-2 system without the addition of compounds EO and PO is 64.2°. However, the water contact angle of the photocurable film is significantly improved after adding either compound EO or PO, reaching a maximum of 83.8° with the addition of EO and a maximum of 83.5° with the addition of PO. Therefore, the compounds of the present invention can significantly improve the surface hydrophobicity of the photocurable film.

[0143] Table 4: Water contact angle of photocurable films obtained using photocurable compositions containing compound EO

[0144] Table 5: Water contact angle of photocurable films obtained using photocurable compositions containing compound PO

[0145] Example 5

[0146] The purpose of this embodiment is to illustrate that the compound of the present invention can improve the tensile properties of photocurable films.

[0147] Photocurable films in the presence of compounds EO and PO were prepared using the exact same method as described in Example 4. The tensile properties of the photocurable films were tested on an electronic universal testing machine (METS Industrial (China) Co., Ltd., E44.304) at a speed of 2 mm / min. -1 The corresponding elongation at break and tensile strength were recorded in the testing software. Each sample was tested three times, and the average value was calculated. The testing procedure complied with the requirements of the national standard GB / T 1040.2-2006. The E4221 / DVE-2 system (EO-0% or PO-0%) served as a blank control group. The test results are shown in Figure 7-8 and Table 6-7.

[0148] As shown in Figure 7 and Table 6, after adding compound EO, the tensile strength of the system showed a trend of first increasing, then decreasing, and then stabilizing, but all were higher than the 5.33 MPa of the blank E4221 / DVE-2 system. The tensile strength of the system was highest at 7.73 MPa when 5 mol% EO was added. The elongation at break of the system showed a trend of first decreasing and then increasing. As shown in Figure 8 and Table 7, after adding compound PO, the tensile strength of the system also showed a trend of first increasing and then decreasing, but all were higher than the 5.33 MPa of the blank E4221 / DVE-2 system. The tensile strength of the system was highest at 9.11 MPa when 15 mol% PO was added, while the elongation at break first decreased from 10.28% for PO-0% to 6.71% for PO-5%, and then increased to 11.33% for PO-20%.

[0149] Table 6: Tensile properties of photocurable films obtained using photocurable compositions containing compound EO

[0150] Table 7: Tensile properties of photocurable films obtained using photocurable compositions containing compound PO

[0151] Example 6

[0152] Photocurable films in the presence of compounds EO and PO were prepared using the exact same method as described in Example 4. Thermogravimetric analysis (TGA) of the photocurable films was then performed using a DTG-60AH (Shimadzu, China) differential thermal-thermogravimetric analyzer. 8–10 mg of sample was placed in an alumina crucible, and the mixture was heated at a flow rate of 50 mL / min. -1 Under a nitrogen atmosphere, the temperature was increased from 30°C to 800°C at a rate of 10°C / min. -1 The holding time was 10 min. The E4221 / DVE-2 system (EO-0% or PO-0%) served as a blank control group. The test results are shown in Figure 9-12 and Table 8-9.

[0153] As can be seen from Figure 9-12 and Table 8-9, the initial decomposition temperature (T) of the photocurable film after the addition of compounds EO and PO is... 5％ ) and maximum thermal weight loss temperature (T max The concentrations of all three elements decreased significantly, but the amount of char residue at 700℃ increased. The synthesized monomers facilitated the thermal degradation process of the photocurable film and promoted char formation in the system.

[0154] Table 8: Thermogravimetric data of photocurable films obtained using photocurable compositions containing compound EO

[0155] Table 9: Thermogravimetric data of photocurable films obtained using photocurable compositions containing compound PO

[0156] Example 7

[0157] Photocurable films in the presence of compounds EO and PO were prepared using the exact same method as described in Example 4. Then, under a nitrogen atmosphere, the glass transition temperature (Tg) of the photocurable films was measured using a DSC-60plus (Shimadzu, China) differential scanning calorimeter. g The measurement was performed, with the temperature rising from 30℃ to 400℃ at a rate of 10℃ / min. -1 The nitrogen flow rate is 50 mL / min. -1 The E4221 / DVE-2 system (EO-0% or PO-0%) served as a blank control group. The test results are shown in Figures 13-14 and Table 10-11.

[0158] As can be seen from Figure 13-14 and Table 10-11, the glass transition temperature (Tg) of the photocurable film after the addition of compounds EO and PO... g The levels of both were significantly reduced, indicating that the synthesized monomers have a certain plasticizing effect.

[0159] Table 10: Glass transition temperatures of photocurable films obtained using photocurable compositions containing compound EO

[0160] Table 11: Glass transition temperatures of photocurable films obtained using photocurable compositions containing compound PO

[0161] Example 8

[0162] The purpose of this embodiment is to illustrate that the compound of the present invention can improve the flame retardant properties of photocurable films to a certain extent.

[0163] Photocurable films in the presence of compounds EO and PO were prepared using the exact same method as described in Example 4. Then, according to ASTM D2863, the limiting oxygen index of the photocurable films was tested using a 5801 digital oxygen indexer. The dimensions of the photocurable films were 100 mm × 6.5 mm × 3 mm. A horizontal burning test was then conducted on the photocurable films according to the requirements of the national standard GB / T 2408-1996 to study their flame retardant properties. The dimensions of the photocurable films used were 125 mm × 13 mm × 3 mm. The E4221 / DVE-2 system (EO-0% or PO-0%) served as a blank control group. The test results are shown in Tables 12-13.

[0164] As shown in Table 12-13, the limiting oxygen index and horizontal combustion test rating of the photocurable film increased after the addition of compounds EO and PO, indicating that the synthesized monomers have a certain flame retardant effect.

[0165] Table 12: Flame retardant properties of photocurable films obtained using photocurable compositions containing compound EO

[0166] Table 13: Flame retardant properties of photocurable films obtained using photocurable compositions containing compound PO

Claims

1. The following compound (Ⅰ): in R1groups are selected from: C1-C6alkoxy, C6-C 10 aryl or C6-C 10 aryloxy; R2groups are the same or different and independently selected from: -(CH2) m -(CO) o -O-(CH2) n -; The R3 groups may be 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 between 0 and 20; n is an integer from 1 to 20; and o is an integer that is either 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 R1 group is a C1-C4 alkoxy, C6-C9 aryl, or C6-C9 aryloxy group; and / or The R3 group is H, a 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.

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

4. The compound of formula (I) according to claim 1, wherein R1 group is a C1-C2 alkoxy or a C6-C8 aryloxy group; and / or R3 is an H, a C1-C2 alkyl group, or a C1-C2 haloalkyl group; and / or m is an integer between 0 and 3; and / or n is an integer between 1 and 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 process for the preparation of a compound of formula (I) according to any one of claims 1 to 5, comprising the reaction of a compound of formula (II): Wherein R1, m, and o are as defined in any one of claims 1-5, and X is OH or a halogen. with a compound of formula (III): Wherein R3 and n are as defined in any one of claims 1-5 Compound of formula (I) was obtained.

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

8. The method according to claim 6 or 7, wherein the reaction is carried out in the presence of an acid-binding agent 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 to 1:2, more preferably 1:1.05 to 1:1.

5.

9. The method according to any one of claims 6-8, 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 a compound of formula (I) according to any one of claims 1-5 as a polymerizable monomer.

11. The photocurable composition according to claim 10, comprising a compound of formula (I), an additional cationicly photopolymerizable reactive monomer or reactive resin, a cationicly polymerizable reactive diluent monomer, a cationic photoinitiator and a photosensitizer, wherein the molar ratio 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.

12. The photocurable composition according to claim 11, wherein the cationic photopolymerizable active monomer or active resin is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate (E4221) or 4-vinylepoxycyclohexane (VOH); the cationic photopolymerizable 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 10-12, wherein it is a photocurable coating composition, a photocurable ink composition, or a photoresist composition.

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

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

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