Alkali-soluble oxetane-based silicon-containing monomer, preparation method therefor, and use thereof

Abstract

The present invention relates to compounds of formula (I), wherein variables m, R1, R2, R3, R4, R5 and R6 are as defined in the description. The present invention also relates to a preparation method for the compounds of formula (I), a photocurable composition comprising the compounds of formula (I), and a photocurable material obtained from the photocurable composition. The present invention achieves the following beneficial effects: (1) the compounds of formula (I) have good photopolymerization activity and can be quickly cured under the action of ultraviolet light; (2) adding the compounds of formula (I) can improve the surface hydrophobicity, hardness, adhesion force, thermal stability, glass transition temperature and tensile property of cured films; and (3) the compounds of formula (I) have good alkali solubility and can realize clear development and imaging.

Description

Alkali-soluble oxetanyl silane monomer, preparation method and application thereof TECHNICAL FIELD

[0001] The present application relates to the field of photocurable materials, in particular to an alkali-soluble oxetanyl silane monomer. The present application also relates to a preparation method of the monomer, a photocurable composition comprising the monomer and a photocured material obtained from the photocurable composition. BACKGROUND

[0002] Photopolymerization is a process that rapidly converts a chemically active liquid monomer or oligomer into a solid polymer by cross-linking induced by ultraviolet or visible light. It is a green and sustainable environmental technology that has been gradually developed since the 1960s. Compared with traditional thermal polymerization, photopolymerization has many advantages, such as being green and environmentally friendly, having no solvent consumption and volatilization, high efficiency, fast speed, low cost, etc. Photopolymerization technology has been widely used in many fields, such as photocurable coatings, photocurable inks and photocurable adhesives. With the continuous development and progress of photocuring technology, photopolymerization technology is now developing more rapidly in advanced fields such as photoresist, laser three-dimensional imaging and three-dimensional modeling. Compared with free radical photopolymerization, cationic photopolymerization systems have slower polymerization rates, but they have the advantages of resistance to oxygen inhibition, small volume shrinkage, good adhesion and high surface hardness. Oxetane has the advantages of small viscosity, low toxicity, small volatility and low volume shrinkage, and has been widely used as a cationic photopolymerization monomer. In addition, organosiloxanes have excellent heat resistance, water repellency, flexibility, electrical insulation and physiological inertness. In addition, alkali-soluble photopolymerization monomers have developed rapidly in recent years. A variety of alkali-soluble photopolymerization monomers have been developed and applied in the electronic and printing industries. SUMMARY

[0003] The purpose of the present application is to provide an alkali-soluble oxetanyl silane monomer. The present inventors have found that the alkali-soluble oxetanyl silane monomer has good polymerization rate and conversion rate and can promote the polymerization of other cationic monomers, while imparting excellent tensile properties, thermal stability, surface hydrophobicity, etc. to the material. Due to the carboxyl structure present in its molecular structure, the monomer has excellent alkali solubility and can be developed under a mask plate.

[0004] Another purpose of the present application is to provide a method for preparing the alkali-soluble oxetanyl silane monomer of the present application. The preparation method is simple, easy to operate, mild in conditions, easy to obtain raw materials and low in cost.

[0005] Specifically, the present application relates to the following aspects:

[0006] 1. A compound of the following formula (I):

[0007] Where m is an integer from 1 to 50; R1, R2, R3, R4, and R5 are the same or different and are independently organic groups having 1 to 12 carbon atoms; and R6 is H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 hydroxyalkyl, C1-C6 alkoxy, or C1-C6 haloalkoxy.

[0008] 2. The compound of formula (I) as described in item 1, wherein m is an integer from 1 to 30; R1 is C1-C1. 12 Alkyl or C1-C 12 Alkyl groups; R2, R3, R4, and R5 may be the same or different, and are independently C6-C. 10 Aryl, C1-C 12 Alkyl, C1-C 12 Alkyl group, independently selected from NR a C2-C with non-adjacent heteroatoms of O and S 12 Alkyl groups or groups independently selected from NR a C2-C with non-adjacent heteroatoms of O and S 12 alkoxy group, where R a It is H or C1-C4 alkyl.

[0009] 3. The compound of formula (I) according to item 1, wherein

[0010] m is an integer from 1 to 20, preferably from 2 to 15; and / or

[0011] R1 is a C1-C6 alkyl or C1-C6 alkoxy; R1 is preferably a C1-C4 alkyl or C1-C4 alkoxy; and / or

[0012] R2, R3, R4, and R5 may be the same or different, and are independently C6-C. 10 aryl, C1-C6 alkyl, C1-C6 alkoxy, or one or more independently selected from NR a C2-C6 alkyl groups with non-adjacent heteroatoms of O and S, wherein R a It is H or C1-C4 alkyl; preferably, R2, R3, R4, and R5 are the same or different, and are independently phenyl, C1-C4 alkyl, C1-C4 alkoxy, or are independently selected from NR by one or more. a C2-C4 alkyl groups with non-adjacent heteroatoms of O and S, wherein R a It is H or C1-C4 alkyl; and / or

[0013] R6is H, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4hydroxyalkyl, C1-C4alkoxy or C1-C4haloalkoxy.

[0014] 4. The compound of formula (I) according to item 1, wherein m is an integer from 1 to 9; R1is C1-C4alkyl or C1-C4alkoxy; R2, R3, R4, R5are the same or different and independently phenyl, C1-C4alkyl, C1-C4alkoxy or C2-C4alkyl interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C1-C4alkyl; R6is H, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4hydroxyalkyl, C1-C4alkoxy or C1-C4haloalkoxy;

[0015] Preferably, m is an integer from 3 to 9; R1is C1-C4alkyl; R2, R3, R4, R5are the same or different and independently C1-C4alkyl; R6is H or C1-C4alkyl.

[0016] 5. The compound of formula (I) according to item 1, wherein the compound of formula (I) is selected from the group consisting of:

[0017] 6. A process for the preparation of a compound of formula (I) according to any one of items 1 to 5, comprising reacting a compound of formula (IV) with a compound of formula (V) to give a compound of formula (I):

[0018] wherein R6is as defined in any one of items 1 and 3 to 5,

[0019] wherein m, R1, R2, R3, R4and R5are as defined in any one of items 1 to 5.

[0020] 7. The process according to item 6, wherein

[0021] the reaction of the compound of formula (IV) with the compound of formula (V) is carried out in the presence of Karstedt's catalyst or Speier's catalyst, preferably the catalyst is present in an amount of 2 to 500 ppm, preferably 80 to 200 ppm, based on the weight of the compound of formula (V); and / or

[0022] the molar ratio of the compound of formula (IV) to the compound of formula (V) is from 1 :0.65 to 1 :1.5, preferably from 1 :0.75 to 1 :1 ; and / or

[0023] the reaction between the compound of formula (IV) and the compound of formula (V) is carried out at a temperature of from 80 to 110 °C, preferably from 85 to 100 °C; and / or

[0024] The reaction between the compound of formula (IV) and the compound of formula (V) is carried out for 6-12 hours, preferably 7-9 hours.

[0025] 8. The process according to claim 6 or 7, wherein the compound of formula (IV) is prepared by the steps of:

[0026] reacting a compound of formula (II):

[0027] with a compound of formula (III),

[0028] wherein

[0029] R6 is as defined in any one of claims 1 and 3-5,

[0030] to obtain a compound of formula (IV).

[0031] 9. The process according to claim 8, wherein

[0032] The reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a basic catalyst, which is preferably triethylamine, potassium bicarbonate, pyridine or any mixture thereof, more preferably the molar ratio of the compound of formula (II) to the basic catalyst is 1 :0.05-1 :0.5, preferably 1 :0.08-1 :0.2; and / or

[0033] The molar ratio of the compound of formula (II) to the compound of formula (III) is 1 :1-1 :1.8, preferably 1 :1.2-1 :1.5; and / or

[0034] The reaction between the compound of formula (II) and the compound of formula (III) is carried out at 20-90 °C, preferably 30-60 °C; and / or

[0035] The reaction between the compound of formula (II) and the compound of formula (III) is carried out for 2-8 hours, preferably 3-6 hours.

[0036] 10. A photocurable composition comprising a compound of formula (I) according to any one of claims 1-5 as a polymerizable monomer.

[0037] 11. A photocured material obtained from the photocurable composition according to claim 10.

[0038] 12. Use of a compound of formula (I) according to any one of claims 1-5 in photocured coatings, adhesives, inks and photoresists. BRIEF DESCRIPTION OF DRAWINGS

[0039] Figure 1 is a graph of the conversion of cycloaliphatic epoxy in a system containing compound (I-1) prepared in Example 1 as a function of irradiation time.

[0040] Figure 2 is a graph of the conversion of cycloaliphatic epoxy in a system containing compound (I-2) prepared in Example 2 as a function of irradiation time.

[0041] Figure 3 is a graph of the conversion of cycloaliphatic epoxy in a system containing compound (I-3) prepared in Example 3 as a function of irradiation time.

[0042] Figure 4 is a graph of the conversion of compound (I-1) in a system containing compound (I-1) prepared in Example 1 as a function of irradiation time.

[0043] Figure 5 is a graph of the conversion of compound (I-2) in a system containing compound (I-2) prepared in Example 2 as a function of irradiation time.

[0044] Figure 6 is a graph of the conversion of compound (I-3) in a system containing compound (I-3) prepared in Example 3 as a function of irradiation time.

[0045] Figure 7 is a graph of the contact angle of a blank E4221 / VOH cured film and cured films containing systems of compounds (I-1) through (I-3) each prepared in Examples 1-3.

[0046] Figure 8 is a graph of the thermogravimetric curve of a blank E4221 / VOH cured film and cured films containing systems of compounds (I-1) through (I-3) each prepared in Examples 1-3.

[0047] Figure 9 is a graph of the mechanical properties of a blank E4221 / VOH cured film and cured films containing systems of compounds (I-1) through (I-3) each prepared in Examples 1-3.

[0048] Figure 10 is a graph of the development of a blank E4221 / VOH cured film and cured films containing systems of compounds (I-1) through (I-3) each prepared in Examples 1-3.

[0049] DETAILED DESCRIPTION

[0050] In the following description of the application, the numerical values in this application can be considered to be modified by the word "about" unless otherwise explicitly indicated. However, the inventors have reported the numerical values in the examples as precisely as possible, although these numerical values include unavoidable errors.

[0051] In the present application, the specific or preferred embodiments of the present application can be combined, unless explicitly excluded. In addition, each element of the embodiments of the present application is a specific preferred selection of the corresponding generic technical feature. If the generic technical feature can be combined with other generic features, the element of the embodiment, i.e. the specific preferred selection, can also be combined with the other generic features. These combinations shall be considered as part of the originally filed content of the present application. DETAILED DESCRIPTION

[0052] According to one aspect of the present application, there is provided a compound of the following formula (I):

[0053] wherein m is an integer from 1 to 50; R1, R2, R3, R4, R5are the same or different and independently an organic group having 1 to 12 carbon atoms; and R6is H, halogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl, C1-C6alkoxy, or C1-C6haloalkoxy.

[0054] In the present application, the prefix "C n -C m " in each case denotes the number of carbon atoms comprised in the group as n-m.

[0055] "Halogen" means fluorine, chlorine, bromine and iodine. In the present application, it is preferred that halogen includes fluorine, chlorine or a combination thereof.

[0056] As used herein, the term "C n -C m"Alkyl" refers to a branched or unbranched saturated hydrocarbon group having 1-12 carbon atoms, preferably 1-6, and particularly preferably 1-4 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl 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-dimethylpropyl Methylbutyl, 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, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 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.

[0057] 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.

[0058] The term "C" used in this article n -C m "Alkoxy" refers to the compound formed by the carbon atom in C2O2. n -C m alkyl corresponding to open chain C n -C m In alkanes, an oxygen atom is bonded to any carbon atom as a linking group. n -C m Alkyl groups, such as C1-C 12Alkoxy groups, more preferably C1-C6 alkoxy groups, and especially 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.

[0059] 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 groups, such as C1-C 12 Haloalkyl, preferably C1-C6 haloalkyl, particularly preferably C1-C4 haloalkyl. 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.

[0060] The term "C" used in this article n -C m "Haloalkoxy" refers to a carbon atom that has been substituted with one or more identical or different halogen atoms. n -C m Alkoxy groups, such as C1-C 12 Haloalkoxy groups, more preferably C1-C6 haloalkoxy groups, and especially preferably C1-C4 haloalkoxy groups. As a C n -C mExamples of haloalkoxy groups that can be mentioned are chloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 4-chlorobutoxy, 5-chloropentoxy, 6-chlorohexyloxy and the isomers thereof, in particular chloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 2-chloroisopropoxy, 4-chlorobutoxy, 3-chloro-sec-butoxy, 2-chloro-tert-butoxy, 5-chloropentoxy, 4-chloroiso-pentoxy, 6-chlorohexyloxy and the like.

[0061] The term "C n -C m Hydroxyalkyl means a C n -C m alkyl group, for example C1-C6hydroxyalkyl, especially preferably C1-C4hydroxyalkyl, for example hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxy- pentyl, hydroxyhexyl and the isomers thereof, in particular hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxy-sec-butyl, hydroxy-tert-butyl, hydroxy-n-pentyl, hydroxy-n-hexyl and the like. n -C m alkyl group, for example C1-C6hydroxyalkyl, especially preferably C1-C4hydroxyalkyl, for example hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxy- pentyl, hydroxyhexyl and the isomers thereof, in particular hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxy-sec-butyl, hydroxy-tert-butyl, hydroxy-n-pentyl, hydroxy-n-hexyl and the like. n -C m alkyl group, for example C1-C6hydroxyalkyl, especially preferably C1-C4hydroxyalkyl, for example hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxy- pentyl, hydroxyhexyl and the isomers thereof, in particular hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxy-sec-butyl, hydroxy-tert-butyl, hydroxy-n-pentyl, hydroxy-n-hexyl and the like.

[0062] In the compounds according to the application, m is generally an integer from 1 to 50, preferably from 1 to 30, in particular preferably an integer from 1 to 20 or from 2 to 15, for example 3, 6, 9 or 15.

[0063] In the compounds according to the application, R1is generally a C1-C 12 alkyl group or a C1-C 12 alkoxy group. Preferably, R1is a C1-C6alkyl group or a C1-C6alkoxy group. In particular, R1is a C1-C4alkyl group or a C1-C4alkoxy group. In particular, R1is a C1-C4alkyl group. For example, R1is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

[0064] In the compounds according to the application, R2, R3, R4, R5are identical or different and are generally independently a C6-C 10 aryl group, a C1-C 12 alkyl group, a C1-C 12 alkoxy group, a C2-C a alkyl group interrupted by one or more non-adjacent heteroatoms independently selected from NR 12 , O, S, or a C2-C a alkoxy group interrupted by one or more non-adjacent heteroatoms independently selected from NR 12 , O, S, wherein R aH, halogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl, C1-C6alkoxy, or C1-C6haloalkoxy. Preferably, R6is H, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4hydroxyalkyl, C1-C4alkoxy, or C1-C4haloalkoxy. Particularly preferably, R6is H or C1-C4alkyl. For example, R6may be H, chloro, bromo, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, t-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-i-propyl, hydroxy-n-butyl, hydroxy-s-butyl, or hydroxy-t-butyl. 10 aryl, C1-C6alkyl, C1-C6alkoxy, or C2-C6alkyl interrupted by one or more non-adjacent heteroatoms independently selected from the group consisting of NR a , O, S, wherein R a is H or C1-C4alkyl, for example C1-C3alkoxy-C1-C3alkyl, C1-C3alkylamino-C1-C3alkyl, or C1-C3alkylthio-C1-C3alkyl. Particularly preferably, R2, R3, R4, R5are the same or different and independently are phenyl, C1-C4alkyl, C1-C4alkoxy, or C2-C4alkyl interrupted by one or more non-adjacent heteroatoms independently selected from the group consisting of NR a , O, S, wherein R a is H or C1-C4alkyl, for example C1-C2alkoxy-C1-C2alkyl, C1-C2alkylamino-C1-C2alkyl, or C1-C2alkylthio-C1-C2alkyl. Especially, R2, R3, R4, R5are the same or different and independently are C1-C4alkyl. For example, R2, R3, R4, R5are the same or different and independently are phenyl, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, or t-butoxy.

[0065] In the compounds of the application, R6is typically H, halogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl, C1-C6alkoxy, or C1-C6haloalkoxy. Preferably, R6is H, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4hydroxyalkyl, C1-C4alkoxy, or C1-C4haloalkoxy. Particularly preferably, R6is H or C1-C4alkyl. For example, R6may be H, chloro, bromo, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, t-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-i-propyl, hydroxy-n-butyl, hydroxy-s-butyl, or hydroxy-t-butyl.

[0066] In some preferred embodiments of the application,

[0067] m is an integer from 1 to 20, preferably from 2 to 15; and / or

[0068] R1is C1-C6alkyl or C1-C6alkoxy; preferably R1is C1-C4alkyl or C1-C4alkoxy; and / or

[0069] R2, R3, R4, R5are the same or different and independently C6-C 10 aryl, C1-C6alkyl, C1-C6alkoxy or C2-C6alkyl interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C1-C4alkyl; preferably R2, R3, R4, R5are the same or different and independently phenyl, C1-C4alkyl, C1-C4alkoxy or C2-C4alkyl interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C1-C4alkyl; and / or

[0070] R6is H, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4hydroxyalkyl, C1-C4alkoxy or C1-C4haloalkoxy.

[0071] In some preferred embodiments of the application,

[0072] m is an integer from 1 to 9; R1is C1-C4alkyl or C1-C4alkoxy; R2, R3, R4, R5are the same or different and independently phenyl, C1-C4alkyl, C1-C4alkoxy or C2-C4alkyl interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C1-C4alkyl; R6is H, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4hydroxyalkyl, C1-C4alkoxy or C1-C4haloalkoxy.

[0073] Preferably m is an integer from 3 to 9; R1is C1-C4alkyl; R2, R3, R4, R5are the same or different and independently C1-C4alkyl; R6is H or C1-C4alkyl.

[0074] In another embodiment of the application, the compound of formula (I) is a compound selected from the group consisting of:

[0075] According to a second aspect of the application, there is provided a process for the preparation of a compound of formula (I) according to the application, comprising reacting a compound of formula (IV) with a compound of formula (V) to give a compound of formula (I):

[0076] wherein R6is as defined for the compound of formula (I),

[0077] wherein m, R1, R2, R3, R4and R5are as defined for the compound of formula (I).

[0078] The compound of formula (V) contains a hydrogen atom on the terminal silicon atom, and therefore, the compound of formula (V) can be referred to as a hydrogen- containing silicone oil. The compound of formula (V) can be synthesized according to a conventional method or can be obtained from a commercial source. The addition reaction of the hydrogen atom bonded to the silicon atom in the compound of formula (V) to the unsaturated carbon-carbon double bond in the compound of formula (IV) is a reaction type known in the art.

[0079] Generally, the reaction is carried out in the presence of a catalyst. As the catalyst suitable for the reaction, Karstedt catalyst or Speier catalyst is generally used. The amount of the catalyst is also conventional. Generally, the amount of the catalyst is 2 to 500 ppm, preferably 80 to 200 ppm, based on the weight of the compound of formula (V).

[0080] The reaction of the compound of formula (IV) with the compound of formula (V) is generally carried out in a solvent. As the type of the solvent, there is no particular limitation as long as the compound of formula (V), the compound of formula (IV) and the catalyst are dissolved and do not participate in the reaction between the compound of formula (IV) and the compound of formula (V), and preferably the solvent is also favorable for the precipitation of the product, i.e., the compound of formula (I). As the solvent, an organic solvent is generally used, and preferably, petroleum ether, dichloromethane, toluene or any mixture thereof is used. The amount of the solvent is also conventional, and generally, the amount of the solvent is 2 to 20 times, preferably 8 to 15 times, the total weight of the compound of formula (V) and the compound of formula (IV).

[0081] The compound of formula (V) and the compound of formula (IV) are generally used in approximately equimolar amounts. Advantageously, the molar ratio of the compound of formula (IV) to the compound of formula (V) is 1 : 0.65 to 1 : 1.5, preferably 1 : 0.75 to 1 : 1.

[0082] To achieve the above reaction, generally, the compound of formula (V) is dissolved in the solvent with the catalyst and aged for a certain period of time, and then the compound of formula (IV) is contacted therewith, and then the temperature is raised to the reaction temperature and maintained for a certain period of time to obtain the compound of formula (I).

[0083] The aging is generally carried out at an elevated temperature, generally at 40 to 70°C, preferably at 45 to 60°C. The aging time is generally 20 to 60 minutes, preferably 30 to 50 minutes.

[0084] The reaction temperature between the compound of formula (IV) and the compound of formula (V) is generally 80 to 110°C, preferably 85 to 100°C.

[0085] The reaction between the compound of formula (IV) and the compound of formula (V) is usually carried out at a reaction temperature for a holding time of 6 to 12 hours, preferably 7 to 9 hours.

[0086] Of course, the reaction can advantageously be carried out with stirring. After completion of the reaction, the compound of formula (I) is obtained by a conventional work-up. The work-up usually comprises filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and further removal of the solvent by distillation under reduced pressure.

[0087] In another embodiment of the process according to the application, a compound of formula (II)

[0088] is reacted with a compound of formula (III),

[0089] wherein

[0090] R6is as defined for the compound of formula (I),

[0091] to give a compound of formula (IV).

[0092] The reaction of the hydroxyl group in the compound of formula (III) with the anhydride in the compound of formula (II) is of the type known in the art.

[0093] Usually, the reaction is carried out in the presence of a basic catalyst. As a basic catalyst suitable for the reaction, for example, triethylamine, potassium bicarbonate, pyridine or any mixture thereof can be mentioned. The amount of the catalyst is also conventional. Usually, the molar ratio of the compound of formula (II) to the basic catalyst is 1 : 0.05 to 1 : 0.5, preferably 1 : 0.08 to 1 : 0.2.

[0094] The reaction of the compound of formula (II) with the compound of formula (III) is usually carried out in a solvent. As the type of the solvent, there is no particular limitation as long as the compound of formula (III), the compound of formula (II) and the corresponding basic catalyst are dissolved and do not participate in the reaction between the compound of formula (II) and the compound of formula (III), and preferably the solvent is also advantageous for the precipitation of the product, i.e. the compound of formula (IV). As the solvent, usually an organic solvent is used, preferably toluene, acetone, butanone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile or any mixture thereof, preferably dichloromethane. The amount of the solvent is also conventional, and usually the amount of the solvent is 2 to 20 times, preferably 8 to 15 times, the total weight of the compound of formula (II) and the compound of formula (III).

[0095] The compound of formula (II) and the compound of formula (III) are usually used in approximately equimolar amounts. Advantageously, the molar ratio of the compound of formula (II) to the compound of formula (III) is 1 : 1 to 1 : 1.8, preferably 1 : 1.2 to 1 : 1.5.

[0096] To achieve the above reaction, the compound of formula (II), the compound of formula (III) and the catalyst are usually dissolved in a solvent, then warmed to the reaction temperature for a period of time to obtain the compound of formula (IV).

[0097] The reaction temperature between the compound of formula (II) and the compound of formula (III) is usually 20-90°C, preferably 30-60°C.

[0098] The holding time of the reaction between the compound of formula (II) and the compound of formula (III) at the reaction temperature is usually 2-8 hours, preferably 3-6 hours.

[0099] Of course, the reaction is advantageously carried out under stirring. After the reaction is completed, the compound of formula (IV) is obtained by a conventional work-up. The work-up usually comprises washing (e.g. washing with water, advantageously followed by water removal using a water-adsorbing compound such as magnesium sulfate or sodium sulfate), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and optionally distillation under reduced pressure to further remove the solvent. If a product of higher purity is desired, recrystallization can also be performed.

[0100] The compound of formula (I) of the present application has good photopolymerization activity and can be rapidly cured under the action of ultraviolet light; its addition can improve the surface hydrophobicity, hardness, adhesion, thermal stability and glass transition temperature as well as the tensile properties of the cured film; it has good alkali solubility and can be clearly developed and imaged.

[0101] According to a third aspect of the present application, there is provided a photocurable composition comprising the compound of formula (I) of the present application as a polymerizable monomer. The photocurable composition, in addition to the compound of formula (I) of the present application, can further comprise a cationic photoinitiator for ring-opening polymerization (a photoinitiator capable of initiating cationic polymerization) and, optionally, other monomers or oligomers containing a vinyl ether double bond, an alicyclic epoxy group or an oxacycloalkyl group, etc., such as 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221) or 4-vinyl-oxacyclohexane (VOH). The photocurable composition of the present application can be a photocurable coating composition, a photocurable ink composition or a photoresist composition, etc. After curing of the composition, the obtained cured product has good tensile properties, excellent hydrophobic properties, good chemical resistance and good heat resistance.

[0102] As the photoinitiator for ring-opening polymerization, commonly used are iodonium salts and sulfonium salts. Advantageously, the iodonium salt photoinitiator and the sulfonium salt photoinitiator have the following general formulas (A) and (B), respectively:

[0103] wherein

[0104] R a , Rb R c R d R e each independently is unsubstituted C6-C 10 aryl, or C6-C 12 alkyl, C1-C 12 alkoxy, phenylthio, phenyl and substituted phenyl; preferably is phenyl or naphthyl, or phenyl or naphthyl substituted with a substituent selected from the group consisting of halogen, nitro, C1-C6alkyl and substituted phenyl, wherein the substituted phenyl comprises one or more substituents selected from the group consisting of halogen, nitro, C1-C6alkyl and C1-C6alkoxy; and 10

[0105] Y and Z are non-nucleophilic anions, such as triflate, tosylate, C1-C6carboxylate, BF4 - , ClO4 - , PF6 - , AsF6 - or SbF6 - .

[0106] For example, as photoinitiator, one or more selected from the group consisting of 4-(phenylthio)phenyl diphenylsulfonium hexafluorophosphate, 4-(phenylthio)phenyl diphenylsulfonium hexafluoroantimonate, bis(4-(diphenylsulfonio)phenyl) sulfide bis-hexafluorophosphate, bis(4-(diphenylsulfonio)phenyl) sulfide bis-hexafluoroantimonate, 10-(4-biphenylyl)-2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10-(4-biphenylyl)-2-isopropylthioxanthone-10-sulfonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate (810), 4-octyloxydiphenyliodonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 4-isobutylphenyl 4'-methylphenyl iodonium hexafluorophosphate, 4-isobutylphenyl 4'-methylphenyl iodonium hexafluoroantimonate, bis(4-dodecylphenyl) iodonium hexafluoroantimonate, bis(4-dodecylphenyl) iodonium hexafluorophosphate, bis(4-tert-butylphenyl) iodonium hexafluorophosphate or bis(4-tert-butylphenyl) iodonium hexafluoroantimonate can be used.

[0107] The amount of photoinitiator used in the present application is conventional. The content of photoinitiator is usually 0.1 to 5 mol %, preferably 0.5 to 2 mol %, based on the total amount of the photocurable composition of the present application.

[0108] ​The photocurable composition according to the present application can further contain a sensitizer. As the sensitizer, for example, mention can be made of benzophenone and derivatives thereof such as 4-(4-methylphenylthio)benzophenone or 4,4'-bis(diethylamino)benzophenone, thioxanthone and derivatives thereof such as 2-isopropylthioxanthone, anthraquinone and derivatives thereof such as 2-ethylanthraquinone, coumarin derivatives such as 5,7-dimethoxy-3-(4-dodecylbenzoyl)coumarin, camphorquinone, phenothiazine and derivatives thereof, 3-(aroylmethylene)thiazolines, rhodanine and derivatives thereof, eosin, rhodamine, acridine, cyanine, merocyanine dyes; preferably benzophenone and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, coumarin and derivatives thereof, and especially preferably 2-isopropylthioxanthone.

[0109] The amount of the sensitizer used in the present application is conventional. The content of the sensitizer is usually 0.1 to 5 mol%, preferably 0.5 to 1 mol% based on the total amount of the photocurable composition according to the present application.

[0110] According to a final aspect of the present application, there is provided a photocured material obtained by photocuring the photocurable composition according to the present application. The photocuring conditions are not particularly limited as long as the photocurable composition according to the present application can be photocured. The photocured material has the advantages of good tensile properties, excellent hydrophobic properties, anti-staining, anti-fingerprint, chemical resistance and heat resistance due to the fact that the compound of formula (I) according to the present application is used as the photocurable monomer.

[0111] The present application will be further described in detail with reference to specific examples. In the present application, all parts and percentages are based on weight unless otherwise explicitly stated.

[0112] Examples

[0113] The experimental methods used in the following examples are conventional unless otherwise specified.

[0114] The materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

[0115] Experimental materials and reagents:

[0116] Tetrahydrophthalic anhydride: AR, Shanghai Aldrin Biochemical Technology Co., Ltd.

[0117] 3-Methyl-3-oxabicyclohexanemethanol: AR, Bide Pharmaceutical

[0118] Triethylamine: AR, Anjieji Chemical

[0119] Toluene: AR, Beijing Chemical Plant

[0120] Diphenyliodonium hexafluorophosphate (810): AR, Shanghai Aldrich Biochemical Technology Co., Ltd.

[0121] 4-Vinyl oxirane (VOH): AR, Anjieji Chemical

[0122] 3,4-Epoxy cyclohexyl methyl 3,4-epoxy cyclohexyl carboxylate (E4221): AR, Shanghai Aldrich Biochemical Technology Co., Ltd.

[0123] 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane platinum(0): Karstedt catalyst, AR, Bid Pharmaceutical

[0124] Anhydrous magnesium sulfate: AR, Beijing Chemical Plant

[0125] 2-Isopropyl thioxanthone (ITX): AR, Shanghai Aldrich Biochemical Technology Co., Ltd.

[0126] Example 1

[0127] First, 10 mmol of tetrahydrophthalic anhydride and 20 mL of dichloromethane were put into a single-neck flask equipped with a dropping funnel, and 1 mmol of triethylamine was added as a catalyst. Then 10 mL of dichloromethane and 15 mmol of 3-methyl-3-oxetanemethanol were added to the dropping funnel, and the dripping was started. After stirring at room temperature for 3 h, the reaction was stopped. After the reaction was completed, the reaction solution was washed with water twice, the organic layer was collected, and an appropriate amount of anhydrous magnesium sulfate was added and stirred overnight. Then the organic phase was rotary evaporated (50°C, 40 mbar) to obtain compound (IV-a) with a yield of 85%.

[0128] 1 H NMR (400 MHz, Chloroform-d) δ 6.09-4.95 (m, 2H), 4.40-4.08 (m, 2H), 4.40-4.08 (m, 2H), 2.88 (dq, J = 27.1, 7.1 Hz, 2H), 2.49 (h, J = 7.7, 6.8 Hz, 4H), 1.10 (s, 3H).

[0129] In a three-necked flask equipped with a temperature probe and a reflux condenser, 5 mmol of hydrosilane (Anedant Chemicals) (corresponding to a compound of formula (V) wherein m = 3, R1is n-butyl and R2, R3, R4and R5are methyl) and 0.317 g of Karstedt catalyst at 100 ppm concentration (Karstedt catalyst, Anedant Chemicals) were dissolved in 100 mL of anhydrous toluene and then warmed to 60 °C for 40 min. Then, 6 mmol of compound (IV-a) were added dropwise to the three-necked flask, which was warmed to 90 °C for 8 h under stirring. The solid impurities were removed by centrifugation, the solution was rotary evaporated at 45 °C and 0.1 MPa and the resulting solution was distilled under reduced pressure at 300 Pa and 40 °C to obtain the product. It was characterized by1H NMR and identified as compound (I-1) with a yield of 62%, hereinafter referred to as AOX-Si3.

[0130] AOX-Si3: 1 H NMR (400 MHz, Chloroform-d) δ 4.32 - 4.13 (m, 2H), 4.07 - 3.87 (m, 4H), 2.95 (q, J = 7.0 Hz, 1H), 2.84 (q, J = 7.0 Hz, 1H), 1.92 (ddtd, J = 75.5, 36.6, 12.7, 6.5 Hz, 6H), 1.44 (p, J = 7.4 Hz, 1H), 1.24 (dp, J = 18.3, 6.8 Hz, 4H), 1.10 (s, 3H), 0.95 (t, J = 7.8 Hz, 3H), 0.73 (hept, J = 6.6 Hz, 2H), 0.01 (t, J = 5.7 Hz, 24H).

[0131] Example 2

[0132] In a three-necked flask equipped with a temperature probe and a reflux condenser, 5 mmol of hydrosilane (Anedant Chemicals) (corresponding to a compound of formula (V) wherein m = 3, R1is n-butyl and R2, R3, R4and R5are methyl) and 0.317 g of Karstedt catalyst at 100 ppm concentration (Karstedt catalyst, Anedant Chemicals) were dissolved in 100 mL of anhydrous toluene and then warmed to 60 °C for 40 min. Then, 6 mmol of compound (IV-a) were added dropwise to the three-necked flask, which was warmed to 90 °C for 8 h under stirring. The solid impurities were removed by centrifugation, the solution was rotary evaporated at 45 °C and 0.1 MPa and the resulting solution was distilled under reduced pressure at 300 Pa and 40 °C to obtain the product. It was characterized by1H NMR and identified as compound (I-1) with a yield of 62%, hereinafter referred to as AOX-Si3.

[0133] AOX-Si 6:1 H NMR (400 MHz, Chloroform-d) δ 4.31 - 4.10 (m, 2H), 4.06 - 3.87 (m, 4H), 2.95 (q, J = 7.1 Hz, 1H), 2.84 (q, J = 7.1 Hz, 1H), 2.18 - 1.69 (m, 6H), 1.44 (p, J = 7.5 Hz, 1H), 1.34 - 1.14 (m, J = 7.1, 5.0 Hz, 4H), 1.06 (s, 3H), 0.93 (t, J = 7.8 Hz, 3H), 0.74 (hept, J = 6.6 Hz, 2H), 0.32 - -0.17 (m, 42H).

[0134] Example 3

[0135] In a three-necked flask equipped with a temperature probe and a reflux condenser, 5 mmol of hydrosilicone oil (Gelest) (corresponding to a compound of formula (V) wherein m = 9, R1is n-butyl and R2, R3, R4and R5are methyl) and 0.856 g of Karstedt catalyst at 100 ppm concentration (Karstedt Catalyst, Gelest) were dissolved in 100 mL of anhydrous toluene and then warmed to 60 °C for 40 min. Then, 6 mmol of compound (IV-a) were added dropwise to the three-necked flask, which was warmed to 90 °C and maintained under stirring for 8 h. The solid impurities were removed by centrifugation, the solution was rotary evaporated at a temperature of 45 °C and a pressure of 0.1 MPa and then distilled under reduced pressure at 300 Pa and 40 °C to obtain the product. It was characterized by nuclear magnetic resonance spectroscopy and identified as compound (I-3), hereinafter referred to as AOX-Si9, with a yield of 66%.

[0136] AOX-Si 9: 1 H NMR (400 MHz, Chloroform-d) δ 4.30 - 4.07 (m, 2H), 4.06 - 3.85 (m, 4H), 2.96 (q, J = 7.0 Hz, 1H), 2.85 (q, J = 7.0 Hz, 1H), 2.25 - 1.65 (m, 6H), 1.44 (p, J = 7.5 Hz, 1H), 1.24 (dp, J = 14.5, 6.9 Hz, 4H), 1.03 (s, 3H), 0.94 (d, J = 7.9 Hz, 3H), 0.74 (q, J = 6.6 Hz, 2H), 0.34 - -0.16 (m, 60H).

[0137] Example 4

[0138] In a three-necked flask equipped with a temperature probe and a reflux condenser, 5 mmol of hydrosilicone oil (Gelest) corresponding to the compound of formula (V) wherein m = 15, R1is n-butyl and R2, R3, R4and R5are methyl and 1.300 g of Karstedt catalyst at 100 ppm concentration (Karstedt Catalyst, Gelest) were dissolved in 100 mL of anhydrous toluene and then warmed to 60 °C for 40 min. Then, 6 mmol of compound (IV-a) were added dropwise to the three-necked flask, which was warmed to 90 °C and kept under stirring for 8 h. The solid impurities were removed by centrifugation, the solution was rotary evaporated at a temperature of 45 °C and a pressure of 0.1 MPa and then distilled under reduced pressure at 300 Pa and 40 °C to obtain the product. The compound (I-4) was identified by1H NMR spectroscopy and had a yield of 68%, hereinafter referred to as AOX-Si 15 .

[0139] AOX-Si 15: 1 H NMR (400 MHz, Chloroform-d) δ 4.32 - 4.09 (m, 2H), 4.06 - 3.90 (m, 4H), 2.97 (q, J = 7.0 Hz, 1H), 2.84 (q, J = 7.0 Hz, 1H), 2.32 - 1.66 (m, 6H), 1.47 (p, J = 7.5 Hz, 1H), 1.27 (dp, J = 14.5, 6.9 Hz, 4H), 1.05 (s, 3H), 0.96 (d, J = 7.9 Hz, 3H), 0.72 (q, J = 6.6 Hz, 2H), 0.32 - -0.14 (m, 96H).

[0140] Example 5

[0141] The aim of this example is to illustrate the photopolymerization properties of the compounds of the application. The process for the preparation of the photocured composition is as follows:

[0142] X1 mol of the above compound (I-1), X2 mol of E4221 (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl carboxylate), X3 mol of VOH (4-vinyl-oxirane), X4 mol of a photoinitiator diphenyl iodonium hexafluorophosphate (810) and X5 mol of a sensitizer 2-isopropylthioxanthone (ITX) were added into a brown bottle and stirred uniformly, and stored in the dark. Taking the photocuring composition AOX-Si3-3.0% as an example, the molar ratio of each component was: compound (I-1) (X1): E4221 (X2): VOH (X3): 810 (X4): ITX (X5) = 3:50:50:1:0.5 (all molar ratios). The molar percentage X1 of the compounds (I-1), (I-2) and (I-3) (i.e. AOX-Si3, AOX-Si6 and AOX-Si9) in each photopolymerization system was shown in Tables 1-3 below, X2+X3 was fixed at 100 and X2:X3 = 1:1 as described above, and X4 and X5 remained unchanged.

[0143] A mixture of a photoinitiator diphenyl iodonium hexafluorophosphate (810) and 2-isopropylthioxanthone (ITX, sensitizer) in a molar ratio of 2:1 was used as a photoinitiation system, and the photopolymerization kinetics in the presence of compounds (I-1) to (I-3) was tested by a real-time infrared (RT-IR) method (real-time infrared spectrometer: Nicolet 5700, Thermo Electron Corporation, USA), and the influence of each on the photopolymerization performance of the E4221 / VOH system at different contents was investigated. The vibration absorption peak of C-O-C of the three-membered oxygen ring of the monomers E4221 and VOH was located at 750 cm -1 , and the vibration absorption peak of C-O-C of the four-membered oxygen ring of the compounds (I-1) to (I-3) as polymerized monomers was 980 cm -1 . The photocurable liquid composed of monomers and a photoinitiator was uniformly coated on a potassium bromide salt slice (a little photocurable liquid was taken by a fine tube, and a point was dotted on the potassium bromide salt slice, and then uniformly spread), and the liquid sample was irradiated by a high-pressure mercury lamp for 900 s, wherein the mercury lamp mainly emitted a wavelength of 365 nm, and was provided with a light guide fiber with a diameter of 5 mm. The light fiber was 10 cm away from the test sample at any end, and the irradiation intensity was 20 mW cm -2 . The real-time conversion rate and the polymerization rate of different epoxy groups, i.e. monomers, were characterized by measuring the change of the peak area of C-O-C bond at 750 cm -1 and 980 cm -1 .

[0144] The results of the photocuring compositions containing compounds (I-1) to (I-3) (i.e. AOX-Si3, AOX-Si6 and AOX-Si9) are shown in Figures 1-3 and Tables 1-3, respectively. As shown in the figures and tables, the addition of compounds (I-1) to (I-3) can significantly improve the conversion and conversion rate of the monomers in the E4221 / VOH system. In addition, the compounds (I-1) to (I-3) can significantly improve the conversion of the alicyclic epoxy with only a small amount of addition (3-12 mol%), and the maximum conversion of the compounds (I-1) to (I-3) is at least 65%. As shown in Figures 4-6, the conversion of the compounds (I-1) to (I-3) is about 80%. Therefore, the compounds of the present application can improve the photopolymerization performance of the monomers in the E4221 / VOH system, and the compounds of the present application have excellent photopolymerization activity.

[0145] Table 1: Monomer conversion at 900 s of the photocuring composition using compound (I-1) (AOX-Si3)

[0146] Table 2: Monomer conversion at 900 s of the photocuring composition using compound (I-2) (AOX-Si6)

[0147] Table 3: Monomer conversion at 900 s of the photocuring composition using compound (I-3) (AOX-Si9)

[0148] Example 6

[0149] The purpose of this example is to illustrate that the compounds of the present application can improve the surface hydrophobicity of the photocured film.

[0150] X1 mol of the above compounds (I-1) to (I-3) (i.e. AOX-Si3, AOX-Si6 and AOX-Si9), X2 mol of E4221, X3 mol of VOH, X4 mol of the photoinitiator diphenyl iodonium hexafluorophosphate (810) and X5 mol of the sensitizer 2-isopropylthioxanthone (ITX) were weighed into a brown bottle and stirred uniformly, and stored in the dark. The molar ratio of each component in the formulation was: monomer (X1): E4221 (X2): VOH (X3): 810 (X4): ITX (X5) = 9:50:50:1:0.5. The stirred photosensitive solution was added to a 6mm x 8mm x 70mm polytetrafluoroethylene mold, and then the mold was placed under a mercury lamp for irradiation (wavelength 365 nm, light intensity 60 mW cm -2 ), and the cured film was removed after irradiation for 900 s, and the water contact angle test was performed.

[0151] The surface hydrophobicity of the photocured films was characterized by a DSA25 water contact angle measuring instrument at 25°C. Meanwhile, a blank E4221 / VOH cured film was prepared as a reference by the same method. The results of the reference and in the presence of compounds (I-1) to (I-3) are shown in Figure 7.

[0152] As shown in Figure 7, when the E4221 / VOH polymerization system is not added with the compound of the present application, the water contact angle of the cured film is 54.3°, while after the addition of one of compounds (I-1) to (I-3), the water contact angle of the cured film is significantly improved, reaching 93.4°, 95.6° and 98.4°, respectively. The contact angle of the cured film obtained by the addition of one of compounds (I-1) to (I-3) all exceeds 75°. Therefore, the compound of the present application can significantly improve the surface hydrophobicity of the cured film.

[0153] Example 7

[0154] The photocured films in the presence of compounds (I-1) to (I-3), respectively, were prepared by the same method as described in Example 6. Then, the thermal resistance of each photocured film was determined by a thermal gravimetric analyzer (DTG-60AH Shimadzu Enterprise Management (China) Co., Ltd.). The test conditions were as follows: nitrogen protection, temperature range 25-600°C, and temperature rising speed 10°C / min. Meanwhile, a blank E4221 / VOH cured film was prepared as a reference by the same method. The results are shown in Table 4 and Figure 8.

[0155] As shown in Table 4 and Figure 8, after the addition of one of compounds (I-1) to (I-3), the initial decomposition temperature (T 5％ ) and the maximum thermal gravimetric temperature (T max ) of the cured film are significantly improved, thus the thermal resistance is significantly improved.

[0156] Table 4: Thermal gravimetric data of photocured films using compounds (I-1) to (I-3) (i.e. AOX-Si3, AOX-Si6 and AOX-Si9)

[0157] Example 8

[0158] The purpose of this example is to illustrate that the compound of the present application can improve the tensile properties of the photocured film.

[0159] The same method as described in Example 6 was used to prepare the respective cured films in the presence of compounds (I-1) to (I-3) respectively. Then the tensile properties of the photocured films were tested using an electronic universal testing machine (Model E44.304, Metzler-Industrietechnik (China) Co., Ltd.) according to the international standard ISO 1184-1983 "Determination of tensile properties of plastics films". The test temperature was 25°C, the humidity was 60%, and the test speed was 1 mm / min. At the same time, a blank E4221 / VOH cured film was prepared as a reference using the same method. The results are shown in Table 5 and Figure 9.

[0160] As shown in Table 5 and Figure 9, the tensile strength of the pure E4221 / VOH photocured film was 0.96 MPa, and the elongation at break was 6.21%. After the addition of one of compounds (I-1) to (I-3), the tensile strength and the elongation at break of the photocured film gradually increased. Therefore, the compounds of the present application can significantly improve the tensile properties of the cured film.

[0161] Example 9

[0162] The purpose of this example is to show that the compounds of the present application can have good alkali solubility and development performance.

[0163] A prepared photosensitive solution was added to a 20 x 30 x 5 mm Teflon mill, and a black mask with BUCT hollow letters was overlaid on top without contact, followed by irradiation under a mercury lamp with an intensity of 20 mW cm -2 for 900 s. After the irradiation, 100 ml of a 2.38% aqueous solution of tetramethylammonium hydroxide was used to rinse repeatedly for 5 times, and the pattern was observed. The results are shown in Table 6 and Figure 10.

[0164] Compared with the E4221 / VOH system, the addition of one of compounds (I-1) to (I-3) has better solubility in a 2.38% aqueous solution of tetramethylammonium hydroxide, and the development effect is significantly improved.

[0165] Table 6: Solubility of compounds (I-1) to (I-3) (i.e. AOX-Si3, AOX-Si6 and AOX-Si9) in a 2.38% aqueous solution of tetramethylammonium hydroxide

Claims

1. Compounds of formula (I): wherein m is an integer from 1 to 50; R1, R2, R3, R4, R5 are the same or different and independently an organic group having 1 to 12 carbon atoms; and R6 is H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 hydroxyalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy.

2. The compound of formula (I) according to claim 1, wherein m is an integer from 1 to 30; R1 is C1-C 12 alkyl or C1-C 12 alkoxy; R2, R3, R4, R5 are the same or different and independently C6-C 10 aryl, C1-C 12 alkyl, C1-C 12 alkoxy, C2-C a alkyl interrupted by one or more non-adjacent heteroatoms independently selected from NR 12 , O, S; C2-C a alkoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR 12 , O, S; wherein R a is H or C1-C4 alkyl.

3. The compound of formula (I) according to claim 1, wherein m is an integer from 1 to 20, preferably from 2 to 15; and / or R1 is C1-C6 alkyl or C1-C6 alkoxy; preferably R1 is C1-C4 alkyl or C1-C4 alkoxy; and / or R2, R3, R4, R5are identical or different and independently C6-C 10 aryl, C1-C6alkyl, C1-C6alkoxy or C2-C6alkyl interrupted by one or more non-adjacent heteroatoms independently selected from the group consisting of NR a , O, S, wherein R a is H or C1-C4alkyl; preferably R2, R3, R4, R5are identical or different and independently phenyl, C1-C4alkyl, C1-C4alkoxy or C2-C4alkyl interrupted by one or more non-adjacent heteroatoms independently selected from the group consisting of NR a , O, S, wherein R a is H or C1-C4alkyl; and / or R6 is H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 hydroxyalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy.

4. The compound of formula (I) according to claim 1, wherein m is an integer from 1 to 9; R1 is C1-C4 alkyl or C1-C4 alkoxy; R2, R3, R4, R5 are the same or different and independently phenyl, C1-C4 alkyl, C1-C4 alkoxy or C2-C4 alkyl interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C1-C4 alkyl; R6 is H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 hydroxyalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; It is preferred that m is an integer from 3 to 9; R1 is C1-C4 alkyl; R2, R3, R4, R5 are the same or different and independently C1-C4 alkyl; and R6 is H or C1-C4 alkyl.

5. The compound of formula (I) according to claim 1, wherein the compound of formula (I) is 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 reacting a compound of formula (IV) with a compound of formula (V) to give a compound of formula (I): wherein R6is as defined in any one of claims 1 and 3-5, wherein m, R1, R2, R3, R4 and R5 are as defined in any one of claims 1 to 5.

7. The process according to claim 6, wherein the reaction of the compound of formula (IV) with the compound of formula (V) is carried out in the presence of Karstedt's catalyst or Speier's catalyst; preferably the amount of catalyst is 2 to 500 ppm, preferably 80 to 200 ppm, based on the weight of the compound of formula (V); and / or the molar ratio of the compound of formula (IV) to the compound of formula (V) is 1 :0.65 to 1 :1.5, preferably 1 :0.75 to 1 :1 ; and / or the reaction between the compound of formula (IV) and the compound of formula (V) is carried out at 80 to 110 °C, preferably at 85 to 100 °C; and / or the reaction between the compound of formula (IV) and the compound of formula (V) is carried out for 6 to 12 hours, preferably for 7 to 9 hours.

8. The process according to claim 6 or 7, wherein the compound of formula (IV) is prepared by the following steps: to form a compound of formula (II): with a compound of formula (III), wherein R6 is as defined in any one of claims 1 and 3 to 5, to give the compound of formula (IV).

9. The process according to claim 8, 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, preferably triethylamine, potassium bicarbonate, pyridine or any mixture thereof; more preferably the molar ratio of the compound of formula (II) to the basic catalyst is 1 :0.05 to 1 :0.5, preferably 1 :0.08 to 1 :0.2; and / or the molar ratio of the compound of formula (II) to the compound of formula (III) is 1 :1 to 1 :1.8, preferably 1 :1.2 to 1 :1.5; and / or the reaction between the compound of formula (II) and the compound of formula (III) is carried out at 20 to 90 °C, preferably at 30 to 60 °C; and / or the reaction between the compound of formula (II) and the compound of formula (III) is carried out for 2 to 8 hours, preferably for 3 to 6 hours.

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

11. A photocured material obtained from the photocurable composition according to claim 10.

12. Use of a compound of formula (I) according to any one of claims 1 to 5 in photocured coatings, adhesives, inks and photoresists.

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