阅读说明：本技术 丁香酚生物基含硅氧杂环丁烷单体及其制备方法 (Eugenol bio-based silicon-containing oxetane monomer and preparation method thereof ) 是由 孙芳 杨宗鑫 邹应全 于 2021-06-21 设计创作，主要内容包括：本发明涉及一种丁香酚生物基含硅氧杂环丁烷单体,制备该单体的方法,包含该单体的可光固化组合物和由该可光固化组合物得到的光固化材料。本发明的丁香酚生物基含硅氧杂环丁烷单体具有良好的聚合速率和转化率且促进其他阳离子单体聚合,并且由其得到的光固化材料具有良好的机械性能和热稳定性,疏水性能优良,抗沾污,抗指纹。(The present invention relates to a eugenol bio-based silicon-containing oxetane monomer, a method for preparing the monomer, a photocurable composition comprising the monomer and a photocurable material obtained from the photocurable composition. The eugenol bio-based silicon-containing oxetane monomer disclosed by the invention has good polymerization rate and conversion rate, can promote the polymerization of other cationic monomers, and the obtained photocuring material has good mechanical property and thermal stability, excellent hydrophobic property, and is anti-staining and anti-fingerprint.)

1. A compound of the formula (I):

wherein

m is 1 to 50;

l is a direct bond or a divalent linking group having 1 to 30 carbon atoms;

R₁、R₂、R₃、R₄、R₅identical or different and independently an organic group having 1 to 12 carbon atoms; and

R₆is H, halogen, C₁-C₆Alkyl radical, C₁-C₆Haloalkyl, C₁-C₆Hydroxyalkyl radical, C₁-C₆Alkoxy or C₁-C₆A haloalkoxy group.

2. A compound according to claim 1, wherein

m is 1 to 30;

R₁is C₁-C₁₂Alkyl or C₁-C₁₂An alkoxy group;

R₂、R₃、R₄、R₅are the same or different and are independently C₆-C₁₀Aryl radical, C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₁₂Alkyl, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₁₂Alkoxy radical, and

l is a direct bond, C₁-C₃₀Alkylene radical, C₁-C₃₀Alkyleneoxy groups substituted by one or more groups independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀Alkylene, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀An alkylene-oxy group, a carboxyl group,

wherein R is_aIs H or C₁-C₄An alkyl group.

3. A compound according to claim 1 or 2, which satisfies at least one, preferably all, of the following definitions:

-m is from 1 to 20, preferably from 2 to 15;

-R₁is C₁-C₆Alkyl or C₁-C₆An alkoxy group; r₁Preferably C₁-C₄Alkyl or C₁-C₄An alkoxy group;

-R₂、R₃、R₄、R₅identical or different and independently of one another is C₆-C₁₀Aryl radical, C₁-C₆Alkyl radical, C₁-C₆Alkoxy or by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₆Alkyl radical, wherein R_aIs H or C₁-C₄An alkyl group; preferably, R is₂、R₃、R₄、R₅Identical or different and independently of one another is phenyl, C₁-C₄Alkyl radical, C₁-C₄Alkoxy or by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₄Alkyl radical, wherein R_aIs H or C₁-C₄An alkyl group;

-R₆is H, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Hydroxyalkyl radical, C₁-C₄Alkoxy or C₁-C₄A haloalkoxy group;

-L is C₂-C₃₀Alkylene radical, C₂-C₃₀Alkyleneoxy groups substituted by one or more groups independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀Alkylene, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀Alkyleneoxy radicals, in which R_aIs H or C₁-C₄An alkyl group.

4. A compound according to claim 1, wherein

m is 1 to 9;

R₁is C₁-C₄Alkyl or C₁-C₄An alkoxy group;

R₂、R₃、R₄、R₅identical or different and independently of one another are phenyl, C₁-C₄Alkyl radical, C₁-C₄Alkoxy or by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₁-C₄Alkyl radical, wherein R_aIs H or C₁-C₄An alkyl group;

R₆is H, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Hydroxyalkyl radical, C₁-C₄Alkoxy or C₁-C₄A haloalkoxy group; and

l is L₁-O-L₂Wherein L is₁And L₂Independently of one another, is a divalent linking group having 1 to 20, preferably 1 to 15, carbon atoms, more preferably C₁-C₁₅An alkylene group;

it is preferable that the first and second liquid crystal layers are formed of,

m is 3 to 9;

R₁is C₁-C₄An alkyl group;

R₂、R₃、R₄、R₅are the same or different and are independently C₁-C₄An alkyl group;

R₆is H or C₁-C₄Alkyl radicals, and

l is L₁-O-L₂Wherein L is₁And L₂Independently of one another are C₁-C₆An alkylene group.

5. The compound according to any one of claims 1 to 4, 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 (VI) with a compound of formula (VII) to give a compound of formula (I)

Wherein L and R₆As defined in any one of claims 1 to 5,

wherein m and R₁、R₂、R₃、R₄And R₅As defined in any one of claims 1 to 5.

7. The method according to claim 6, wherein L is L₁-O-L₂Wherein L is₁And L₂Independently of one another, are divalent linking groups having 1 to 20, preferably 1 to 15, carbon atoms, more preferably C₁-C₁₅Alkylene, especially C₁-C₆An alkylene group.

8. The process according to claim 6 or 7, wherein the compound of formula (VI) is prepared by:

(1) reacting a compound of formula (ii):

with a compound of the formula (III),

wherein L is₁Is a divalent linking group having 1 to 20, preferably 1 to 15 carbon atoms, more preferably C₁-C₁₅Alkylene, especially C₁-C₆Alkylene and X is halogen, for example fluorine, chlorine, bromine or iodine,

to obtain the compound of formula (IV)

Wherein L is₁As defined for the compound of formula (III);

and

(2) reacting a compound of formula (IV) with a compound of formula (V) to give a compound of formula (VI)

Wherein L is₂Is a divalent linking group having 1 to 20, preferably 1 to 15 carbon atoms, more preferably C₁-C₁₅Alkylene, especially C₁-C₆Alkylene radical, R₆As defined in any one of claims 1 to 5, and X is halogenElements such as chlorine, bromine or iodine.

9. The method according to claim 8, wherein the reaction in step (1) satisfies at least one of the following conditions:

-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 sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably in a molar ratio of the compound of formula (ii) to the basic catalyst of from 1:1 to 1: 5;

-the molar ratio of compound of formula (ii) to compound of formula (iii) is from 1:0.75 to 1: 1.5;

the reaction between the compound of formula (II) and the compound of formula (III) is carried out at a temperature of 30 to 120 ℃, preferably 40 to 70 ℃;

the reaction between the compound of formula (II) and the compound of formula (III) is carried out for 3 to 16 hours, preferably for 4 to 10 hours.

10. The method according to claim 8 or 9, wherein the reaction in step (2) satisfies at least one of the following conditions:

-the reaction of the compound of formula (iv) with the compound of formula (vi) is carried out in the presence of a basic catalyst, preferably sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably in a molar ratio of the compound of formula (iv) to the basic catalyst of from 1:1 to 1: 5;

-the molar ratio of compound of formula (iv) to compound of formula (vi) is from 1:0.75 to 1: 1.5;

-the reaction between the compound of formula (iv) and the compound of formula (vi) is carried out at 40-100 ℃, preferably at 60-90 ℃; preferably, the reaction is carried out for 3 to 24 hours, preferably 4 to 10 hours.

11. A process according to any one of claims 6 to 10 wherein the reaction of the compound of formula (vi) with the compound of formula (vii) satisfies at least one of the following conditions:

the reaction of the compound of the formula (VI) with the compound of the formula (VII) is carried out in the presence of Karstedt's catalyst or SpeI er catalyst, preferably in an amount of from 2 to 500ppm, based on the weight of the compound of the formula (VII);

-the molar ratio of compound of formula (vi) to compound of formula (vii) is from 1:0.75 to 1: 1.5;

the reaction between the compound of formula (VI) and the compound of formula (VII) is carried out at a temperature of 80 to 110 ℃, preferably 85 to 100 ℃;

the reaction between the compound of formula (VI) and the compound of formula (VII) is carried out for 3 to 6 hours, preferably 3.5 to 5.5 hours.

12. A photocurable composition comprising as polymerized monomers a compound of formula (i) according to any one of claims 1 to 5.

13. A photocurable material obtained from the photocurable composition of claim 12.

14. Use of compounds of formula (I) according to any one of claims 1 to 5 in photocurable coatings, adhesives, inks and photoresists.

15. A compound of formula (VI):

wherein L and R₆As defined in any one of claims 1 to 5.

Technical Field

The invention relates to the field of photocuring materials, in particular to a eugenol bio-based silicon-containing oxetane monomer. The present invention also relates to a process for preparing the monomer, a photocurable composition comprising the monomer and a photocurable material obtained from the photocurable composition.

Background

Photopolymerization is a process of using light to initiate the conversion of liquid oligomers or monomers with active substances into solid products. Compared with the traditional thermal polymerization technology, the high-efficiency pollution-free production can be realized by photopolymerization without using a volatile organic solvent, and a large amount of energy is saved. Therefore, the photopolymerization technology is regarded as a green process by the characteristics of low specific energy consumption requirement, quick curing, solvent-free formula, no pollution, room temperature treatment, environmental protection and the like, and is widely applied to the fields of photocuring coatings, adhesives, ink printing and the like.

Cationic photopolymerization has attracted attention for its advantages over radical photopolymerization systems, such as being free from oxygen inhibition, low shrinkage, post-curable, good mechanical properties of photocurable materials, and good adhesion to various substrates. The oxacycloalkane monomer belongs to a cationic photocuring system. The oxacycloalkane monomer is the main raw material of high-end cationic photocuring product, and the system has low viscosity and low toxicity. However, ultraviolet light curing has been rapidly developed with the advantages of energy saving, environmental protection, high efficiency, etc., and simultaneously, higher requirements are put forward on the aspects of heat resistance, water repellency, surface contamination resistance, corrosion resistance, fingerprint resistance, etc. of the light curing material. Consumers increasingly demand the appearance of products, and in addition to beautiful color and comfortable hand feeling, the products also require the surfaces to have fingerprint resistance and stain resistance, so that the product surface is not easy to leave fingerprints and other marks when in use, or the marks are easy to wipe.

In addition, most of the prepolymers and monomers currently used for photopolymerization are still fossil-based. Due to the nonrenewable nature of fossil resources and the pollution to the environment, there is an urgent need to replace fossil-based prepolymers or monomers with renewable bio-based prepolymers or monomers, making photopolymerization technology more environmentally friendly. Currently, there are fewer types of photo-curable cationic monomers that can meet the aforementioned requirements, and there is a need to develop more types of cationically curable monomers.

Disclosure of Invention

In view of the above-mentioned state of the art, the present inventors have conducted extensive and intensive studies on eugenol biobased materials in order to find a novel class of cationically photocurable monomers consisting of bio-monomers

The material is prepared from the base material, and has the advantages of high polymerization rate, good tensile property, good heat resistance, excellent hydrophobic property, stain resistance, fingerprint resistance and the like after photocuring. The inventors have unexpectedly found that the cationically photopolymerizable eugenol bio-based silicon-containing oxetane monomer of formula (I) of the invention has good polymerization rate and conversion rate and promotes polymerization of other cationic monomers, and that the photocurable material obtained therefrom has good mechanical properties, in particular tensile properties and thermal stability, excellent hydrophobic properties and resistance to staining, fingerprint.

Accordingly, it is an object of the present invention to provide a eugenol biobased silaceous oxetane monomer that is prepared from biobased materials. The monomer has good polymerization rate and conversion rate, promotes the polymerization of other cationic monomers, and the photocuring material obtained from the monomer has good mechanical properties, particularly tensile property and heat resistance, excellent hydrophobic property, stain resistance, fingerprint resistance, chemical corrosion resistance and strong aging resistance.

It is another object of the present invention to provide a method for preparing the eugenol bio-based silaceous oxetane monomer of the present invention. The preparation method is simple and feasible, mild in condition, easily available in raw materials and low in price.

It is a further object of the present invention to provide a photocurable composition comprising a eugenol biobased silatrane monomer according to the invention.

It is a further object of the present invention to provide a photocurable material obtained from the photocurable composition of the present invention.

It is a further object of the present invention to provide the use of the compounds of formula (I) according to the invention in photocurable coatings, adhesives and inks.

The technical solution for achieving the above object of the present invention can be summarized as follows:

1. a compound of the formula (I):

wherein

m is 1 to 50;

l is a direct bond or a divalent linking group having 1 to 30 carbon atoms;

R₁、R₂、R₃、R₄、R₅identical or different and independently an organic group having 1 to 12 carbon atoms; and

R₆is H, halogen, C₁-C₆Alkyl radical, C₁-C₆Haloalkyl, C₁-C₆Hydroxyalkyl radical, C₁-C₆Alkoxy or C₁-C₆A haloalkoxy group.

2. The compound according to item 1, wherein

m is 1 to 30;

R₁is C₁-C₁₂Alkyl or C₁-C₁₂An alkoxy group;

R₂、R₃、R₄、R₅are the same or different and are independently C₆-C₁₀Aryl radical, C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₁₂Alkyl, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₁₂Alkoxy radical, and

l is a direct bond, C₁-C₃₀Alkylene radical, C₁-C₃₀Alkyleneoxy groups substituted by one or more groups independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀Alkylene, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀An alkylene-oxy group, a carboxyl group,

wherein R is_aIs H or C₁-C₄An alkyl group.

3. A compound according to item 1 or 2, which satisfies at least one, preferably all, of the following definitions:

-m is from 1 to 20, preferably from 2 to 15;

-R₁is C₁-C₆Alkyl or C₁-C₆An alkoxy group; r₁Preferably C₁-C₄Alkyl or C₁-C₄An alkoxy group;

-R₂、R₃、R₄、R₅identical or different and independently of one another is C₆-C₁₀Aryl radical, C₁-C₆Alkyl radical, C₁-C₆Alkoxy or by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₆Alkyl radical, wherein R_aIs H or C₁-C₄An alkyl group; preferably, R is₂、R₃、R₄、R₅Identical or different and independently of one another is phenyl, C₁-C₄Alkyl radical, C₁-C₄Alkoxy or by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₄Alkyl radical, wherein R_aIs H or C₁-C₄An alkyl group;

-R₆is H, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Hydroxyalkyl radical, C₁-C₄Alkoxy or C₁-C₄A haloalkoxy group;

-L is C₂-C₃₀Alkylene radical, C₂-C₃₀Alkyleneoxy groups substituted by one or more groups independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀Alkylene, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀Alkyleneoxy radicals, in which R_aIs H or C₁-C₄An alkyl group.

4. The compound according to item 1, wherein

m is 1 to 9;

R₁is C₁-C₄Alkyl or C₁-C₄An alkoxy group;

R₂、R₃、R₄、R₅the same or different, and the same or different,and independently is phenyl, C₁-C₄Alkyl radical, C₁-C₄Alkoxy or by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₁-C₄Alkyl radical, wherein R_aIs H or C₁-C₄An alkyl group;

R₆is H, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Hydroxyalkyl radical, C₁-C₄Alkoxy or C₁-C₄A haloalkoxy group; and

l is L₁-O-L₂Wherein L is₁And L₂Independently of one another, is a divalent linking group having 1 to 20, preferably 1 to 15, carbon atoms, more preferably C₁-C₁₅An alkylene group;

it is preferable that the first and second liquid crystal layers are formed of,

m is 3 to 9;

R₁is C₁-C₄An alkyl group;

R₂、R₃、R₄、R₅are the same or different and are independently C₁-C₄An alkyl group;

R₆is H or C₁-C₄Alkyl radicals, and

l is L₁-O-L₂Wherein L is₁And L₂Independently of one another are C₁-C₆An alkylene group.

5. A compound according to any one of items 1 to 4, 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 items 1 to 5, comprising:

reacting a compound of formula (VI) with a compound of formula (VII) to give a compound of formula (I)

Wherein L and R₆As defined in any one of items 1 to 5,

wherein m and R₁、R₂、R₃、R₄And R₅As defined in any one of items 1 to 5.

7. The method according to item 6, wherein L is L₁-O-L₂Wherein L is₁And L₂Independently of one another, are divalent linking groups having 1 to 20, preferably 1 to 15, carbon atoms, more preferably C₁-C₁₅Alkylene, especially C₁-C₆An alkylene group.

8. The process according to item 6 or 7, wherein the compound of formula (VI) is prepared by:

(1) reacting a compound of formula (ii):

with a compound of the formula (III),

wherein L is₁Is a divalent linking group having 1 to 20, preferably 1 to 15 carbon atoms, more preferably C₁-C₁₅Alkylene, especially C₁-C₆Alkylene and X is halogen, for example fluorine, chlorine, bromine or iodine,

to obtain the compound of formula (IV)

Wherein L is₁As defined for the compound of formula (III);

and

(2) reacting a compound of formula (IV) with a compound of formula (V) to give a compound of formula (VI)

Wherein L is₂Is a divalent linking group having 1 to 20, preferably 1 to 15 carbon atoms, more preferably C₁-C₁₅Alkylene, especially C₁-C₆Alkylene radical, R₆As defined in any one of items 1 to 5, and X is halogen, for example chlorine, bromine or iodine.

9. The method according to item 8, wherein the reaction in step (1) satisfies at least one of the following conditions:

-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 sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably in a molar ratio of the compound of formula (ii) to the basic catalyst of from 1:1 to 1: 5;

-the molar ratio of compound of formula (ii) to compound of formula (iii) is from 1:0.75 to 1: 1.5;

the reaction between the compound of formula (II) and the compound of formula (III) is carried out at a temperature of 30 to 120 ℃, preferably 40 to 70 ℃;

the reaction between the compound of formula (II) and the compound of formula (III) is carried out for 3 to 16 hours, preferably for 4 to 10 hours.

10. The method according to item 8 or 9, wherein the reaction in step (2) satisfies at least one of the following conditions:

-the reaction of the compound of formula (iv) with the compound of formula (vi) is carried out in the presence of a basic catalyst, preferably sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably in a molar ratio of the compound of formula (iv) to the basic catalyst of from 1:1 to 1: 5;

-the molar ratio of compound of formula (iv) to compound of formula (vi) is from 1:0.75 to 1: 1.5;

-the reaction between the compound of formula (iv) and the compound of formula (vi) is carried out at 40-100 ℃, preferably at 60-90 ℃; preferably, the reaction is carried out for 3 to 24 hours, preferably 4 to 10 hours.

11. The process according to any one of items 6 to 10, wherein the reaction of the compound of formula (vi) with the compound of formula (vii) satisfies at least one of the following conditions:

the reaction of the compound of the formula (VI) with the compound of the formula (VII) is carried out in the presence of Karstedt's catalyst or SpeI er catalyst, preferably in an amount of from 2 to 500ppm, based on the weight of the compound of the formula (VII);

-the molar ratio of compound of formula (vi) to compound of formula (vii) is from 1:0.75 to 1: 1.5;

the reaction between the compound of formula (VI) and the compound of formula (VII) is carried out at a temperature of 80 to 110 ℃, preferably 85 to 100 ℃;

the reaction between the compound of formula (VI) and the compound of formula (VII) is carried out for 3 to 6 hours, preferably 3.5 to 5.5 hours.

12. A photocurable composition comprising a compound of formula (I) according to any one of items 1 to 5 as a polymerized monomer.

13. A photocurable material obtained from the photocurable composition of item 12.

14. Use of a compound of formula (I) according to any one of items 1 to 5 in photocurable coatings, adhesives, inks and photoresists.

15. A compound of formula (VI):

wherein L and R₆As defined in any one of items 1 to 5.

Drawings

Figure 1 is a graph of E4221 conversion as a function of irradiation time in a system comprising compound 1 prepared in example 1.

Figure 2 is a graph of E4221 conversion as a function of irradiation time in a system comprising compound 2 prepared in example 2.

Figure 3 is a graph of E4221 conversion as a function of irradiation time in a system comprising compound 3 prepared in example 3.

Figure 4 is a graph of the conversion of compound 1 versus irradiation time for a system containing compound 1 prepared in example 1.

Figure 5 is a graph of the conversion of compound 2 over irradiation time for a system containing compound 2 prepared in example 2.

Figure 6 is a graph of the conversion of compound 3 versus irradiation time for a system containing compound 3 prepared in example 3.

Fig. 7 is a contact angle plot for a blank E4221 cured film and cured films of systems comprising compounds 1-3 prepared from each of examples 1-3.

FIG. 8 is a thermogravimetric plot of a blank E4221 cured film and cured films of systems comprising compounds 1-3 prepared for each of examples 1-3.

FIG. 9 is a graph of the mechanical properties of a blank E4221 cured film and cured films of systems comprising compounds 1-3 prepared from each of examples 1-3.

Detailed Description

Embodiments of the present invention will be described below. However, the present invention is not limited to the following embodiments.

Herein, the numerical ranges are used to indicate ranges in which the numerical values recited before and after are respectively the minimum value and the maximum value.

Specific values (including range endpoints) disclosed herein for related features can be combined with each other to form new ranges.

According to one aspect of the present invention, there is provided a compound of formula (i):

wherein

m is 1 to 50;

l is a direct bond or a divalent linking group having 1 to 30 carbon atoms;

R₁、R₂、R₃、R₄、R₅identical or different and independently an organic group having 1 to 12 carbon atoms; and

R₆is H, halogen, C₁-C₆Alkyl radical, C₁-C₆Haloalkyl, C₁-C₆Hydroxyalkyl radical, C₁-C₆Alkoxy or C₁-C₆A haloalkoxy group.

In the present invention, the prefix "C_n-C_m"in each case denotes that the number of carbon atoms contained in the radical is n to m.

"halogen" refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferred that the halogen comprises fluorine, chlorine or a combination thereof.

The term "C" as used herein_n-C_mAlkyl "means a branched or unbranched saturated hydrocarbon radical having n-m, for example 1-12, preferably 1-6, particularly preferably 1-4, carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and isomers thereof. C₁-C₆The alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, t-butyl, pentyl, isopentyl, hexyl and isomers thereof. C₁-C₄The alkyl group may be methyl, ethyl, propyl, 1-methylethyl, butyl, or,1-methylpropyl, 2-methylpropyl, 1-dimethylethyl and isomers thereof.

The term "C" as used herein₆-C_mAryl "refers to monocyclic, bicyclic or higher ring aromatic hydrocarbon radicals containing from 6 to m carbon atoms, for example from 6 to 10 carbon atoms. As C₆-C_mAs examples of the aryl group, there may be mentioned phenyl, tolyl, ethylphenyl, propylphenyl, butylbenzyl, xylyl, methylethylphenyl, diethylphenyl, methylpropylphenyl, naphthyl and the like; phenyl or naphthyl, especially phenyl, is preferred.

The term "C" as used herein_n-C_mAlkoxy "means at C_n-C_mOpen chain C corresponding to alkyl_n-C_mC having an oxygen atom as a linking group bonded to any carbon atom of the alkane_n-C_mAlkyl radicals, e.g. C₁-C₁₂Alkoxy, more preferably C₁-C₆Alkoxy, particularly preferably C₁-C₄An alkoxy group. C₁-C₆The alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy, isopentoxy, hexoxy, and isomers thereof. C₁-C₄The alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and isomers thereof.

The term "C" as used herein_n-C_mHaloalkyl "means C substituted with one or more halogen atoms which may be the same or different_n-C_mAlkyl radicals, e.g. C₁-C₁₂Haloalkyl, preferably C₁-C₆Haloalkyl, particularly preferably C₁-C₄A haloalkyl group. As C_n-C_mExamples of haloalkyl radicals which may be mentioned are the monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, 1-chloromethylethyl, monochlorobutyl, 1-chloromethylpropyl, 2-chloromethylpropyl, 1-dichloromethylethyl, monochloropentyl, 1-chloromethylbutyl, 2-chloromethylbutyl, 3-chloromethylbutyl, 2-dichloromethylpropyl, 1-chloroethylpropyl, monochlorohexyl, 1-dichloromethylpropylMethylpropyl, 1, 2-dichloromethylpropyl, 1-chloromethylpentyl, 2-chloromethylpentyl, 3-chloromethylpentyl, 4-chloromethylpentyl, 1-dichloromethylbutyl, 1, 2-dichloromethylbutyl, 1, 3-dichloromethylbutyl, 2, 2-dichloromethylbutyl, 2, 3-dichloromethylbutyl, 3-dichloromethylbutyl, 1-chloroethylbutyl, 2-chloroethylbutyl, 1, 2-trichloromethylpropyl, 1,2, 2-trichloromethylpropyl, 1-chloroethyl-1-methylpropyl, 1-ethyl-2-chloromethylpropyl and isomers thereof.

The term "C" as used herein_n-C_mHaloalkoxy "means C substituted by one or more of the same or different halogen atoms_n-C_mAlkoxy radicals, e.g. C₁-C₁₂Haloalkoxy, more preferably C₁-C₆Haloalkoxy, particularly preferably C₁-C₄A haloalkoxy group. As C_n-C_mAs examples of the haloalkoxy group, there may be mentioned monochlorooxy group, 2-chloroethoxy group, 3-chloropropoxy group, 2-chloroisopropoxy group, 4-chloro-n-butoxy group, 3-chloro-sec-butoxy group, 2-chloro-tert-butoxy group, 5-chloropentyloxy group, 4-chloropentyloxy group, 6-chlorohexyloxy group and isomers thereof.

The term "C" as used herein_n-C_mHydroxyalkyl "means at C_n-C_mOpen chain C corresponding to alkyl_n-C_mC having a hydroxy group bonded to any carbon atom of the alkane_n-C_mAlkyl radicals, e.g. C₁-C₆Hydroxyalkyl, particularly preferably C₁-C₄Hydroxyalkyl radicals, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl and isomers thereof.

The term C as used herein₁-C₃₀Alkylene radicals including C₁-C₂₆Alkylene radical, C₁-C₁₈Alkylene radical, C₁-C₁₂Alkylene radical, C₁-C₆Alkylene radical, C₂-C₂₆Alkylene radical, C₂-C₁₈Alkylene radical, C₂-C₁₂Alkylene radical, C₂-C₆Alkylene radical, C₃-C₂₆Alkylene radical, C₃-C₁₈Alkylene, or a mixture thereof,C₃-C₁₂Alkylene or C₃-C₆An alkylene group.

The term C as used herein₁-C₃₀Alkyleneoxy radicals comprising C₁-C₂₆Alkyleneoxy group, C₁-C₁₈Alkyleneoxy group, C₁-C₁₂Alkyleneoxy group, C₁-C₆Alkyleneoxy group, C₂-C₂₆Alkyleneoxy group, C₂-C₁₈Alkyleneoxy group, C₂-C₁₂Alkyleneoxy group, C₂-C₆Alkyleneoxy group, C₃-C₂₆Alkyleneoxy group, C₃-C₁₈Alkyleneoxy group, C₃-C₁₂Alkyleneoxy or C₃-C₆An alkylene oxide group.

In this context, the propylene group between the silicon and the benzene ring in the compounds of formula (I) may be-CH₂-CH₂-CH₂-or-CH (CH)₃)-CH₂-, and is preferably-CH (CH)₃)-CH₂-。

Herein, the propenyl group may be-CH ═ CH-CH₃or-CH₂-CH＝CH₂And is preferably-CH ═ CH-CH₃。

According to the invention, m is typically 1 to 50, such as 1 to 40, 1 to 30, 1 to 20, 1 to 18, 1 to 15, 1 to 12, 1 to 9, 2 to 40, 2 to 30, 2 to 20, 2 to 18, 2 to 15, 2 to 12, 2 to 9, 3 to 40, 3 to 30, 3 to 20, 3 to 18, 3 to 15, 3 to 12 or 3 to 9, such as 3,4, 5, 6, 7, 8 or 9.

R₁、R₂、R₃、R₄、R₅Identical or different and independently are organic radicals having from 1 to 12 carbon atoms, for example organic radicals having from 1 to 6 or from 1 to 4 carbon atoms.

According to a preferred embodiment of the invention, R₁Is usually C₁-C₁₂Alkyl or C₁-C₁₂An alkoxy group. Preferably, R is₁Is C₁-C₆Alkyl or C₁-C₆An alkoxy group. It is particularly preferred that R₁Is C₁-C₄Alkyl or C₁-C₄An alkoxy group. Especially R₁Is C₁-C₄An alkyl group. For example, R₁Is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

According to a preferred embodiment of the invention, R₂、R₃、R₄、R₅Are identical or different and are usually independently C₆-C₁₀Aryl radical, C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy or by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₁-C₁₂Alkyl radical, wherein R_aIs H or C₁-C₄An alkyl group. Preferably, R is₂、R₃、R₄、R₅Are the same or different and are independently C₆-C₁₀Aryl radical, C₁-C₆Alkyl radical, C₁-C₆Alkoxy or by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₁-C₆Alkyl radical, wherein R_aIs H or C₁-C₄An alkyl group. It is particularly preferred that R₂、R₃、R₄、R₅Identical or different and independently of one another are phenyl, C₁-C₄Alkyl radical, C₁-C₄Alkoxy or by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₁-C₄Alkyl radical, wherein R_aIs H or C₁-C₄An alkyl group. Especially R₂、R₃、R₄、R₅Are the same or different and are independently C₁-C₄An alkyl group. For example, R₂、R₃、R₄、R₅The same or different and are independently phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy or tert-butoxy.

It will be understood by those skilled in the art that spacing by said non-adjacent heteroatoms means that there are non-adjacent heteroatoms between two carbon atoms, for example two carbon atoms of said divalent linking group.For example, an ethylene group interrupted by O may be represented as: -CH₂-O-CH₂-。

According to the invention, R₆Usually H, halogen, C₁-C₆Alkyl radical, C₁-C₆Haloalkyl, C₁-C₆Hydroxyalkyl radical, C₁-C₆Alkoxy or C₁-C₆A haloalkoxy group. Preferably, R is₆Is H, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Hydroxyalkyl radical, C₁-C₄Alkoxy or C₁-C₄A haloalkoxy group. It is particularly preferred that R₆Is H or C₁-C₄An alkyl group. For example, R₆Can be H, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxy-sec-butyl or hydroxy-tert-butyl.

According to the invention, L is a direct bond or a divalent linking group having 1 to 30 carbon atoms, for example a divalent linking group having 1 to 28, 1 to 18, 1 to 12, 2 to 30, 2 to 28, 2 to 18 or 2 to 12 carbon atoms, for example a divalent linking group having 2,3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. According to one embodiment, the divalent linking group has one or more groups independently selected from NR_aO, S, preferably O, wherein R is_aIs H or C₁-C₄An alkyl group.

In a preferred embodiment, L is a direct bond, C₁-C₃₀Alkylene radical, C₁-C₃₀Alkyleneoxy groups substituted by one or more groups independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀Alkylene, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀Alkyleneoxy radicals, in which R_aIs H or C₁-C₄An alkyl group.

In a preferred embodiment, L is a direct bond, C₁-C₁₈Alkylene radical, C₁-C₁₈Alkyleneoxy groups substituted by one or more groups independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₁₈Alkylene, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₁₈Alkyleneoxy radicals, in which R_aIs H or C₁-C₄An alkyl group.

In a preferred embodiment, L is a direct bond, C₁-C₁₂Alkylene radical, C₁-C₁₂Alkyleneoxy groups substituted by one or more groups independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₁₂Alkylene, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₁₂Alkyleneoxy radicals, in which R_aIs H or C₁-C₄An alkyl group.

In a preferred embodiment, L is a direct bond, C₂-C₁₂Alkylene radical, C₂-C₁₂Alkyleneoxy groups substituted by one or more groups independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₁₂Alkylene, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₁₂Alkyleneoxy radicals, in which R_aIs H or C₁-C₄An alkyl group.

In a preferred embodiment, L is L₁-O-L₂，L₁And L₂Independently of one another, are divalent linking groups having 1 to 20, preferably 1 to 15, 1 to 12, 1 to 6, 2 to 20, 2 to 15, 2 to 12 or 2 to 6 carbon atoms. Preferably L₁And L₂Independently of one another are C₁-C₁₅Alkylene, preferably C₁-C₁₀Alkylene, preferably C₁-C₆Alkylene, for example methylene, ethylene, propylene, butylene, pentylene or hexylene. For example, L₁Is C₁-C₆Alkylene, preferably C₂-C₆Alkylene and L₂Is C₁-C₆Alkylene, preferably C₁-C₄An alkylene group.

In one embodiment of the present invention, the propylene group between the silicon and the benzene ring in the compound of formula (I) is-CH₂-CH₂-CH₂-or-CH (CH)₃)-CH₂-, preferably-CH (CH)₃)-CH₂-。

In one embodiment of the invention, the variables in the compounds of formula (I) are defined as follows:

m is 1 to 30;

l is a direct bond or a divalent linking group having 1 to 12 carbon atoms;

R₁、R₂、R₃、R₄、R₅identical or different and independently an organic group having 1 to 6 carbon atoms; and

R₆is H, halogen, C₁-C₆Alkyl radical, C₁-C₆Haloalkyl, C₁-C₆Hydroxyalkyl radical, C₁-C₆Alkoxy or C₁-C₆A haloalkoxy group.

In one embodiment of the invention, the variables in the compounds of formula (I) are defined as follows:

m is 1 to 15;

l is a direct bond or a divalent linking group having 1 to 12 carbon atoms;

R₁、R₂、R₃、R₄、R₅identical or different and independently an organic group having 1 to 6 carbon atoms; and

R₆is H, halogen, C₁-C₆Alkyl radical, C₁-C₆Haloalkyl, C₁-C₆Hydroxyalkyl radical, C₁-C₆Alkoxy or C₁-C₆A haloalkoxy group.

In one embodiment of the invention, the variables in the compounds of formula (I) are defined as follows:

m is 1 to 30;

R₁is C₁-C₁₂Alkyl or C₁-C₁₂An alkoxy group; and

R₂、R₃、R₄、R₅are the same or different and are independently C₆-C₁₀Aryl radical, C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₁₂Alkyl, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₁₂Alkoxy radical, and

l is a direct bond, C₁-C₃₀Alkylene radical, C₁-C₃₀Alkyleneoxy groups substituted by one or more groups independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀Alkylene, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀An alkylene-oxy group, a carboxyl group,

wherein R is_aIs H or C₁-C₄An alkyl group.

In a preferred embodiment of the invention, the compounds of formula (I) according to the invention satisfy at least one, preferably all, of the following definitions:

-m is from 1 to 20, preferably from 2 to 15;

-R₁is C₁-C₆Alkyl or C₁-C₆An alkoxy group; r₁Preferably C₁-C₄Alkyl or C₁-C₄An alkoxy group;

-R₂、R₃、R₄、R₅identical or different and independently of one another is C₆-C₁₀Aryl radical, C₁-C₆Alkyl radical, C₁-C₆Alkoxy or by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₆Alkyl radical, wherein R_aIs H or C₁-C₄An alkyl group; preferably, R is₂、R₃、R₄、R₅The same asOr different and independently phenyl, C₁-C₄Alkyl radical, C₁-C₄Alkoxy or by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₄Alkyl radical, wherein R_aIs H or C₁-C₄An alkyl group;

-R₆is H, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Hydroxyalkyl radical, C₁-C₄Alkoxy or C₁-C₄A haloalkoxy group;

-L is C₂-C₃₀Alkylene radical, C₂-C₃₀Alkyleneoxy groups substituted by one or more groups independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀Alkylene, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀Alkyleneoxy radicals, in which R_aIs H or C₁-C₄An alkyl group.

In a preferred embodiment of the present invention,

m is 1 to 20;

R₁is C₁-C₁₂Alkyl or C₁-C₁₂An alkoxy group;

R₂、R₃、R₄、R₅are the same or different and are independently C₆-C₁₀Aryl radical, C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₁₂Alkyl, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₁₂Alkoxy radical, wherein R_aIs H or C₁-C₄Alkyl radicals, and

l is a direct bond, C₁-C₃₀Alkylene radical, C₁-C₃₀Alkyleneoxy groups substituted by one or more groups independently selected from NR_aO, S of a non-adjacent heteroatomSpaced C₂-C₃₀Alkylene, or substituted by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₂-C₃₀Alkyleneoxy radicals, in which R_aIs H or C₁-C₄An alkyl group.

In a preferred embodiment of the invention, the variables in the compounds of formula (I) have the following definitions:

m is 1 to 9;

R₁is C₁-C₄Alkyl or C₁-C₄An alkoxy group;

R₂、R₃、R₄、R₅identical or different and independently of one another are phenyl, C₁-C₄Alkyl radical, C₁-C₄Alkoxy or by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₁-C₄Alkyl radical, wherein R_aIs H or C₁-C₄An alkyl group;

R₆is H, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Hydroxyalkyl radical, C₁-C₄Alkoxy or C₁-C₄A haloalkoxy group; and

l is L₁-O-L₂Wherein L is₁And L₂Independently of one another, is a divalent linking group having 1 to 20, preferably 1 to 15, carbon atoms, more preferably C₁-C₁₅An alkylene group.

In a preferred embodiment of the present invention,

m is 1 to 12;

R₁is C₁-C₄Alkyl or C₁-C₄An alkoxy group;

R₂、R₃、R₄、R₅identical or different and independently of one another are phenyl, C₁-C₄Alkyl radical, C₁-C₄Alkoxy or by one or more radicals independently selected from NR_aO, S non-adjacent heteroatom-spaced C₁-C₄Alkyl radical, wherein R_aIs H or C₁-C₄An alkyl group;

R₆is H, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Hydroxyalkyl radical, C₁-C₄Alkoxy or C₁-C₄A haloalkoxy group; and

l is L₁-O-L₂Wherein L is₁And L₂Independently of one another are C₁-C₁₅An alkylene group.

In a preferred embodiment of the present invention,

m is 3 to 9;

R₁is C₁-C₄An alkyl group;

R₂、R₃、R₄、R₅are the same or different and are independently C₁-C₄An alkyl group;

R₆is H or C₁-C₄Alkyl, especially H or ethyl, and

l is L₁-O-L₂Wherein L is₁And L₂Independently of one another are C₁-C₆An alkylene group.

In another embodiment of the present invention, the compound of formula (i) is one or more compounds selected from the group consisting of:

according to a second aspect of the present invention there is provided a process for the preparation of a compound of formula (I) according to the invention,

the method comprises the following steps:

reacting a compound of formula (VI) with a compound of formula (VII) to give a compound of formula (I)

Wherein L and R₆As defined above for the compounds of formula (I).

Wherein m and R₁、R₂、R₃、R₄And R₅As defined above for the compounds of formula (I).

In one embodiment of the invention, L in the compound of formula (I) is L₁-O-L₂Wherein L is₁And L₂As defined above, C is preferred₁-C₁₅Alkylene, more preferably C₁-C₆An alkylene group. The compounds of formula (VI) may be prepared by the following steps:

(1) reacting a compound of formula (ii):

with a compound of the formula (III),

wherein L is₁Is a divalent linking group having 1 to 20, preferably 1 to 15 carbon atoms, more preferably C₁-C₁₅Alkylene, especially C₁-C₆Alkylene and X is halogen, for example fluorine, chlorine, bromine or iodine,

to obtain the compound of formula (IV)

Wherein L is₁As defined for the compound of formula (III);

and

(2) reacting a compound of formula (IV) with a compound of formula (V) to give a compound of formula (VI)

Wherein L is₂Is a divalent linking group having 1 to 20, preferably 1 to 15 carbon atoms, more preferably C₁-C₁₅Alkylene, especially C₁-C₆Alkylene and R₆As defined above for compounds of formula (I) and X is halogen, for example chlorine, bromine or iodine.

In step (1), the reaction of the phenolic hydroxyl group in the compound of formula (II) with the halogen in the compound of formula (III) is of a type known in the art, and the reaction produces a hydrogen halide. Generally, the reaction is carried out in the presence of a basic catalyst. As basic catalysts suitable for this reaction, sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof may be mentioned. The amount of catalyst used is also conventional. In general, the molar ratio of the compound of formula (II) to the basic catalyst is from 1:1 to 1:5, preferably from 1:1 to 1: 3. 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 (ii), the compound of formula (iii) 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 it is preferable that the solvent also contributes to precipitation of the product, i.e., the compound of formula (iv). As the solvent, an organic solvent is generally used, and toluene, acetone, butanone, toluene, tetrahydrofuran, cyclohexane, 1, 4-dioxane, dichloromethane, acetonitrile, or any mixture thereof is preferably used. The amount of solvent is also conventional and is generally 1.0 to 3 times the total weight of the compound of formula (II) and the compound of formula (III). The compounds of the formulae (II) and (III) are generally used in approximately equimolar amounts. Advantageously, the compound of formula (II) and the compound of formula (III) are used in a molar ratio of from 1:0.75 to 1:1.5, or from 1:1 to 1: 1.3. To achieve the above reaction, the compound of formula (II) is generally dissolved in a solvent, a basic catalyst is added, then the compound of formula (III) is added, and after the addition is complete the resulting reaction mixture is stirred well and then warmed to 30-120℃, preferably to 40-70℃. The reaction is usually continued for 3 to 16 hours, preferably for 4 to 10 hours, after the temperature is raised. The reaction is, of course, advantageously carried out with stirring. After the reaction is finished, the compound of the formula (IV) is obtained through conventional post-treatment. This work-up generally comprises extraction or washing (for example with water, which is then advantageously freed from water using an absorbent compound such as magnesium sulfate or sodium sulfate), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and distillation under reduced pressure to further remove the solvent. If a product with higher purity is to be obtained, the product can also be obtained by recrystallization or column chromatography.

In step (1), the-CH on the benzene ring in the compound of formula (II)₂-CH＝CH₂The position of the double bond in (A) may be changed in the presence of a basic catalyst to form-CH ═ CH-CH₃。

In step (2), the reaction of the terminal hydroxyl group in the compound of formula (IV) with the halogen in the compound of formula (V) is known and produces a hydrogen halide. Generally, the reaction is carried out in the presence of a catalyst. As a catalyst suitable for this reaction, sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof may be mentioned. The amount of catalyst used is also conventional. In general, the molar ratio of compound of formula (IV) to catalyst is from 1:1 to 1:5, preferably from 1:1 to 1: 3. 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 the compound of formula (iv), the compound of formula (v) and the corresponding catalyst can be dissolved and do not participate in the reaction between the compound of formula (iv) and the compound of formula (v), and it is preferable that the solvent also contributes to precipitation of the product, i.e., the compound of formula (vi). As the solvent, an organic solvent is generally used, and toluene, acetone, butanone, toluene, tetrahydrofuran, cyclohexane, 1, 4-dioxane, dichloromethane, acetonitrile, or any mixture thereof is preferably used. The amount of solvent is also conventional, and in general, the amount of solvent is 1.0 to 3 times the total weight of the compound of formula (IV) and the compound of formula (V). The compounds of the formula (IV) and (V) are generally used in approximately equimolar amounts. Advantageously, the molar ratio of compound of formula (IV) to compound of formula (IV) is from 1:0.75 to 1:1.5, or from 1:1 to 1: 1.2. To achieve the above reaction, the compound of formula (IV) and the catalyst are generally dissolved in a solvent, and a solution of the compound of formula (V) in the solvent is then added, after which the temperature is raised to 40-100 deg.C, preferably 60-90 deg.C. The reaction is usually continued for 3 to 24 hours, preferably for 4 to 10 hours, after the temperature is raised. The reaction is, of course, advantageously carried out with stirring. After the reaction is finished, the compound of the formula (VI) is obtained by conventional post-treatment. This work-up generally comprises extraction or washing (for example with water, which is then advantageously freed from water using an absorbent compound such as magnesium sulfate or sodium sulfate), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and distillation under reduced pressure to further remove the solvent. If a higher purity product is to be obtained, impurities may also be isolated by recrystallization or column chromatography.

In the reaction of the compound of formula (VI) with the compound of formula (VII), the silicon atom of the compound of formula (VII) contains a hydrogen atom, and therefore, the compound of formula (VII) may be referred to as a hydrogen-containing silicone oil. The addition reaction of a silicon atom-bonded hydrogen atom in the compound of formula (VII) with an unsaturated carbon-carbon double bond in the compound of formula (VI) is of a type known in the art. Generally, the reaction is carried out in the presence of a catalyst. As catalysts suitable for this reaction, Karstedt's catalyst or SpeI er's catalyst are generally used. The amount of catalyst used is also conventional. In general, the catalyst is used in an amount of 2 to 500ppm, preferably 10 to 300ppm, based on the weight of the hydrogen-containing silicone oil. The reaction of the compound of the formula (VI) with the compound of the formula (VII) is usually carried out in a solvent. As the type of the solvent, there is no particular limitation as long as the compound of the formula (VI), the compound of the formula (VII) and the catalyst can be dissolved and do not participate in the reaction between the compound of the formula (VI) and the compound of the formula (VII), and it is preferable that the solvent also contributes to precipitation of the product, i.e., the compound of the formula (I). As the solvent, an organic solvent is generally used, and petroleum ether, dichloromethane, toluene, xylene or any mixture thereof is preferably used. The amount of solvent used is also conventional and is generally 1.5 to 3 times the total weight of the compound of formula (VI) and the compound of formula (VII). The compounds of the formula (VI) and of the formula (VII) are generally used in approximately equimolar amounts. Advantageously, the compound of formula (VI) and the compound of formula (VII) are used in a molar ratio of from 1:0.75 to 1: 1.5. In order to carry out the above reaction, the compound of formula (VI) and the catalyst are dissolved in a solvent, aged for a period of time, then contacted with the compound of formula (VII), and then heated to the reaction temperature for a period of time to obtain the compound of formula (I). Aging is usually carried out at elevated temperatures, generally at from 40 to 70 ℃. The aging time is usually from 30 to 60 minutes. The reaction temperature between the compound of the formula (VI) and the compound of the formula (VII) is generally from 80 to 110 ℃ and preferably from 85 to 100 ℃. The reaction between the compound of the formula (VI) and the compound of the formula (VII) is generally maintained at the reaction temperature for a period of from 3 to 6 hours, preferably from 3.5 to 5.5 hours. The reaction is, of course, advantageously carried out with stirring. After the reaction is finished, the compound product of the formula (I) is obtained through conventional post-treatment. This work-up usually involves filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and distillation under reduced pressure to further remove the solvent. Recrystallization is also possible if a higher purity product is to be obtained.

The compounds of formula (VI) of the invention are novel. Accordingly, one aspect of the present invention relates to compounds of formula (VI):

wherein L and R₆As defined above.

In the compound of formula (VI), the propenyl group is-CH₂-CH₂-CH₂-or-CH (CH)₃)-CH₂-, preferably-CH ═ CH-CH₃。

The compound of formula (I) is a cationic photocuring monomer, has high polymerization rate and high conversion rate, can promote the polymerization of other cationic monomers, and the photocuring material obtained after photocuring polymerization has good mechanical properties, particularly good tensile property, excellent hydrophobic property, stain resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance and good heat resistance.

According to a third aspect of the present invention, there is provided a photocurable composition comprising a compound of formula (I) of the present invention as a polymerizable monomer. The photocurable composition may comprise, in addition to the compound of formula (I) according to the invention, a ring-opening polymerizable cationic photoinitiator (a photoinitiator capable of initiating cationic polymerization) and optionally other cationically photocurable group-containing monomers, oligomers, for example 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate (E4221), such as vinyl ether double bonds, cycloaliphatic epoxy groups, oxirane groups or oxetane groups.

In the photocurable composition of the present invention, the amount of the compound of formula (I) of the present invention may be at least 0.5 mol%, at least 1 mol%, at least 2 mol%, for example, 0.5 to 12 mol%, or 0.5 to 10 mol%, or 1 to 10 mol%, based on the total amount of polymerized monomers.

The photocurable composition of the present invention may be a photocurable coating composition, a photocurable ink composition, a photoresist composition, or the like. After the composition is cured, the obtained cured product has good tensile property, excellent hydrophobic property, stain resistance, fingerprint resistance, chemical corrosion resistance and strong aging resistance.

As the photoinitiator for ring-opening polymerization, iodonium salts and sulfonium salts are generally used. Advantageously, the iodonium salt photoinitiator and the sulfonium salt photoinitiator have the following general formulae (A) and (B), respectively

Wherein

R_a、R_b、R_c、R_d、R_eEach independently is unsubstituted C₆-C₁₀Aryl, or selected from halogen, nitro, carbonyl, C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, thiophenyl, phenyl and substituted phenyl substituents substituted C₆-C₁₀Aryl, preferably phenyl or naphthyl, or selected from halogen, nitro, C₁-C₆Phenyl or naphthyl substituted by alkyl and substituted phenyl substituents, wherein the substituents areThe substituted phenyl group contains one or more substituents selected from halogen, nitro and C₁-C₆Alkyl and C₁-C₆A group of alkoxy groups; and

y, Z are non-nucleophilic anions, e.g. triflate, BF₄ ^-、ClO₄ ^-、PF₆ ^-、AsF₆ ^-、SbF₆ ^-。

For example, as the photoinitiator, one or more selected from the group consisting of 4- (phenylthio) phenyl diphenylsulfonium hexafluorophosphate, 4- (phenylthio) phenyl diphenylsulfonium hexafluoroantimonate, bis (4- (diphenylsulfonium) phenyl) sulfide bis hexafluorophosphate, bis (4- (diphenylsulfonium) phenyl) sulfide bis hexafluoroantimonate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate (810), 4-octyloxydiphenyliodonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 4-isobutylphenyl 4' -methylphenylidium hexafluorophosphate, and mixtures thereof, 4-isobutylphenyl 4' -methylphenyliodilium hexafluoroantimonate, bis (4-dodecylbenzene) iodonium hexafluorophosphate, bis (4-tert-butylbenzene) iodonium hexafluoroantimonate.

The photocurable composition of the present invention may also contain a sensitizer. As sensitizers, mention may be made, for example, of 2-isopropylthioxanthone.

For the purposes of the present invention, the amounts of photoinitiator are conventional. The photoinitiator is generally present in an amount of 0.5 to 5 mol%, preferably 1 to 3 mol%, based on the total molar amount of polymerized monomers in the photocurable composition of the present invention.

According to one aspect of the present invention, there is provided a photocurable material obtained from the photocurable composition of the present invention. According to the present invention, the material is obtained by photocuring the photocurable composition of the present invention. The photocuring material has good mechanical properties, particularly tensile property and excellent hydrophobic property, and has the advantages of contamination resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance and good heat resistance.

The compounds of formula (I) according to the invention are also useful in photocurable coatings, adhesives, inks and photoresists. The invention therefore also relates to the use of the compounds of the formula (I) in photocurable coatings, adhesives, inks and photoresists.

Examples

The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.

Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

Example 1

200mmol of eugenol, 200mL of acetonitrile, 240mmol of potassium carbonate and 240mmol of bromopropanol are placed in a three-neck flask and stirred. Heating to 60 ℃, reacting for 6h, and finishing the reaction. And taking the supernatant of the obtained sample, and performing rotary evaporation to remove the solvent. And adding 400mL of ethyl acetate into the liquid obtained after rotary evaporation, washing with water for three times, and then removing the ethyl acetate by rotary evaporation, wherein the yield of the final product 1-a is 57.4%.

[1-a]:¹H NMR(400MHz,DMSO-d₆)δ6.92-6.63(m,3H),5.94(ddt,J＝8.8,7.0,6.7Hz,1H),5.13-4.95(m,2H),4.50(t,J＝5.2Hz,1H),3.98(t,J＝6.4Hz,2H),3.74(s,3H),3.56(td,J＝6.3,5.1Hz,2H),3.29(dt,J＝6.8,1.5Hz,2H),1.84(p,J＝6.3Hz,2H)。

9.6g (24mmol) of NaH was first added to a three-necked flask containing 10mL of tetrahydrofuran and stirred. Then 20mmol of 1-a is added into a three-neck flask, 22mmol of 3-ethyl-3-chloromethyl oxetane is added into the reaction system, the mixture is stirred evenly and heated to 50 ℃ for condensation and reflux. The reaction was terminated after 6 hours. After the reaction liquid is cooled, water is added to quench the reaction, and then the solvent is removed by rotary evaporation. The product in water was then extracted 3 times with 30mL of ethyl acetate, respectively. The collected organic layer was washed 3 times with water. The organic layer solution was dried overnight by adding anhydrous magnesium sulfate. Finally, the dried liquid was rotary evaporated to remove ethyl acetate. Finally, column chromatography is used for separation to obtain 1-b, and the yield is 59.1%.

[1-b]:¹H NMR(400MHz,Chloroform-d)δ6.95-6.78(m,3H),6.43-6.25(m,1H),6.11(dq,J＝7.7,6.6Hz,1H),4.41(dd,J＝6.9,5.8Hz,4H),4.12(t,J＝6.4Hz,2H),3.87(d,J＝2.2Hz,3H),3.73-3.62(m,2H),3.56(d,J＝2.3Hz,2H),2.12(q,J＝6.1Hz,2H),1.87(dd,J＝6.6,1.7Hz,3H),1.74(qd,J＝7.5,1.7Hz,2H),0.88(t,J＝7.5Hz,3H)。

In a three-necked flask equipped with a temperature probe and a reflux condenser, 2.06g (5mmol) of hydrogen-containing silicone oil (corresponding to the compound of formula (VII) wherein m is 3, R₁Is n-butyl, and R₂、R₃、R₄And R₅Methyl) and 0.412g of Karstedt catalyst (Karstedt catalyst, ansamitra chemical) at a concentration of 100ppm were dissolved in the solvent anhydrous toluene and then heated to 60 ℃ for 40 min. Thereafter, 1.932g (6mmol) of compound 1-b was added dropwise to the three-necked flask, and the temperature was raised to 90 ℃ and maintained for 4 hours under stirring. Centrifuging to remove solid impurities, rotary evaporating at 45 deg.C and 0.1MPa with rotary evaporator, and vacuum distilling at 300Pa and 40 deg.C to obtain the final product. By nuclear magnetic hydrogen spectroscopy, compound 1 was identified with a yield of 51%, sometimes referred to hereinafter as Eugenol-Si₃。

[Eugenol-Si₃]:¹H NMR(400MHz,Chloroform-d)δ7.03-6.38(m,3H),4.45(dd,J＝6.9,5.8Hz,4H),4.24-4.06(m,2H),3.89(d,J＝2.2Hz,3H),3.70(t,J＝6.1Hz,2H),3.59(s,2H),2.12-2.04(m,2H),1.94-1.86(m,2H),1.77(q,J＝7.5Hz,3H),1.41-1.28(m,4H),0.97-0.84(m,9H),0.62-0.55(m,2H),0.16-0.10(m,24H)。

Example 2

In a three-neck flask provided with a temperature probe and a reflux condenser tube, hydrogen-containing silicone oil is added3.17g (5mmol) (corresponding to formula (viii), where m is 6, R₁Is n-butyl, and R₂、R₃、R₄And R₅Methyl) and 0.634g of Karstedt catalyst (Karstedt catalyst, ansamitra chemical) at a concentration of 100ppm were dissolved in the solvent anhydrous toluene and then warmed to 60 ℃ for 40 min. Thereafter, 1.932g (6mmol) of compound 1-b was added dropwise to the three-necked flask, and the temperature was raised to 90 ℃ and maintained for 4 hours under stirring. Centrifuging to remove solid impurities, rotary evaporating at 45 deg.C and 0.1MPa with rotary evaporator, and vacuum distilling at 300Pa and 40 deg.C to obtain the final product. By nuclear magnetic hydrogen spectroscopy, compound 2 was identified with a yield of 90%, sometimes referred to hereinafter as Eugenol-Si₆。

[Eugenol-Si₆]:¹H NMR(400MHz,Chloroform-d)δ6.83-6.50(m,3H),4.43(dd,J＝6.9,5.8Hz,4H),4.16-4.06(m,2H),3.89(d,J＝2.2Hz,3H),3.68(t,J＝6.1Hz,2H),3.57(s,2H),2.12-2.04(m,2H),1.94-1.86(m,2H),1.75(q,J＝7.5Hz,3H),1.41-1.25(m,4H),0.95-0.82(m,9H),0.61-0.48(m,2H),0.13-0.02(m,42H)。

Example 3

In a three-necked flask with temperature probe and reflux condenser, 4.28g (5mmol) of hydrogen-containing silicone oil (corresponding to the compound of formula (viii), wherein m is 9, R₁Is n-butyl, and R₂、R₃、R₄And R₅Methyl) and 0.856g of Karstedt's catalyst (Karstedt's catalyst, Annagi chemical) at 100ppm concentration were dissolved in the solvent anhydrous toluene and then warmed to 60 ℃ for 40 min. Thereafter, 1.932g (6mmol) of compound 1-b was added dropwise to the three-necked flask, and the temperature was raised to 90 ℃ and maintained for 4 hours under stirring. Centrifuging to remove solid impurities, rotary evaporating at 45 deg.C and 0.1MPa with rotary evaporator, and vacuum distilling at 300Pa and 40 deg.C to obtain the final product. It was characterized by nuclear magnetic hydrogen spectroscopy to determine Compound 3 at a yield of 91%, sometimes referred to hereinafter as Eugenol-Si₉。

[Eugenol-Si₉]:¹H NMR(400MHz,Chloroform-d)δ6.98-6.52(m,3H),4.45(dd,J＝6.9,5.8Hz,4H),4.21-4.06(m,2H),3.89(d,J＝2.2Hz,3H),3.70(td,J＝6.1,2.1Hz,2H),3.59(d,J＝1.8Hz,2H),2.20-2.06(m,2H),1.94-1.83(m,2H),1.77(q,J＝7.5Hz,3H),1.43-1.26(m,4H),0.98-0.84(m,9H),0.62-0.49(m,2H),0.14-0.10(m,60H)。

Example 4

In a three-necked flask with temperature probe and reflux condenser, 6.5g (5mmol) of hydrogen-containing silicone oil (corresponding to the compound of formula (viii), wherein m is 15, R₁Is n-butyl, and R₂、R₃、R₄And R₅Methyl) and 1.300g of Karstedt catalyst (Karstedt catalyst, ansamitra chemical) at a concentration of 100ppm were dissolved in the solvent anhydrous toluene and then heated to 60 ℃ for 40 min. Thereafter, 1.932g (6mmol) of compound 1-b was added dropwise to the three-necked flask, and the temperature was raised to 90 ℃ and maintained for 4 hours under stirring. Centrifuging to remove solid impurities, rotary evaporating at 45 deg.C and 0.1MPa with rotary evaporator, and vacuum distilling at 300Pa and 40 deg.C to obtain the final product. It was characterized by nuclear magnetic hydrogen spectroscopy to determine Compound 4 at a yield of 92%, sometimes referred to hereinafter as Eugenol-Si₁₅。

[Eugenol-Si₁₅]:¹H NMR(400MHz,Chloroform-d)δ6.98-6.52(m,3H),4.45(dd,J＝6.9,5.8Hz,4H),4.21-4.06(m,2H),3.89(d,J＝2.2Hz,3H),3.70(td,J＝6.1,2.1Hz,2H),3.59(d,J＝1.8Hz,2H),2.20-2.06(m,2H),1.94-1.83(m,2H),1.77(q,J＝7.5Hz,3H),1.43-1.26(m,4H),0.98-0.84(m,9H),0.62-0.55(m,2H),0.14-0.10(m,96H)。

Example 5

This example is intended to illustrate the photopolymerizability of the compounds of the invention. The photocurable composition was prepared as follows:

weighing proper amount of X₁mol of the above-mentioned compound 1, X₂mol of E4221(3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate), X₃mol photoinitiators Diphenyliodonium hexafluorophosphate (810) and X₄Adding the photosensitizer 2-Isopropyl Thioxanthone (ITX) into a brown bottle, stirring uniformly, and storing in dark. Curing the composition with light₃3.0% as an example, the molar ratio of each component is as follows: [ Compound 1 (X)₁)+E4221(X₂)]:810(X₃):ITX(X₄) 3:97:3:1.5 (all molar ratios), wherein in embodiments of the present disclosure, X in the photocurable composition₁+X₂Is fixed at 100. The photocurable compositions containing compounds 2-3 were prepared in a manner consistent with compound 1. Compounds 1,2 and 3 according to the invention (i.e.Eugenol-Si) in the respective optical compositions₃、Eugenol-Si₆And Eugenol-Si₉) Mole percent X₁As shown in tables 1-3 below, X is as described above₁+X₂Fixed at 100, X₃And X₄Remain unchanged.

A mixture of a photoinitiator diphenyl iodonium hexafluorophosphate (810) and 2-isopropyl thioxanthone (ITX, sensitizer) in a molar ratio of 2:1 is used as a photoinitiation system, the real-time infrared (RT-IR) method is adopted to test the photopolymerization kinetic properties of the compounds 1-3, and the influence of different contents on the photopolymerization property of E4221 is examined. The vibration absorption peak of C-O-C of the used monomer E4221 ternary oxygen heterocycle is located at 750cm^-1The vibration absorption peak of C-O-C of the quaternary oxygen heterocycle of the compound 1-3 as a polymerized monomer at the position is 980cm^-1The liquid sample was irradiated with a high pressure mercury lamp for 900s, which emits mainly at 365nm and has an optical fiber with a diameter of 5mm, by uniformly spreading a photo-curable liquid consisting of a monomer and a photoinitiator on a potassium bromide salt plate (dipping a little of the photo-curable liquid on the potassium bromide salt plate with a tubule, dropping it once, and then spreading it uniformly). The distance between one end of the optical fiber and the test sample is 10cm, and the irradiation intensity is 20mW cm^-2. By measuring at 750cm^-1And 980cm^-1The change of the peak area of C-O-C bond represents different epoxy groupsClusters, i.e., the real-time conversion of monomer and the polymerization rate.

Comprising compounds 1-3 (i.e.Eugenol-Si)₃、Eugenol-Si₆And Eugenol-Si₉) The respective results of the photocurable compositions of (1) to (3) and tables (1) to (3) (in the figures and tables hereinafter, Eugenol-Si is used as₃3.0% as an example, which represents X in the formulation₁3.0 mol%). The results show that the addition of compounds 1-3 can significantly improve the conversion and rate of conversion of E4421 monomer. In addition, the compounds 1 to 3 can be added in small amounts (3 to 12 mol%) to significantly increase the conversion of the monomer E4221, the maximum conversion of which is at least 70%. And as can be seen from FIGS. 4-6, the conversion rates of the compounds 1-3 are all around 74%. Therefore, the compound can improve the photopolymerization performance of the E4221 monomer and has excellent photopolymerization activity.

Table 1: use of Compound 1 (Eugenol-Si)₃) Monomer conversion at 900s of the photocurable composition of (1)

Table 2: use of Compound 2 (Eugenol-Si)₆) Monomer conversion at 900s of the photocurable composition of (1)

Table 3: use of Compound 3 (Eugenol-Si)₉) Monomer conversion at 900s of the photocurable composition of (1)

Example 6

The present example is intended to demonstrate that the compounds of the present invention can improve the surface hydrophobicity of a photocurable film.

Weighing proper amount of X₁mol of the above-mentioned compound 1-3 (i.e., Eugenol-Si)₃、Eugenol-Si₆And Eugenol-Si₉)，X₂mol of E4221, X₃mol photoinitiators Diphenyliodonium hexafluorophosphate (810) and X₄Adding the photosensitizer 2-Isopropyl Thioxanthone (ITX) into a brown bottle, uniformly stirring, and storing in a dark place, wherein the formula comprises the following components in a molar ratio: monomer (X)₁)：E4221(X₂):810(X₃):ITX(X₄) 3:97:3: 1.5. Adding the uniformly stirred photosensitive solution into a polytetrafluoroethylene mold with the thickness of 6mm multiplied by 8mm multiplied by 70mm, and then placing the mold under a mercury lamp for irradiation (the wavelength is 365nm, and the light intensity is 60mW cm)^-2) And taking out the cured film after the irradiation time is 900s, and carrying out a water contact angle test.

And characterizing the surface hydrophobicity of the photocuring film by using a DSA25 type water contact angle tester, wherein the test temperature is 25 ℃. Meanwhile, a blank E4221 cured film was prepared as a reference using the same method. The results for reference and compounds 1-3 are shown in FIG. 7.

As can be seen from FIG. 7, when the compound of the present invention was not added to the E4221 polymerization system, the water contact angle of the cured film was 58.4 °, and the water contact angles of the cured films were significantly increased to 82.4 °, 89.4 ° and 94.2 °, respectively, after the compounds 1-3 were additionally added. In addition, the contact angles of the cured films obtained by additionally adding one of the compounds 1 to 3 were all over 82 °. Therefore, the compound of the invention can remarkably improve the surface hydrophobicity of the cured film, thereby resisting contamination and fingerprints.

Example 7

Cured films of each of the compounds 1 to 3 were obtained in the same manner as described in example 6. Then, the heat resistance of each photocurable film was measured using a thermal gravimetric analyzer (DTG-60AH Shimadzu corporation, China). The test conditions were: under the protection of nitrogen, the temperature range is 25-700 ℃, and the heating speed is 10 ℃/min. Meanwhile, a blank E4221 cured film was prepared as a reference using the same method. The results are shown in FIG. 8 and Table 4.

As can be seen from Table 4 and FIG. 8, the addition of the compoundAfter any of the objects 1 to 3, the initial decomposition temperature (T) of the film is cured_5％) And decomposition temperature (T) when the weight loss of the first stage of the maximum thermal weight loss temperature is fastest_max1) And the decomposition temperature (T) at the time of the second stage when weight loss is fastest_max2) The heat resistance is improved remarkably.

TABLE 4

System of	T5％(℃)	Tmax1(℃)	Tmax2(℃)
				E4221	267	379	-
Eugenol-Si3	317	399	584
				Eugenol-Si6	319	410	587
Eugenol-Si9	322	413	590

Example 8

This example is intended to demonstrate that the compounds of the present invention are capable of improving the tensile properties of photocurable films. Cured films of each of the compounds 1 to 3 were obtained in the same manner as described in example 6. Then, the tensile properties of the photocured film were measured by an electronic universal tester test (model E44.304, Meitess Industrial systems (China) Co., Ltd.) in accordance with International Standard ISO 1184-. The test temperature is 25 ℃, the humidity is 60 percent, and the test speed is 1 mm/min. Meanwhile, a blank E4221 cured film was prepared as a reference using the same method. The results are shown in FIG. 9 and Table 5.

As can be seen from fig. 9 and table 5, the tensile strength of the pure E4221 photocurable film was 6.10MPa, and the elongation at break was 1.7%. After the additional addition of the compound 1-3 monomers, the tensile strength and elongation at break of the photo-cured film were gradually increased. Therefore, the compound of the present invention can significantly improve the tensile properties of the cured film.

TABLE 5

System of	Tensile Strength (MPa)	Elongation at Break (%)
			E4221	6.1	1.7
Eugenol-Si3	8.7	3.0
			Eugenol-Si6	9.4	4.7
Eugenol-Si9	10.6	5.9