Bifunctional oxetanyl silicon-containing monomer, and preparation method therefor and use thereof

Abstract

The present invention relates to the compound of formula (I), wherein the variables m, R1, R2, R3, R4, R5 and R6 are as defined in the specification. The present invention also relates to a preparation method for the compound of formula (I), a photocurable composition containing the compound of formula (I), a photocurable material prepared from the photocurable composition, and the use of the compound of formula (I) in the field of photocurable materials. The present invention has the following beneficial effects: (1) the compound of formula (I) has relatively good photopolymerization activity, and can be rapidly cured under the action of ultraviolet light; and (2) by means of the addition of the compound of formula (I), the surface hydrophobicity, heat resistance and tensile properties of a cured film can be improved.

Description

Bifunctional oxetanyl silicon-containing monomer, method for preparing and use thereof TECHNICAL FIELD

[0001] The present application relates to the field of photocurable materials, in particular to a bifunctional oxetanyl silicon-containing monomer. The present application also relates to a method for preparing the monomer, a photocurable composition comprising the monomer, a photocured material obtained from the photocurable composition and the use of the monomer in the field of photocurable materials. BACKGROUND

[0002] Photopolymerization is a process that rapidly converts a chemically active liquid monomer or oligomer into a solid polymer by cross-linking initiated 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. Although there are monomers containing organosiloxane and oxetane structures, there is still a need for monomers containing organosiloxane and oxetane structures that can impart better properties to materials, such as surface hydrophobicity, heat resistance and tensile properties. SUMMARY

[0003] The purpose of the present application is to provide a bifunctional oxetanyl silicon-containing monomer. The present inventors have found, through research, that the bifunctional oxetanyl silicon-containing monomer has good polymerization rate and conversion rate and can promote the polymerization of other cationic monomers, while imparting excellent tensile properties, heat resistance, surface hydrophobicity, etc. to the material.

[0004] Another purpose of the present application is to provide a method for preparing the bifunctional oxetanyl silicon-containing monomer of the present application. The preparation method is simple and easy to operate, has mild conditions, raw materials are easy to obtain and the cost is low.

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

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

[0007] 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.

[0008] 2. The compound of formula (I) according to item 1, wherein m is an integer from 1 to 30; R1is C1-C 12 alkyl or C1-C 12 alkoxy; R2, R3, R4, R5are 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, or 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-C4alkyl.

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

[0012] 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

[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 80-110 °C, preferably 85-100 °C; and / or

[0024] the reaction between the compound of formula (II) and the compound of formula (III) is carried out for 6-12 hours, preferably 8-10 hours.

[0025] 8. The process according to item 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] R6is as defined in any one of items 1 and 3-5,

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

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

[0032] the reaction between the compound of formula (II) and the compound of formula (III) is carried out in the presence of a basic catalyst, which is preferably potassium hydroxide, sodium hydroxide, sodium hydride or any mixture thereof, more preferably the molar ratio of the compound of formula (II) to the basic catalyst is 1 : 1.5-1 : 5, preferably 1 : 2-1 : 3; and / or

[0033] the molar ratio of the compound of formula (II) to the compound of formula (III) is 1 : 2.1-1 : 3, preferably 1 : 2.2-1 : 2.5; and / or

[0034] the reaction between the compound of formula (II) and the compound of formula (III) is carried out at 50-90 °C, preferably 55-70 °C; and / or

[0035] the reaction between the compound of formula (II) and the compound of formula (III) is carried out for 6-12 hours, preferably 8-10 hours.

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

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

[0038] 12. Use of a compound of formula (I) according to any one of items 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] DETAILED DESCRIPTION

[0049] 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 inevitably include certain errors.

[0050] In this application, unless explicitly excluded, the specific or preferred embodiments of the application can be combined. In addition, each element of the embodiments of the application is a specific preferred choice 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 choice, can also be combined with the other generic features. These combinations should be considered as part of the original disclosure of this application. DETAILED DESCRIPTION

[0051] According to one aspect of the present application, there is provided a compound of the following formula (I):

[0052] 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.

[0053] In the present application, the prefix "C n -C m " in each case denotes the number of carbon atoms comprised in the radical.

[0054] "Halogen" means fluorine, chlorine, bromine and iodine. In the present application, it is preferred that halogen includes fluorine, chlorine or a combination thereof.

[0055] As used herein, the term "C n -C m alkyl" means a branched or unbranched saturated hydrocarbon group having n-m, for example 1 to 12, preferably 1 to 6, particularly preferably 1 to 4 carbon atoms, such as, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, in particular methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-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, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl and the like. C1-C6alkyl can be methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers thereof, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, t-butyl, n-pentyl, isopentyl, n-hexyl and the like. C1-C4alkyl can be methyl, ethyl, propyl, butyl and isomers thereof, in particular methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.

[0056] 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.

[0057] The term "C" used in this article n -C m "Alkoxy" refers to the compound formed by the carbon atom in C2O2. n -C m alkyl corresponding to open chain C n -C m In alkanes, an oxygen atom is bonded to any carbon atom as a linking group. n -C m Alkyl groups, such as C1-C 12 Alkoxy groups, 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.

[0058] 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 mExamples 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.

[0059] 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 m Examples of haloalkoxy groups include chloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 4-chlorobutoxy, 5-chloropentoxy, 6-chlorohexoxy and their isomers, especially chloromethoxy, 2-chloroethoxy, 3-chloron-propoxy, 2-chloroisopropoxy, 4-chloron-butoxy, 3-chlorosec-butoxy, 2-chlorotert-butoxy, 5-chloron-pentoxy, 4-chloroisopentoxy, 6-chloron-hexoxy, etc.

[0060] The term "C" used in this article n -C m "Hydroxyalkyl" refers to the hydroxyalkyl group in C n -C m alkyl corresponding to open chain C n -C m In alkanes, a carbon atom with a hydroxyl group bonded to it is a C-axis. n -C m Alkyl groups, such as C1-C6 hydroxyalkyl groups, especially C1-C4 hydroxyalkyl groups, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl and their isomers, particularly hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxysec-butyl, hydroxytert-butyl, hydroxy-n-pentyl, hydroxy-n-hexyl, etc.

[0061] In the compounds according to the application, m is generally an integer from 1 to 50, preferably from 1 to 30, in particular from 1 to 20 or from 2 to 15, for example 3, 6, 9 or 15.

[0062] In the compounds according to the application, R1is generally C1-C 12 alkyl or C1-C 12 alkoxy. Preferably, R1is C1-C6alkyl or C1-C6alkoxy. In particular, R1is C1-C4alkyl or C1-C4alkoxy. In particular, R1is C1-C4alkyl. For example, R1is methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl or t-butyl.

[0063] In the compounds according to the application, R2, R3, R4, R5are identical or different and are generally 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, or 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-C4alkyl, for example C1-C6alkoxy-C1-C6alkyl, C1-C6alkylamino-C1-C6alkyl or C1-C6alkylthio-C1-C6alkyl. Preferably, R2, R3, R4, R5are identical or different and are 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, for example C1-C3alkoxy-C1-C3alkyl, C1-C3alkylamino-C1-C3alkyl or C1-C3alkylthio-C1-C3alkyl. In particular, R2, R3, R4, R5are identical or different and are 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 aR2, R3, R4, R5are the same or different and independently H, halogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl, C1-C6alkoxy, or C1-C6haloalkoxy. Preferably, R2, R3, R4, R5are the same or different and independently H, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4hydroxyalkyl, C1-C4alkoxy, or C1-C4haloalkoxy. Particularly preferably, R2, R3, R4, R5are the same or different and independently H or C1-C4alkyl. For example, R2, R3, R4, R5may 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.

[0064] In the compounds of the present 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.

[0065] In some preferred embodiments of the present application,

[0066] m is an integer from 1 to 20, preferably from 2 to 15; and / or

[0067] R1is C1-C6alkyl or C1-C6alkoxy; preferably R1is C1-C4alkyl or C1-C4alkoxy; and / or

[0068] R2, R3, R4, R5are the same or different and independently H, halogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl, C1-C6alkoxy, or C1-C6haloalkoxy. Preferably, R2, R3, R4, R5are the same or different and independently H, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4hydroxyalkyl, C1-C4alkoxy, or C1-C4haloalkoxy. Particularly preferably, R2, R3, R4, R5are the same or different and independently H or C1-C4alkyl. For example, R2, R3, R4, R5may 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 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

[0069] R6is H, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4hydroxyalkyl, C1-C4alkoxy, or C1-C4haloalkoxy.

[0070] In some preferred embodiments of the application,

[0071] 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.

[0072] 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.

[0073] In another embodiment of the application, the compound of formula (I) is a compound selected from the group consisting of:

[0074] 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):

[0075] wherein R6is as defined for a compound of formula (I),

[0076] wherein m, R1, R2, R3, R4and R5are as defined for a compound of formula (I).

[0077] 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 hydridosilicone. The compound of formula (V) can be synthesized according to conventional methods or can be obtained from commercial sources. 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.

[0078] Generally, the reaction is carried out in the presence of a catalyst. As a suitable catalyst for the reaction, Karstedt's catalyst or Speier's catalyst is generally used. The amount of catalyst is also conventional. Generally, the amount of catalyst is 2 to 500 ppm, preferably 80 to 200 ppm, based on the weight of the compound of formula (V).

[0079] The reaction of the compound of formula (IV) with the compound of formula (V) is usually carried out in a solvent. As the type of the solvent, there is no particular limitation as long as it can dissolve the compound of formula (V), the compound of formula (IV) and the catalyst and does not participate in the reaction between the compound of formula (IV) and the compound of formula (V), and it is preferred that the solvent is also advantageous for the product, i.e. the compound of formula (I), to be precipitated. As the solvent, an organic solvent is usually used, and it is preferred to use petroleum ether, dichloromethane, toluene or any mixture thereof. 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 (V) and the compound of formula (IV).

[0080] 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.

[0081] In order to carry out the above reaction, usually the compound of formula (V) is dissolved in the solvent together with the catalyst and aged for a certain period of time, and then the compound of formula (IV) is added thereto, 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).

[0082] The aging is usually carried out at an elevated temperature, usually at 40 to 70°C, preferably at 45 to 60°C. The aging time is usually 20 to 60 minutes, preferably 30 to 50 minutes.

[0083] The reaction temperature between the compound of formula (IV) and the compound of formula (V) is usually 80 to 110°C, preferably 85 to 100°C.

[0084] The reaction time at the reaction temperature between the compound of formula (IV) and the compound of formula (V) is usually 6 to 12 hours, preferably 7 to 9 hours.

[0085] The reaction can, of course, advantageously be carried out under stirring. After the 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 distillation under reduced pressure to remove the solvent.

[0086] In another embodiment of the process according to the present application, a compound of formula (II):

[0087] is reacted with a compound of formula (III),

[0088] wherein

[0089] R6is as defined for the compound of formula (I),

[0090] to obtain a compound of formula (IV).

[0091] The reaction of the chlorine in the compound of formula (III) with the hydroxyl group in the compound of formula (II) is of the type known in the art.

[0092] Generally, the reaction is carried out in the presence of a basic catalyst. As a suitable basic catalyst for the reaction, for example, potassium hydroxide, sodium hydroxide, sodium hydride or any mixture thereof can be mentioned. The amount of catalyst is also conventional. Generally, the molar ratio of the compound of formula (II) to the basic catalyst is 1 : 1.5 to 1 : 5, preferably 1 : 2 to 1 : 3.

[0093] The reaction of the compound of formula (II) with the compound of formula (III) is generally carried out in a solvent. As the type of solvent, there is no particular limitation as long as the compound of formula (III), the compound of formula (II) and the corresponding basic catalyst can be dissolved and do not participate in the reaction between the compound of formula (II) and the compound of formula (III), and preferably the solvent also favors the precipitation of the product, i.e. the compound of formula (IV). As the solvent, generally an organic solvent is used, preferably toluene, acetone, butanone, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile or any mixture thereof is used, preferably tetrahydrofuran. The amount of solvent is also conventional, generally the amount of 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).

[0094] The molar ratio of the compound of formula (II) to the compound of formula (III) is 1 : 2.1 to 1 : 3, preferably 1 : 2.2 to 1 : 2.5.

[0095] To achieve the above reaction, generally the compound of formula (II), the compound of formula (III) and the catalyst are dissolved in a solvent, then warmed to the reaction temperature for a period of time to obtain the compound of formula (IV).

[0096] The reaction temperature between the compound of formula (II) and the compound of formula (III) is generally 50 to 90°C, preferably 55 to 70°C.

[0097] The holding time of the reaction between the compound of formula (II) and the compound of formula (III) at the reaction temperature is generally 6 to 12 hours, preferably 8 to 10 hours.

[0098] Of course, the reaction is advantageously carried out under stirring. After the completion of the reaction, the compound of formula (IV) is obtained by conventional work-up. The work-up generally includes washing (for example washing with water, after which water washing is advantageously followed by removal of water 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, optionally distillation under reduced pressure to further remove the solvent. If a product of higher purity is to be obtained, recrystallization is also possible.

[0099] The compound of formula (I) of this invention has good photopolymerization activity and can be rapidly cured under ultraviolet light; its addition can improve the surface hydrophobicity, heat resistance and tensile properties of the cured film.

[0100] According to a third aspect of the present invention, a photocurable composition is provided, comprising a compound of formula (I) as a polymerizable monomer. In addition to comprising the compound of formula (I) of the present invention, the photocurable composition may also comprise a cationic photoinitiator for ring-opening polymerization (a photoinitiator capable of initiating cationic polymerization) and optionally other monomers or oligomers containing cationic photocurable groups such as vinyl ether double bonds, alicyclic epoxy groups, or oxetane groups, for example, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate (E4221) or 4-vinylepoxycyclohexane (VOH). The photocurable composition of the present invention can be a photocurable coating composition, an adhesive composition, a photocurable ink composition, or a photoresist composition, etc. After curing, the resulting cured product exhibits good tensile properties, excellent hydrophobicity, and good heat resistance.

[0101] Iodonium salts and thioonium salts are commonly used photoinitiators for ring-opening polymerization. Advantageously, the iodonium salt photoinitiators and thioonium salt photoinitiators respectively have the following general formulas (A) and (B):

[0102] in

[0103] R a R b R c R d and R e Each is an unreplaced C6-C. 10 aryl, or selected from halogen, nitro, carbonyl, C1-C 12 Alkyl, C1-C 12 Alkoxy, phenylthio, phenyl, and substituted phenyl groups substituted at C6-C 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

[0104] Y and Z are non-nucleophilic anions, such as trifluoromethanesulfonate, toluenesulfonate, C1-C6 carboxylate, BF4-, ClO4-, PF6-, AsF6-, or SbF6-.

[0105] For example, as the photoinitiator, one or more selected from the group consisting of 4-(phenylthio)phenyl diphenylsulfonium hexafluorophosphate, 4-(phenylthio)phenyl diphenylsulfonium hexafluoroantimonate, bis(4-(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.

[0106] The amount of the photoinitiator used in the present application is conventional. The content of the 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.

[0107] The photocurable composition of the present application can further contain a sensitizer. As the sensitizer, for example, benzophenone and its derivatives such as 4-(4-methylphenylthio)benzophenone or 4,4'-bis(diethylamino)benzophenone, thioxanthone and its derivatives such as 2-isopropylthioxanthone, anthraquinone and its derivatives such as 2-ethylanthraquinone, coumarin derivatives such as 5,7-dimethoxy-3-(4-dodecylbenzoyl)coumarin, camphorquinone, phenothiazine and its derivatives, 3-(aroylmethylene)thiazolines, rhodanine and its derivatives, eosin, rhodamine, acridine, cyanine, merocyanine dyes; preferably benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, coumarin and its derivatives, and especially preferably 2-isopropylthioxanthone can be mentioned.

[0108] 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 of the present application.

[0109] According to a fourth aspect of the present application, there is provided a photocured material obtained by photocuring the photocurable composition of the present application. The photocuring conditions are not particularly limited as long as the photocurable composition of the present application is photocured. The photocured material has the advantages of good tensile properties, excellent hydrophobic properties, and good heat resistance due to the fact that the compound of formula (I) of the present application is contained as a photocurable monomer.

[0110] According to a last aspect of the present application, there is provided the use of a compound of formula (I) as a photocurable monomer in the field of photocurable materials.

[0111] The application will be further described in conjunction with specific examples. In the present application, all parts and percentages are by 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] 3-ethyl-3-chloromethyl oxetane AR Hubei Guren Science and Technology Co., Ltd.

[0117] cis-1,2-dimethylol vinyl AR Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0118] tetrahydrofuran CR Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0119] sodium hydride AR Angene Chemicals

[0120] toluene AR Beijing Chemical Plant

[0121] diphenyliodonium hexafluorophosphate (810) AR Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0122] 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221) AR Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0123] 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum(0) (Karstedt catalyst) AR Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0124] anhydrous magnesium sulfate AR Bide Pharmaceutical

[0125] 2-isopropylthioxanthone (ITX) AR Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0126] Example 1

[0127] Example 1A mixture of 240 mmol NaH dispersed in paraffin was washed with 200 mL of super dry petroleum ether solvent in three portions to remove the paraffin inside the NaH. Then, the washed NaH was added to a 250 mL three-necked flask containing 100 mL of anhydrous tetrahydrofuran. Then, 100 mmol of cis-1,2-dimethylol vinyl was added to a dropping funnel containing 100 mL of anhydrous tetrahydrofuran, which was slowly dropped into the three-necked flask under the condition of ice water bath. After the dropping was completed, the ice water bath was removed and the stirring of the reaction was continued for 1 h. Then, 220 mmol of 3-ethyl-3-chloromethyl oxetane was added to the reaction system, which was stirred uniformly and then warmed to 55°C and condensed to reflux. The reaction was completed after 10 h. 100 mL of water was slowly added to remove the remaining NaH in the reaction system, and then the tetrahydrofuran solvent in the system was removed by rotary evaporation. The solution was extracted with 100 mL of dichloromethane solvent for three times. The organic layer was collected and washed with water for 3 times, then anhydrous magnesium sulfate was added to the organic phase and dried overnight. The magnesium sulfate was removed by filtration, and finally, the product was obtained by distillation under reduced pressure, with the fraction of 140°C-150°C being collected, with a yield of 75.6%.

[0128] 1H NMR (400 MHz, Chloroform-d) δ 5.57 (t, J = 4.1 Hz, 2H), 4.04 (d, J = 4.8 Hz, 4H), 3.86 (dd, J = 149.3, 12.5 Hz, 8H), 3.52 (s, 4H), 0.87 - 0.69 (m, 6H), 1.66 (q, J = 8.1 Hz, 4H), 0.85 (t, J = 8.0 Hz, 6H).

[0129] In a three-necked flask equipped with a temperature probe and reflux condenser, 5 mmol of hydrogen-containing silicone oil (Gelest) (corresponding to the compound of formula (V) wherein m = 3, R1is n-butyl, and R2, R3, R4and R5are methyl) and 0.317 g of Karstedt catalyst with a concentration of 100 ppm were dissolved in 100 mL of anhydrous toluene, which was then warmed to 60°C for 40 min. Then, 6 mmol of compound (IV-a) was added dropwise to the three-necked flask, which was warmed to 90°C and stirred for 8 h. The solid impurities were removed by centrifugation, and the obtained 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 product was identified as compound (I-1) by1H NMR, with a yield of 62%, which is hereinafter referred to as DOX-Si3.

[0130] DOX-Si3: 1H NMR (400 MHz, Chloroform-d) δ 4.10–3.63 (m, 8H), 3.61–3.48 (m, 2H), 3.48–3.31 (m, 6H), 1.88 (ddt, J = 48.2, 12.5, 6.7 Hz, 2H), 1.79–1.47 (m, 4H), 1.41 (p, J = 7.0 Hz, 1H), 1.24 (dp, J = 14.7, 6.9 Hz, 4H), 0.94 (t, J = 7.7 Hz, 3H), 0.86 (td, J = 8.2, 3.8 Hz, 6H), 0.73 (hept, J = 6.5 Hz, 2H), 0.02 (dd, J = 11.8, 7.6 Hz, 24H).

[0131] Example 2

[0132] 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 = 6, R1is n-butyl and R2, R3, R4and R5are methyl) and 0.634 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-2), hereinafter referred to as DOX-Si6, with a yield of 64%.

[0133] DOX-Si6: 1 H NMR (400 MHz, Chloroform-d) δ 4.12–3.62 (m, 8H), 3.61–3.30 (m, 8H), 1.87 (ddq, J = 50.6, 13.9, 7.1 Hz, 2H), 1.78–1.56 (m, 4H), 1.41 (p, J = 7.0 Hz, 1H), 1.26 (qq, J = 14.5, 7.2 Hz, 4H), 0.93 (t, J = 7.8 Hz, 3H), 0.85 (td, J = 8.0, 2.6 Hz, 6H), 0.73 (hept, J = 6.8, 6.3 Hz, 2H), 0.18–-0.08 (m, 42H).

[0134] Example 3

[0135] In a three-necked flask equipped with a temperature probe and a reflux condenser, 5 mmol of hydrosilicone fluid (Gelest) corresponding to the 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 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 the resulting solution was distilled under reduced pressure at 300 Pa and 40 °C to obtain the product. The compound (I-3) was identified by1H NMR spectroscopy and had a yield of 66%, hereinafter referred to as DOX-Si9.

[0136] DOX-Si9: 1 H NMR (400 MHz, Chloroform-d) δ 4.16 - 3.63 (m, 8H), 3.64 - 3.28 (m, 8H), 1.87 (ddq, J = 54.2, 13.9, 7.1 Hz, 2H), 1.76 - 1.54 (m, 4H), 1.40 (p, J = 7.0 Hz, 1H), 1.35 - 1.18 (m, J = 7.1, 5.0 Hz, 4H), 0.94 (t, J = 7.8 Hz, 3H), 0.84 (t, J = 8.2 Hz, 6H), 0.73 (hept, J = 6.8, 6.3 Hz, 2H), 0.44 - -0.40 (m, 60H).

[0137] Example 4

[0138] In a three-necked flask equipped with a temperature probe and a reflux condenser, 5 mmol of hydrosilicone fluid (Gelest) corresponding to the 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 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 the resulting solution was distilled under reduced pressure at 300 Pa and 40 °C to obtain the product. The compound (I-3) was identified by1H NMR spectroscopy and had a yield of 66%, hereinafter referred to as DOX-Si9. 15 .

[0139] DOX-Si15 : 1 H NMR (400 MHz, Chloroform-d) δ 4.16 - 3.63 (m, 8H), 3.64 - 3.28 (m, 8H), 1.87 (ddq, J = 54.2, 13.9, 7.1 Hz, 2H), 1.76 - 1.54 (m, 4H), 1.40 (p, J = 7.0 Hz, 1H), 1.35 - 1.18 (m, J = 7.1, 5.0 Hz, 4H), 0.94 (t, J = 7.8 Hz, 3H), 0.84 (t, J = 8.2 Hz, 6H), 0.73 (hept, J = 6.8, 6.3 Hz, 2H), 0.44 - -0.40 (m, 96H).

[0140] Example 5

[0141] The purpose of this example is to illustrate the photopolymerization performance of the compound of the present application. The preparation process of the photocuring composition is as follows:

[0142] X1 mol of the above compound (I-1), X2 mol of E4221 (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylate), X3 mol of VOH (4-vinyl epoxycyclohexane), X4 mol of the photoinitiator diphenyl iodonium hexafluorophosphate (810) and X5 mol of the sensitizer 2-isopropylthioxanthone (ITX) are weighed into a brown bottle and stirred uniformly, and stored in the dark. Taking the photocuring composition DOX-Si3-3.0% as an example, the molar ratio of each component is: 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. DOX-Si3, DOX-Si6 and DOX-Si9) in each photopolymerization system is shown in Tables 1-3 below, X2+X3 is fixed at 100 and X2:X3 = 1:1 as described above, and X4 and X5 remain unchanged.

[0143] A mixture of the photoinitiator diphenyl iodonium hexafluorophosphate (810) and 2-isopropylthioxanthone (ITX, sensitizer) in a molar ratio of 2:1 is used as the photoinitiating system, and the photopolymerization kinetic performance in the presence of compounds (I-1) to (I-3) is tested by the 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 is investigated. The vibration absorption peak of C-O-C of the ternary oxygen heterocycle of the monomers E4221 and VOH used is located at 750 cm -1The vibration absorption peak of C-O-C of the tetraoxacycle of compounds (I-1) to (I-3) as the polymerization monomer is 980 cm -1 The photocurable liquid composed of the monomer and the photoinitiator was uniformly applied on the potassium bromide salt tablet (a little photocurable liquid was taken up with a fine tube, a dot was put on the potassium bromide salt tablet, and then it was uniformly spread), and the liquid sample was irradiated with 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 either end, and the irradiation intensity was 20 mW cm -2 The real-time conversion rate and the polymerization rate of the monomer 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. DOX-Si3, DOX-Si6 and DOX-Si9) are shown in Figures 1-3 and Tables 1-3, respectively (in the figures and the following tables, for example, DOX-Si3-3.0% means that the content of X1 in the formula is 3.0 mol%). The results show that the addition of compounds (I-1) to (I-3) can significantly improve the conversion rate and the conversion rate of the monomer of the E4221 / VOH system. In addition, the conversion rate of the alicyclic epoxy can be significantly improved by adding a small amount (3-12 mol%) of compounds (I-1) to (I-3), and the maximum conversion rate reaches at least about 65%. As can be seen from Figures 4-6, the conversion rate of compounds (I-1) to (I-3) is about 80%. Therefore, the compounds of the present application can improve the photopolymerization performance of the monomer of the E4221 / VOH system, and the compounds of the present application have excellent photopolymerization activity.

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

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

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

[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-mentioned compounds (I-1) to (I-3) (i.e. DOX-Si3, DOX-Si6 and DOX-Si9), X2 mol of E4221, X3 mol of VOH, 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, the molar ratio of each component in the formula was: monomer (X1): E4221 (X2): VOH (X3): 810 (X4): ITX (X5) = 9:50:50:1:0.5. The uniformly stirred photosensitive liquid was added into a 6 mm x 8 mm x 70 mm 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 taken out after irradiation for 900 s, and water contact angle test was performed.

[0151] The surface hydrophobicity of the photocured film was characterized by using a DSA25 water contact angle tester, and the test temperature was 25°C. At the same time, a blank E4221 / VOH cured film was prepared by the same method as a reference. 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 does not add the compounds of the present application, the water contact angle of the cured film is 54.3°, and after adding one of the compounds (I-1) to (I-3), the water contact angle of the cured film is significantly improved, reaching 96.6°, 99.7° and 102.5°, respectively. The contact angle of the cured film obtained by adding one of the compounds (I-1) to (I-3) is more than 80°. Therefore, the compounds of the present application can significantly improve the surface hydrophobicity of the cured film.

[0153] Example 7

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

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

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

[0157] Example 8

[0158] The purpose of this example is to show that the compounds of the present application can improve the tensile properties of photocured films.

[0159] The photocured films in the presence of compounds (I-1) to (I-3) respectively were prepared in exactly the same way as described in Example 6. Then the tensile properties of the photocured films were tested by 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 photocured film was prepared by the same method as a reference. The results are shown in Table 5 and Figure 9.

[0160] As can be seen from 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 adding one of compounds (I-1) to (I-3) respectively, the tensile strength and the elongation at break of the photocured films were gradually increased. Therefore, the compounds of the present application can significantly improve the tensile properties of the photocured films.

[0161] Table 5: Tensile properties data of photocured films using compounds (I-1) to (I-3) (i.e. DOX-Si3, DOX-Si6 and DOX-Si9)

Claims

1. Compound of formula (I): 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.

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 R1is C1-C6alkyl or C1-C6alkoxy; preferably R1is C1-C4alkyl or C1-C4alkoxy; 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 R6is H, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4hydroxyalkyl, C1-C4alkoxy or C1-C4haloalkoxy.

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; R1is C1-C4alkyl; R2, R3, R4, R5are the same or different and independently C1-C4alkyl; and R6is H or C1-C4alkyl.

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, R4and R5are 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 from 2 to 500 ppm, preferably from 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 from 1 :0.65 to 1 :1.5, preferably from 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 a temperature from 80 to 110 °C, preferably from 85 to 100 °C; and / or the reaction between the compound of formula (IV) and the compound of formula (V) is carried out for a period of time from 6 to 12 hours, preferably from 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 R6is 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 potassium hydroxide, sodium hydroxide, sodium hydride or any mixture thereof; more preferably the molar ratio of the compound of formula (II) to the basic catalyst is from 1 :1.5 to 1 :5, preferably from 1 :2 to 1 :3; and / or the molar ratio of the compound of formula (II) to the compound of formula (III) is from 1 :2.1 to 1 :3, preferably from 1 :2.2 to 1 :2.5; and / or the reaction between the compound of formula (II) and the compound of formula (III) is carried out at a temperature from 50 to 90 °C, preferably from 55 to 70 °C; and / or the reaction between the compound of formula (II) and the compound of formula (III) is carried out for a period of time from 6 to 12 hours, preferably from 8 to 10 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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