CN110845736A

CN110845736A - Energy-curable epoxy graft-modified silicone resins, energy-curable compositions containing the same, and applications

Info

Publication number: CN110845736A
Application number: CN201810955871.7A
Authority: CN
Inventors: 钱晓春; 衡京; 胡春青; 邱琪玲; 翁云峰
Original assignee: Changzhou Tronly New Electronic Materials Co Ltd; Changzhou Tronly Advanced Electronic Materials Co Ltd
Current assignee: Changzhou Tronly New Electronic Materials Co Ltd; Changzhou Tronly Advanced Electronic Materials Co Ltd
Priority date: 2018-08-21
Filing date: 2018-08-21
Publication date: 2020-02-28

Abstract

The invention provides an energy-curable epoxy graft modified silicone resin, an energy-curable composition containing the same and application. One or more oxetane groups are grafted on a branched chain of at least one repeating unit in the epoxy grafting modified organic silicon resin, and each oxetane group has a structure shown in a general formula (I) or a general formula (II). And (3) covalently grafting an oxetane group on a branched chain of the organic silicon resin to obtain the epoxy graft modified organic silicon resin. After the oxetane is covalently grafted on the branched chain of the organic silicon resin, a coating film formed by the composition containing the epoxy graft modified organic silicon resin capable of being cured by energy has good flexibility, solvent resistance and mechanical property, and has high adhesive force to a coated substrate. The epoxy modified organic silicon resin has good compatibility with resin, auxiliaries and the like, and can realize low VOC and even zero VOC emission.

Description

Energy-curable epoxy graft-modified silicone resins, energy-curable compositions containing the same, and applications

Technical Field

The invention relates to the field of energy-curable, in particular to an energy-curable epoxy graft modified silicone resin, an energy-curable composition containing the same and application thereof.

Background

The organic silicon resin has good heat resistance, water resistance, weather resistance and electric insulation, so the organic silicon resin has potential application in the fields of electronics, light industry, chemical industry, aerospace and the like. However, silicone resins need to be cured at high temperatures for a long time, and are prone to deformation of common substrates. And the adhesion force of the organic silicon resin to the base material is poor, the organic solvent resistance is poor, and the mechanical strength of the formed film is not high. The defects in the aspects greatly limit the further application of the silicone resin.

In order to overcome the defects, the prior art mainly adopts two methods of mixing with epoxy resin and modifying by chemically grafting epoxide for improving the performance. However, the surface energy of the organic silicon resin is large, and the difference of the solubility parameter of the organic silicon resin and the epoxy resin is large, so that the organic silicon resin has the defects of poor compatibility and easy layering when being mixed with the epoxy resin for use, and the performance cannot be effectively improved; after the solvent is added, although the layering phenomenon can be improved to a certain extent, the problem of high VOC emission is caused. The direct chemical grafting of epoxides onto silicone resins requires long reaction times at higher temperatures and is inefficient. Meanwhile, most of chemically grafted epoxides contain glycidyl compounds, and although the chemically grafted silicone resin has better curing performance, the conversion rate is low in the curing process. Therefore, it is imperative to search for epoxy-modified silicone resins that are simple in preparation conditions and excellent in curing properties on the basis of the existing studies.

Disclosure of Invention

The invention mainly aims to provide an energy-curable epoxy-grafted modified silicone resin, an energy-curable composition containing the same and application thereof, so as to solve the problems that the compatibility is poor, the VOC emission is high, the preparation of chemical-grafted epoxy (glycidyl-containing compound) of the silicone resin is not easy and the curing performance is not excellent when the existing silicone resin is blended with epoxy resin and other resins.

In order to achieve the above object, according to the present invention, there is provided an energy-curable epoxy graft-modified silicone resin, wherein one or more oxetane groups are grafted to a branch of at least one repeating unit in the epoxy graft-modified silicone resin, each oxetane group having a structure represented by general formula (i) or general formula (ii):

wherein R is₁Is represented by C₁～C₄₀Linear or branched n-valent alkyl of (2), C₂～C₃₀N-valent alkenyl or C₆～C₄₀N-valent aryl of (A), R₁Any one of-CH₂May be substituted by oxygen atoms, ester groups or

Substituted and two oxygen atoms are not directly connected, R₁Any one hydrogen atom in the (A) can be substituted by alkyl, halogen or nitro, and n is an integer of 1-12;

R₂and R₄Each independently represents hydrogen, halogen, nitro, C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₅Alkenyl or C₆～C₃₀Aryl of (A), R₂And R₄Any one of-CH₂-may be substituted by an oxygen atom or-COO-, and two oxygen atoms are not directly connected, R₂And R₄Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

R₃and R₅Each independently represents C₁～C₄₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₂Linear or branched alkenyl of (C)₆～C₃₆Aryl of (A), R₃And R₅Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₃And R₅Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

a represents C₁～C₂₀A straight-chain or branched alkylene group of (A), any one of-CH₂-may be substituted by oxygen or-COO-, and the two oxygen atoms are not directly linked, and any one hydrogen atom in a may be substituted by alkyl, halogen or nitro;

m and Q each independently represent C₁～C₂₀Wherein any one of M and Q is selected from the group consisting of-CH₂May be substituted by oxygen atoms, -COO-orAnd two oxygen atoms are not directly connected, and any one hydrogen atom in M and Q can be substituted by alkyl, halogen or nitro.

By applying the technical scheme of the invention, after the oxetane group is covalently grafted on the branched chain of the organic silicon resin, the epoxy grafted modified organic silicon resin is obtained. After the oxetane is covalently grafted on the branched chain of the organic silicon resin, a coating film formed by the composition containing the epoxy graft modified organic silicon resin capable of being cured by energy has good flexibility, solvent resistance and mechanical property, and has high adhesive force to a coated substrate. The epoxy modified organic silicon resin has good compatibility with resin, auxiliary agent and the like, so that a reactive diluent which can participate in curing can be used without using a diluent solvent in the use process, and low VOC and even zero VOC emission can be realized. To sum up, the energy-curable epoxy grafted modified silicone resin composition provided by the application has good flexibility, solvent resistance and mechanical properties, has high adhesive force to a coated substrate, and can realize the effects of low VOC (volatile organic compound) and even zero VOC (volatile organic compound) emission.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

As described in the background art, the existing silicone resin has the problems of poor compatibility when being blended with epoxy resin and other resins, high VOC emission, difficult preparation of chemical grafting epoxide (glycidyl-containing compound) of the silicone resin and poor curing performance. In order to solve the technical problem, the application provides an epoxy graft modified silicone resin, wherein one or more oxetane groups are grafted on a branch chain of at least one repeating unit in the epoxy graft modified silicone resin, and each oxetane group has a structure shown in a general formula (I) or a general formula (II):

R₃and R₅Each independently represents C₁～C₄₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₂-C₁₂Linear or branched alkenyl of (C)₆～C₃₆Aryl of (A), R₃And R₅Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₃And R₅Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

m and Q each independently represent C₁～C₂₀Wherein any one of M and Q is-CH₂May be substituted by oxygen atoms, -COO-or

And two oxygen atoms are not directly connected, and any one hydrogen atom in M and Q can be substituted by alkyl, halogen or nitro.

And (3) covalently grafting an oxetane group on a branched chain of the organic silicon resin to obtain the epoxy graft modified organic silicon resin. In the energy-curable epoxy graft modified organic silicon resin composition, after oxetane is covalently grafted on a branched chain of organic silicon resin, a coating film formed by the curable epoxy graft modified organic silicon resin has good flexibility, solvent resistance and mechanical property, and has high adhesive force to a coating substrate. The epoxy modified organic silicon resin has good compatibility with resin, auxiliary agent and the like, so that a small amount of reactive diluent capable of participating in curing can be used without using a diluent solvent in the use process, and low VOC and even zero VOC emission can be realized. To sum up, the energy-curable epoxy grafted modified silicone resin composition provided by the application has good flexibility, solvent resistance and mechanical properties, has high adhesive force to a coated substrate, and can realize the effects of low VOC (volatile organic compound) and even zero VOC (volatile organic compound) emission.

It should be noted that the term "n-valent" in the term "n-valent alkyl" means that there are n substituents on the alkyl group, and similarly, "n-valent alkenyl" means that there are n substituents on the alkenyl group, and other expressions referring to "n-valent group" in this application are interpreted identically; and x in the chemical structure represents the attachment position.

Accordingly, "n" in formula (I) means R₁The number of substituents on the radical, e.g. R when n is 2₁The number of substituents on the group is 2.

The composition prepared by adopting the epoxy graft modified organic silicon resin with the structure and capable of being cured by energy has good solvent resistance and mechanical property, and has the advantages of coating a substrateHigher adhesive force, and can realize low VOC and even zero VOC emission and the like. In order to further improve the combination of properties of the coating formed by the coating, the substituents in the structures shown in the formula (I) and the formula (II) can be further preferably selected, and R is₃And R₅Each independently represent

R₆Is represented by C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₂-C₈Linear or branched alkenyl or C₆～C₃₀Aryl of (a); r₇Represents C₁～C₂₀Linear or branched alkylene of (a); r₈Represents hydrogen, halogen, nitro, C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₅Alkenyl of (C)₆～C₃₀Wherein R is₆、R₇And R₈Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₆、R₇And R₈Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

preferably, R₆Is represented by C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₈Linear or branched alkenyl of (C)₆～C₂₄Aryl of (a); r₇Is represented by C₁～C₁₅Linear or branched alkylene of (a); r₈Represents hydrogen, halogen, nitro, C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl of (C)₆～C₂₄₂Wherein R is₆、R₇And R₈In (1)Yi one-CH₂-may be substituted by an oxygen atom or-COO-with two oxygen atoms not directly connected, R₆、R₇And R₈Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

In a preferred embodiment, R₁Is represented by C₁～C₃₀Linear or branched n-valent alkyl of (2), C₂～C₂₀N-valent alkenyl of, C₆～C₃₀N-valent aryl of (A), R₁Any one of-CH₂May be substituted by oxygen atoms, -COO-or

Substituted and two oxygen atoms are not directly connected, R₁Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

More preferably, R₁Is represented by C₁～C₂₀Linear or branched n-valent alkyl of (2), C₂～C₁₅N-valent alkenyl of, C₆～C₂₄N-valent aryl of (A), R₁Any one of-CH₂May be substituted by oxygen atoms, -COO-or

In a preferred embodiment, R₂And R₄Each independently represents hydrogen, halogen, nitro, C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl or C₆～C₂₄Aryl of (A), R₂And R₄Any one of-CH₂-may be substituted by an oxygen atom or-COO-with two oxygen atoms not directly connected, R₂And R₄Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

Preferably, R₂And R₄Each independently represents hydrogen, halogen, nitro, C₁～C₁₅Straight or branched alkyl of (2), C₃～C₁₅Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl or C₆～C₁₂Aryl of (A), R₂And R₄Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₂And R₄Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

In a preferred embodiment, A represents C₁～C₁₅Any one of-CH in A, a straight chain or branched alkylene group₂-may be substituted by oxygen or-COO-with two oxygen atoms not directly connected, and any one hydrogen atom in a may be substituted by alkyl, halogen or nitro.

In a preferred embodiment, M and Q each independently represent C₁～C₁₅Is straight or branched alkyl, any one CH of M and Q₂May be substituted by oxygen atoms, -COO-or

Substituted and two oxygen atoms are not directly connected, and any one hydrogen atom of M and Q may be substituted by alkyl, halogen or nitro.

In order to reduce the difficulty of synthesizing the epoxy graft modified silicone resin and enable the epoxy graft modified silicone resin to have the advantage of low viscosity, n is preferably selected from integers of 1-6.

The method of chemically grafting the compound having one or more oxetanyl groups on the side chains of the repeating units of the silicone resin may employ a grafting method which is conventional in the art. Preferably, the preparation is carried out by the following method:

(1) polyester type epoxy graft modified silicone resin: carrying out esterification reaction on hydroxyl groups in the repeating units of the organic silicon resin and polycarboxylic acid/cyclic anhydride to obtain carboxyl groups except the esterification reaction, carrying out ring-opening reaction on the carboxyl groups and epoxy ethyl in the oxetane and epoxy ethyl compound, and finally sealing the residual terminal hydroxyl groups after the ring-opening of the epoxy ethyl by using a sealing compound;

(2) polyether epoxy graft modified silicone resin: and (3) carrying out ring-opening reaction on hydroxyl groups in the repeating units of the organic silicon resin and epoxy ethyl in the oxetane-containing compound and the epoxy ethyl compound, and then sealing the residual terminal hydroxyl groups after the ring-opening of the epoxy ethyl by using a sealing compound.

Preferably, the preparation process and preparation conditions for grafting one or more oxetane group compounds on the side chain of the repeating unit of the silicone resin by a chemical grafting method are as follows:

(1) polyester epoxy graft modified silicone resin.

(1.1) a polyester type epoxy graft modified silicone resin prepared by a cyclic acid anhydride.

The method comprises the following steps: under the condition of existence of a pyridine catalyst, hydroxyl in the organic silicon resin and cyclic anhydride are subjected to esterification ring-opening reaction at the temperature of 80-120 ℃ for 3-6 h. The pyridine catalyst is used in an amount of 0.1 to 6% by mass, more preferably 3 to 3% by mass, based on the total mass of the reaction raw materials (silicone resin and cyclic acid anhydride).

Step two: in the presence of triphenylphosphine, performing esterification ring-opening reaction on carboxyl obtained after ring-opening of cyclic anhydride and epoxy ethyl in an oxetane and epoxyethyl-containing compound shown in a general formula (III) or (IV) at the reaction temperature of 80-120 ℃ for 3-6 h, wherein the dosage of the triphenylphosphine catalyst is 0.1-8% of the total mass of the used reaction raw materials, and the more preferable dosage is 2-6%.

Step three: and (2) blocking the residual hydroxyl-terminated groups in the organic silicon resin by adopting acyl halide shown in a general formula (VII), epoxy ethyl-containing compound shown in a general formula (VIII), oxetane group-containing compound shown in a general formula (IX), acid anhydride shown in a general formula (X) or unsaturated bond-containing compound shown in a general formula (XI) in the presence of a basic catalyst, wherein the reaction temperature is 30-40 ℃, and the reaction time is 2-5 h. The molar ratio of the used amount of the basic catalyst to the used reaction raw material (the product obtained in the step two, calculated by the molar amount of the hydroxyl groups in the product) is 1-3: 1, and the molar ratio of the used amount of the basic catalyst to the hydroxyl groups in the reaction raw material (the product obtained in the step two, calculated by the molar amount of the hydroxyl groups in the product) is further preferably 1-1.5: 1.

(1.2) polyester type epoxy graft modified silicone resin prepared by polycarboxylic acid.

The method comprises the following steps: in the presence of an acid catalyst, carrying out esterification reaction on hydroxyl in the organic silicon resin and polycarboxylic acid at the reaction temperature of 80-120 ℃ for 3-6 h; the amount of the acidic resin catalyst is 0.1 to 6% by weight, more preferably 3 to 3% by weight, based on the total weight of the reaction raw materials (silicone resin and polycarboxylic acid).

Step two: in the presence of triphenylphosphine, carrying out esterification ring-opening reaction on carboxyl which does not participate in the esterification reaction and epoxy ethyl in the oxetane and epoxyethyl-containing compound shown in the general formula (III) or (IV), wherein the reaction temperature is 80-120 ℃, and the reaction time is 3-6 h; the dosage of the triphenylphosphine catalyst is 0.1 per thousand to 8 percent of the total weight of the used reaction raw materials, and the more preferable dosage is 2 per thousand to 6 percent.

Step three: under the condition of a basic catalyst, the residual hydroxyl-terminated groups in the organic silicon resin are blocked by using acyl halide shown in a general formula (VII), epoxy ethyl group-containing compound shown in a general formula (VIII), oxetane group-containing compound shown in a general formula (IX), acid anhydride shown in a general formula (X) or unsaturated bond-containing compound shown in a general formula (XI). The reaction temperature is 30-40 ℃, the reaction time is 2-5 h, the molar ratio of the use amount of the basic catalyst to the used reaction raw materials (the product obtained in the step two, calculated by the molar amount of hydroxyl groups in the product) is 1-3: 1, and the molar ratio of the use amount of the basic catalyst to the hydroxyl groups in the reaction raw materials (the product obtained in the step two, calculated by the molar amount of hydroxyl groups in the product) is further preferably 1-1.5: 1.

(2) Polyether type epoxy graft modified organic silicon resin

The method comprises the following steps: under the condition of a basic catalyst, hydroxyl in the organic silicon resin and epoxy ethyl in the compound containing oxetane and epoxy ethyl shown in the general formula (III) or (IV) are subjected to ring-opening reaction. The reaction temperature is 80-120 ℃, the reaction time is 3-6 h, and the dosage of the alkaline catalyst is 0.1-8% of the total weight of the used reaction raw materials, and the further preferable dosage is 2-6%.

Step two: under the condition of a basic catalyst, the residual hydroxyl-terminated groups in the organic silicon resin are blocked by using acyl halide shown in a general formula (VII), epoxy ethyl group-containing compound shown in a general formula (VIII), oxetane group-containing compound shown in a general formula (IX), acid anhydride shown in a general formula (X) or unsaturated bond-containing compound shown in a general formula (XI). The reaction temperature is 30-40 ℃, the reaction time is 2-5 h, the molar ratio of the consumption of the alkaline catalyst to the used reaction raw materials (the product obtained in the second step, calculated by the molar weight of hydroxyl groups in the product) is 1-3: 1, the molar ratio of the used amount of the basic catalyst to the hydroxyl in the reaction raw material (the product obtained in the second step, calculated by the molar weight of the hydroxyl in the product) is preferably 1-1.5: 1. The basic catalyst used in the first and second steps may be the same or different.

Further, the oxetane and oxiranyl group-containing compound chemically grafted to the repeating units of the silicone resin has a structure represented by general formula (III) and/or general formula (IV).

Wherein the variable R in the above-mentioned general formulae (III) and/or (IV)₁、R₂、R₄A, M, Q and n are as defined in general formula (I) or (II).

Illustratively, the oxetane and oxiranyl group-containing compound having a structure represented by general formula (iii) and/or general formula (iv) may be:

(m is an integer of 1 to 30, preferably, m is an integer of 1 to 10),

(n is an integer of 1 to 10, preferably 1 to 5),

Further, the polycarboxylic acid to which the oxetane and epoxyethyl group-containing compound is chemically grafted to the repeating units of the silicone resin has a structure represented by the general formula (v):

wherein R is₉Is represented by C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₆～C₂₄And optionally, R₉One or more hydrogen atoms in the group (A) can be independently substituted by alkyl, halogen or nitro, and p is an integer of 2-6; preferably, R₉Is represented by C₁～C₁₂Straight or branched alkyl of (2), C₃～C₁₆Cycloalkyl or substituted cycloalkyl of (A), C₆～C₁₈P is an integer of 2 to 4.

Exemplary polycarboxylic acids of formula (V) are oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, isophthalic acid, cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, terephthalic acid, trimellitic acid, 1,2, 4-cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, cyclobutanetetracarboxylic acid, 1,2,3, 4-butanetetracarboxylic acid or 1,4,5, 8-naphthalenetetracarboxylic acid.

Further, the cyclic anhydride to chemically graft the oxetane and epoxyethyl containing compound onto the repeating units of the silicone resin has a structure as shown in formula (vi):

wherein R is₁₀Is represented by C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₆～C₂₄And optionally, R₁₀May each independently be substituted with a group selected from carboxy, alkyl, halogen or nitro; preferably, R₁₀Is represented by C₁～C₁₂Straight or branched alkyl of (2), C₃～C₁₆Cycloalkyl or substituted cycloalkyl of (A), C₆～C₁₈And optionally, R₁₀May each be independently substituted with a group selected from carboxyl or alkyl.

Illustratively, the cyclic acid anhydride represented by the general formula (VI) is maleic anhydride, succinic anhydride, 2- (2-oct-3-enyl) succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride, cis-cyclohexane-1, 2-dicarboxylic anhydride, nadic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, dimethyl tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, n-dodecylsuccinic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, methylnorbornene-2, 3-dicarboxylic anhydride or 5-norbornene-2, 3-dicarboxylic anhydride.

Further, the acyl halide used for capping the hydroxyl group has a structure represented by the general formula (VII):

wherein R is₆The same as defined above; x is a halogen atom.

Preferably, R₆Is C₁～C₁₂Straight or branched alkyl of (2), C₃～C₁₆Cycloalkyl or substituted cycloalkyl of (A), C₆～C₁₈Aryl of (2), wherein R₆Wherein the methylene group is optionally substituted with an oxygen atom or an ester group, and the two oxygen atoms are not directly connected; and optionally, R₆May each be independently substituted with a group selected from alkyl, halogen or nitro.

Illustratively, the acid halide represented by the general formula (VII) may be acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, n-valeryl chloride, isovaleryl chloride, trimethylacetyl chloride, t-butylacetyl chloride, benzoyl chloride, cyclohexanoyl chloride, methacryloyl chloride, 2-ethoxyacetyl chloride, phthaloyl chloride, o-chloro terephthaloyl chloride, biphenyldicarbonyl chloride, propionyl bromide, baccaproyl bromide, 2-bromooctanoyl bromide, p-bromophenylacetyl bromide, pivaloyl iodomethyl ester or acryloyl iodide.

Further, the epoxyethyl group-containing compound for terminating the hydroxyl group has a structure represented by the general formula (VIII):

wherein R is₇The same as defined above; x is a halogen atom.

Preferably, R₇Is C₁～C₈In which R is a linear or branched alkyl group, in which₇The methylene group in (A) can be optionally substituted by an oxygen atom and an ester group, and two oxygen atoms are not directly connected; and optionally, R₇May each be independently substituted with a group selected from alkyl, halogen or nitro.

Illustratively, the oxirane group-containing compound represented by (VIII) may be epichlorohydrin, chloroethane, chlorobutylene oxide, 2- ((2-chloroethoxy) methyl) ethylene oxide, 2- ((2- (chloromethoxy) ethoxy) methyl) ethylene oxide, bromopropylene oxide, [ (1,1,2, 2-tetrafluoroethoxy) methyl ] ethylene oxide, or 2-trifluoromethylethylene oxide.

Further, the oxetane-containing compound for end-capping the hydroxyl group has a structure shown by the general formula (IX):

wherein R is₇、R₈The same as defined above; x is a halogen atom.

Preferably, R₈Is hydrogen, halogen, nitro, C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Of (a) an alkeneBase, C₆～C₂₄Aryl of (A), R₈Wherein the methylene group is optionally substituted with an oxygen atom or an ester group, and the two oxygen atoms are not directly connected; and optionally, R₈May each be independently substituted with a group selected from alkyl, halogen or nitro.

Preferably, R₇Is C₁～C₈Straight or branched alkyl of R₇Wherein the methylene group is optionally substituted with an oxygen atom or an ester group, and the two oxygen atoms are not directly connected; and optionally, R₇May each be independently substituted with a group selected from alkyl, halogen or nitro.

Illustratively, the oxetane-containing compound may be 2-methyl-2-iodomethyloxetane, 3-diiodomethyl-1-oxetane, 3-bromomethyl-3-methyl-1-oxetane, 3- (3-bromophenyl) oxetane, 3-bromophenyl-3-methyloxetane, 3-chloromethyl-3-methyloxetane, 3-bis (chloromethyl) oxetane, 3-fluoromethyl-3-chloromethyloxetane, 3-chloromethyl-3-iodomethyl-1-oxetane, 3-bromomethyl-3-chloromethyl-1-oxetane, 3-iodomethyloxetane, 3-iodooxetane, 3-bromomethyloxetane, 3-chlorooxetane or 3-iodomethyl-3-methyloxetane.

Further, the acid anhydride compound for blocking a hydroxyl group has a structure represented by the general formula (X):

wherein R is₁₁、R₁₂Is represented by C₁～C₆Linear or branched alkyl.

Illustratively, R₁₁、R₁₂Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl or isohexyl.

Further, the unsaturated bond-containing compound for capping the hydroxyl group has a structure represented by the general formula (XI):

wherein R is₇The same as defined above; x is a halogen atom.

Illustratively, the unsaturated bond-containing compound represented by the formula (XI) may be 3-chloropropene, 3-bromopropylene, 3-chloromethoxy-1-propene, vinyl 2-chloroacetate, 6-chloro-3-methyl-1-hexene, 3-chloro-1-butene or 3-bromomethoxy-1-propene. The blocking agent may be used alone or in combination of two or more.

Further, the pyridine-based catalyst may be exemplified by pyridine, 4-dimethylaminopyridine, or bisulfate pyridine. Wherein, the catalyst can be used singly or in combination of two or more.

Further, the acidic catalyst may be phosphoric acid, boric acid, organic sulfonic acid, hydrochloride, sulfate, or acidic resin; preferably, the acid catalyst is an acid resin, wherein the acid resin catalyst may be, for example, 732 resin, D72 resin, DA345 resin, DA330 resin, D005-T resin, A-25 resin, or A-35 resin. Wherein, the catalyst can be used singly or in combination of two or more.

Further, the basic catalyst may be lithium amide (e.g., lithium diisopropylamide, lithium hexamethyldisilazide, etc.), alkali metal hydroxide (e.g., sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.), alkali metal carbonate (e.g., sodium carbonate, potassium carbonate, etc.), alkali metal bicarbonate (e.g., sodium bicarbonate, potassium bicarbonate, etc.). More preferably, the basic catalyst is an alkali metal hydroxide. Wherein, the catalyst can be used singly or in combination of two or more.

Further, a solvent may or may not be used in the reactions of the respective steps in the above production process. The solvent used in the reaction is not particularly limited as long as it does not affect the reaction. Illustratively, the solvent may be acetonitrile, propionitrile, benzonitrile, toluene, xylene, dichloromethane, cyclohexane, and the like. Wherein the above solvents may be used alone or in combination of two or more. Further, the amount of the solvent used in the reaction can be appropriately adjusted depending on the actual reaction conditions such as the uniformity and the stirring property of the reaction system.

For a better understanding of the present application, the present application also provides an energy curable composition comprising an energy curable epoxy graft modified silicone resin, the energy curable composition comprising the epoxy graft modified silicone resin described above, and further comprising a resin and an auxiliary agent.

In the energy-curable epoxy graft modified organic silicon resin composition, after oxetane is covalently grafted on a branched chain of organic silicon resin, a coating film formed by the curable epoxy graft modified organic silicon resin has good flexibility, solvent resistance and mechanical property, and has high adhesive force to a coating substrate. The epoxy modified organic silicon resin has good compatibility with resin, auxiliary agent and the like, so that a low-boiling-point solvent can not be used for dilution in the using process, and low VOC and even zero VOC emission can be realized. To sum up, the energy curable epoxy grafted modified silicone resin-containing energy curable composition provided by the application has good flexibility, solvent resistance and mechanical properties, has high adhesion to a coated substrate, and can realize low VOC and even zero VOC emission effects.

In a preferred embodiment, the energy curable composition comprises 5-80 parts by weight of epoxy graft modified silicone resin, 5-60 parts by weight of resin and 1-50 parts by weight of auxiliary agent.

In order to further improve the comprehensive properties of flexibility, solvent resistance, mechanical property, adhesion to a coated substrate and the like of the energy curable composition, more preferably, the energy curable composition comprises 20-60 parts by weight of epoxy graft modified silicone resin, 20-50 parts by weight of resin and 2-40 parts by weight of auxiliary agent.

In a preferred embodiment, the resin includes, but is not limited to, one or more of the group consisting of a silicone resin, a rosin resin, an alkyd resin, a phenolic resin, a saturated polyester resin, a polyurethane resin, a polyurea resin, a chlorinated polyethylene resin, a cellulose nitrate, an amino resin, a fluorocarbon resin, an epoxy resin, a hyperbranched resin, and an acrylic resin, or a modified product of the above resin. Wherein, the modified product of the resin is obtained by modifying the existing resin (such as organic silicon resin and phenolic resin) by a chemical or physical method (such as grafting or blending).

Preferably, the resin is selected from one or more of the group consisting of epoxy resins, hyperbranched resins, and epoxy graft-modified silicone resins, rosin resins, alkyd resins, phenolic resins, saturated polyester resins, polyurethane resins, polyurea resins, cellulose nitrate, amino resins, fluorocarbon resins, and acrylic resins.

In a preferred embodiment, the auxiliaries include, but are not limited to, one or more of the group consisting of flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, heat stabilizers, antioxidants, light stabilizers, compatibilizers, colorants, stabilizers, release agents, antistatic agents, pigments, dyes, and flame retardants.

In a preferred embodiment, the energy curable composition further comprises an initiator; preferably, the initiator is a cationic initiator.

In a preferred embodiment, the energy curable composition further comprises 0.5 to 10 parts by weight of a cationic initiator.

More preferably, the cationic initiator is selected from one or more of diazonium salts, onium salts and organometallic complexes capable of forming strong acids upon application of an external energy source;

preferably, the cationic initiator is selected from the group consisting of diazonium fluoroborate, pyrazole diazonium inner salt, triptycene diazonium salt, diazoaminobenzene, triarylsulfonium hexafluorophosphate, triarylsulfonium antimonate, 4' -dimethyldiphenyliodonium hexafluorophosphate, 4,4 '-dimethyldiphenyliodonium hexafluorophosphate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, diphenyl- (4-phenylsulfide) phenylsulfonium hexafluorophosphate, bis (4-diphenylthiophenyl) sulfide dihexafluoroantimonate, 4-isobutylphenyl-4' -methylphenyliodionium hexafluorophosphate and 6-cumeneferrocenium hexafluorophosphate.

In order to provide a wider range of applications for the composition comprising the epoxy graft-modified silicone resin, in a preferred embodiment, the composition is cured by at least one of light, heat or electron radiation; preferably, the composition is cured by UV light. The UV light source may be a light source or radiation source made to emit light in the ultraviolet range (i.e. between 10nm and 420 nm), and may for example be selected from: fluorescent lamps, fluorescent black light lamps, short wave ultraviolet lamps, lasers, ultraviolet gas lasers, high power gas lasers (e.g., nitrogen lasers or excimer lasers), ultraviolet laser diodes, ultraviolet solid state lasers, electron beams, illuminators, monochromatic light sources, Light Emitting Diodes (LEDs), LED arrays, ultraviolet LEDs, gas discharge lamps, argon and deuterium lamps, Hg-Cd lamps, arc lamps, flash lamps, Xe or halogen lamps, or any other suitable light source.

Another aspect of the present application also provides the use of an energy curable composition containing an energy curable epoxy graft modified silicone resin as described above in energy curable manufacturing. Preferably, the energy curable articles are inks, coatings and adhesives. By way of example, the inks may be listed: relief, intaglio, lithographic and mesh inks; the coating materials include: building coatings, anticorrosive coatings, automotive coatings, dew-proof coatings, antirust coatings, waterproof coatings, moisture-retaining coatings, elastic coatings; the adhesive may be exemplified by: solvent-based adhesives, emulsion-based adhesives, reactive (thermal curing, UV curing, moisture curing) adhesives, hot melt adhesives, remoistenable adhesives, pressure-sensitive adhesives.

The coating formed by the curable epoxy graft modified organic silicon resin composition effectively solves the problems of poor adhesive force, solvent resistance and mechanical property of the existing organic silicon resin formula, low curing speed, low compatibility with each component and high VOC emission caused by adding a solvent for dilution. In addition, the preparation conditions and the process of the organic silicon resin chemically grafted and containing one or more oxetanyl groups are simple. The advantages make it widely applicable in the field of energy curing with low or even no emission of VOC.

The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.

Example 1

Preparation of raw material 3: into a four-necked flask, 116g (1mol) of the raw material B was charged, and 2.9g (1% by mass of the sum of the raw material A and the raw material B) of sodium hydroxide was further charged, 172g (1mol) of the raw material A2h was dropwise added at 100 ℃ and the reaction was continued for 4 hours after the completion of the dropwise addition, whereby 288g of the intermediate A was obtained. Further, 92.5g (1mol) of the starting material C and 60g (1.5mol) of sodium hydroxide were charged into the flask, and reacted at 40 ℃ for 4 hours to obtain 344g of the starting material 3 by leaching. The synthetic route is as follows:

preparation of product 1: 83g (containing 1mol of hydroxyl) of the raw material 1, 86g (1mol) of the raw material 2, 0.9g (5 ‰ of the mass of the raw material 1 and the raw material 2) of pyridine and 200mL of toluene were put into a four-necked flask, mixed uniformly, and reacted at 85 ℃ for 3 hours to obtain 169g of the intermediate (1). 344g (1mol) of the starting material 3 and 2.6g (5 ‰ of the mass sum of the intermediate 1 and the starting material 3) of triphenylphosphine were further charged into the flask, and reacted at 100 ℃ for 5 hours to obtain 513g of the intermediate (2). 92.5g (1mol) of the starting material 4 and 40g (1mol) of sodium hydroxide were further charged into the flask, and reacted at 40 ℃ for 5 hours to obtain 569g of product 1 by filtration and desolventization.

Physicochemical parameters of product 1: the epoxy equivalent was 201g/mol and the acid number was 0.2mg KOH/g.

The synthetic route is as follows:

example 2

Preparation of starting material 3': the preparation conditions and the charge amount of the raw material 3 in example 1 were the same, except that the 3-ethyl-3-oxetanylcarbinol of the raw material B was replaced with ethanol.

Preparation of product 2: a four-necked flask was charged with 73.5g (containing 1mol of hydroxyl group) of raw material 1 ', 104g (1mol) of raw material 2 ', 1.8g (1% by mass of the sum of raw material 1 ' and raw material 2 ') of D72 resin and 200mL of xylene, and after uniformly mixing, the mixture was reacted at 105 ℃ for 4 hours to obtain 159.5g of intermediate (1 '). 274g (1mol) of the starting material 3 'and 2.2g (5 ‰ of the mass sum of the intermediate 1' and the starting material 3 ') of triphenylphosphine were further charged into the flask, and reacted at 90 ℃ for 5 hours to obtain 433.8g of the intermediate (2'). 78.5g (1mol) of the starting material 4' and 48g (1.2mol) of a mixture of sodium hydroxide and potassium hydroxide were further charged into the flask, reacted at 35 ℃ for 5 hours, and then subjected to leaching to give 475.8g of product 2.

Physicochemical parameters of product 2: the epoxy equivalent was 499g/mol and the acid number was 0.2mg KOH/g.

The synthetic route is as follows:

example 3

Preparation of raw material 3': the preparation conditions and the charge amount of the raw material 3 in example 1 were the same except that the 3-ethyl-3-oxetanylcarbinol of the raw material B was replaced by 2-methoxyethanol.

Preparation of product 3: 145g (1mol of hydroxyl group-containing) of the starting material 1 ", 100g (1mol) of the starting material 2", 4.9g (2% of the sum of the masses of the starting material 1 "and the starting material 2") of 4-dimethylaminopyridine were charged into a four-necked flask, and after uniformly mixing, they were reacted at 100 ℃ for 4 hours to obtain 245g of an intermediate (1 "). 304g (1mol) of the starting material 3 'and 5.5g (1% by mass of the sum of the intermediate 1' and the starting material 3 ') of triphenylphosphine were further charged into the flask, and reacted at 80 ℃ for 6 hours to obtain 549g of an intermediate (2'). 102g (1mol) of the starting material 4' and 60g (1.5mol) of potassium hydroxide were further charged into the flask, and reacted at 40 ℃ for 5 hours to obtain 591g of the product 3 after leaching.

Physicochemical parameters of product 3: the epoxy equivalent was 622g/mol and the acid number was 0.3mg KOH/g.

The synthetic route is as follows:

examples 4 to 16

Referring to the preparation methods and feeding molar ratios of examples 1 to 3, products 4 to 16 having the following structural formulae were synthesized from the respective raw materials.

Physicochemical parameters of product 4: the epoxy equivalent was 202g/mol and the acid value was 0.3mg KOH/g.

Physicochemical parameters of product 5: the epoxy equivalent was 324g/mol and the acid number was 0.3mg KOH/g.

Physicochemical parameters of product 6: the epoxy equivalent was 277g/mol and the acid number was 0.4mg KOH/g.

Physicochemical parameters of product 7: the epoxy equivalent was 237g/mol and the acid value was 0.2mg KOH/g.

Physicochemical parameters of product 8: the epoxy equivalent was 221g/mol and the acid value was 0.2mg KOH/g.

Physicochemical parameters of product 9: the epoxy equivalent was 319g/mol and the acid number was 0.3mg KOH/g.

Physicochemical parameters of product 10: the epoxy equivalent was 225g/mol and the acid number was 0.2mg KOH/g.

Physicochemical parameters of product 11: the epoxy equivalent was 170g/mol and the acid number was 0.2mg KOH/g.

Physicochemical parameters of product 12: the epoxy equivalent was 246g/mol and the acid number was 0.2mg KOH/g.

Physicochemical parameters of product 13: the epoxy equivalent was 409g/mol and the acid number was 0.3mg KOH/g.

Physicochemical parameters of product 14: the epoxy equivalent was 234g/mol and the acid value was 0.3mg KOH/g.

Physicochemical parameters of product 15: the epoxy equivalent was 246g/mol and the acid number was 0.4mg KOH/g.

Physicochemical parameters of product 16: the epoxy equivalent was 317g/mol, and the acid value was 0.2 mgKOH/g.

Evaluation of Performance

The application properties of the epoxy-containing graft-modified silicone resin composition of the present invention in the field of energy curing were evaluated by formulating an exemplary energy-curable composition.

Parts of each component are parts by weight unless otherwise indicated. The curing sources for the following formulations in the performance tests all use an ultraviolet light source as an energy source without specific mention, but this is not intended to limit the source of curing energy according to the invention.

The energy curable compositions to be tested were each formulated according to the formulation in table 1 (parts by weight).

TABLE 1

Note: the names/compositions of the components denoted by the symbols in table 1 are shown in table 2.

TABLE 2

Code number	Composition (I)
		A-1	Silicone resin (Laiyang Shengbang chemical Co., Ltd., SI-MQ102)
A-2	Epoxy modified silicone resin (Xinyue, ES1001N)
		B-1	Mixing solvent: acetone and xylene (mass ratio 3: 7)
C-1	Acrylic resin (Joncryl 678, Basff Co., Ltd.)
		C-2	Polyester resin (Korea SK group, ES900)
C-3	UVR-6110 (Nantong Haojin chemical Co., Ltd.)
		D-1	Photoinitiator (CURREASE Co., Easepi6976)
D-2	Thermal initiator (Changzhou powerful new material Co., Ltd., TR-TAG-50101)
		E-1	Flatting agent (BYK corporation, BYK-333)

(1) curing speed test

The curing speed test uses an ultraviolet light source as an energy source, but is not intended to limit the curing energy source of the present invention.

The raw materials were prepared in the weight parts shown in table 1, and after mixing uniformly in a dark room, about 1mg of the sample was weighed and spread on an aluminum crucible. The sample was cured by scanning using a Perkin Elmer differential scanning calorimeter (DSC8000) equipped with a mercury arc lamp ultraviolet source (OmniCure-S2000).

The time to maximum cure exotherm from UV initiation was recorded, as well as the time required to reach a 90% UV cure exotherm, with shorter times to peak and shorter times to 90% conversion being indicative of good cure performance.

Adhesion test (2)

The cured films were tested at a temperature of 23 ℃ and a relative humidity of 50%. The method for evaluating the scratching of the paint film is specified in GB/T9286-1998, the paint film is cut into hundreds of grains, the knife point scratches the substrate during cutting, the knife point is sharp, and the angle between the knife point and the paint film is 45 degrees. Brushing the paint chips with a soft brush, adhering the 3M transparent adhesive tape on the scribed hundreds of lattices, and applying force to firmly adhere the adhesive tape on the film coating surface and the scribed parts. One end of the 3M tape was held and angled at 60 degrees within 2min, the tape was torn off smoothly within 1 second, and evaluated as follows.

Level 0: the cutting edge is completely smooth without falling off;

level 1: a little coating falls off at the intersection of the cuts, but the cross cutting area is not influenced by more than 5 percent;

and 2, stage: the coating at the intersection of the cuts and/or along the edges of the cuts falls off, being affected by significantly more than 5%, but not significantly more than 15%;

and 3, level: the coating falls off partially or completely as large fragments along the cutting edge and/or partially or completely on different parts of the grid, and the affected cross cutting area is obviously more than 15 percent but not more than 35 percent;

4, level: the coating is peeled off along the large fragments of the cutting edge, and/or some squares are partially or completely peeled off, and the affected cross cutting area is obviously more than 35 percent, but not more than 65 percent;

and 5, stage: the degree of exfoliation was over grade 4.

Solvent resistance test of (3)

The solvent resistance of the energy cured samples was tested using GB/T23989-one 2009 as a standard. The curable composition solution was spin-coated onto a 6-inch (150mm diameter) substrate to form a 30 μm thick coating, and the coating was heat-dried at 150 ℃ for 2min and further at 200 ℃ for 2 min. Before the test, the test plate coated with the film layer is adjusted for 1h under the conditions of 23 ℃ and 50% of relative humidity, and then the test is carried out at the temperature of 18-27 ℃.

The method comprises the steps of immersing absorbent cotton in dimethylbenzene to be in a wet state (no liquid drops should be dropped by hand), wiping a test area with the absorbent cotton, wiping forwards and backwards firstly, wiping forwards and backwards for one time of reciprocating wiping, controlling the one time of reciprocating wiping to be about 1s, and wiping for 25 times of reciprocating wiping in total, after the wiping frequency of a solvent is finished, visually checking a coating area of a test plate under scattered sunlight to see whether the test plate is damaged or not to expose a substrate, evaluating the test plate to be good to be ○ when the substrate is not observed, and evaluating the test plate to be poor to be x when the substrate is observed.

Mechanical property test (flexibility)

Testing the cured film under the conditions of 23 ℃ of temperature and 70% of relative humidity, taking a GB/T1731-93 paint film flexibility test method as a basis, sequentially winding the outer side of the tinplate coated with the cured coating on a rod shaft of 10 mm, 5 mm, 4 mm, 3 mm, 2 mm and 1 mm along the length direction, bending for 2-3s, observing by using a magnifying lens, and expressing the flexibility of the ultraviolet curing coating by using the diameter of the smallest rod shaft damaged by the coating layer.

VOC emission test

The energy cured samples were tested for VOC emissions using ASTM D5403-1993. Weighing 0.2g of sample, coating the sample on a weighed aluminum plate, and weighing again; the sample coated aluminum plate was fully cured by scanning the sample using a PerkinElmer differential scanning calorimeter (DSC8000) equipped with a mercury arc lamp uv source (OmniCure-S2000). Cooling the solidified sample for 15min at room temperature, and weighing; the solidified and cooled sample was placed in a vented oven at 110 ℃ for drying for 1h, and then the sample was placed in a desiccator to cool to room temperature and weighed.

Process volatiles 100 × [ (B-C)/(B-a) ]; latent volatiles × [ (C-D)/(B-a) ];

total volatiles% + processing volatiles + latent volatiles%,

wherein: a-weight of aluminum plate, g; b-weight of sample and aluminum plate, g; c-weight of sample and aluminum plate after sample curing, g; d-weight of sample and aluminum plate after curing after heating, g.

The above evaluation results are summarized in table 3.

TABLE 3

As can be seen from the performance evaluation table in table 3, the energy-curable composition containing the epoxy graft-modified silicone resin of the present invention has a certain improvement in curing speed, flexibility, adhesion, and solvent resistance compared to a mixed energy-curable composition of a silicone resin and other resins, and has the advantage of no VOC emission because the compatibility of the epoxy graft-modified silicone resin with other components is high, and no solvent is required to be added during use. In addition, the glycidyl modified silicone resin energy curing composition has the same comprehensive performance as the epoxy grafted modified silicone resin energy curing composition, but the substance of the invention has simple preparation process and can be industrially produced and applied.

In conclusion, the epoxy grafted modified organic silicon resin provided by the invention shows excellent curing performance when applied to an energy curing formula, and is free of VOC (volatile organic compound) emission, green and environment-friendly. Therefore, the epoxy graft modified organic silicon resin has excellent performances of high adhesive force, good flexibility, fast curing and the like, and is not easy to cause environmental pollution. The epoxy grafted modified organic silicon resin is applied to different formulas, and has a wide commercial application prospect in the field of environment-friendly energy curing.

Application of energy-curable epoxy graft modified organic silicon resin in fields of printing ink, coating and adhesive

< energy curable coating >

Adding epoxy graft modified organic silicon resin (product 2) or organic silicon resin (SiMQ 102, Saint Pont chemical Co., Ltd., Laiyang), acrylic resin (Joncryl 678, Bassfungsu Co., Ltd.), and photoinitiator (triarylsulfonium salt, manufactured by CURREASE, Easepi6976) into a stirring tank, stirring at high speed at normal temperature until the mixture is uniform, then adding titanium dioxide and stirring for 4h, then adding macromolecular dispersant (BYK, BYK110), stirring for 2h, mixing uniformly and filtering to obtain the possible-amount cured coating.

The contents of the components of the above examples and comparative examples are shown in Table 4 (parts by weight).

TABLE 4

The energy curable coatings prepared in the above examples and comparative examples were uniformly coated on the surface of a metal substrate (cold rolled steel sheet, galvanized steel sheet or silicon steel sheet), and the coated metal substrate was placed in a Dymax curing apparatus and cured with a medium pressure mercury lamp for 60s (3.3J/cm)²UVA) and curing, and then carrying out performance test, adhesion test and VOC emission test on the cured product according to the same methods as the above test methods, and testing the hardness according to the national standard GB/T6739-86, wherein the test results are shown in Table 5.

TABLE 5

Sample (I)	Adhesiveness (grade)	Hardness of	VOC emission (%)
				Examples	0	3H	0
Comparative example	2	2H	20.0

As can be seen from Table 5 above, the energy curable coating provided by the present invention has high hardness, good adhesion, and no VOC emissions.

< energy curable ink >

Under the condition of no illumination, epoxy graft modified silicone resin (product 6) or silicone resin (SiMQ 102, St. Pont chemical Co., Ltd., Laiyang), polyester resin (SK, ES900) and photoinitiator (triarylsulfonium salt, manufactured by CURREASE, Easepi6976) are added into a stirring tank, stirred at normal temperature and high speed until being uniformly mixed, then filler (diatomite) is added and stirred for 4h, then auxiliary agents (BYK, BYK381) are added and stirred for 2h, and after being uniformly ground, insoluble substances are filtered by a polytetrafluoroethylene filter with the aperture of 0.45 mu m, so that the energy-curable ink is prepared.

The contents of the components of the above examples and comparative examples are shown in Table 6 (parts by weight).

TABLE 6

Components	Examples	Comparative example
			Product 6	50	0
Silicone resin	0	50
			Polyester resin	22	22
Photoinitiator	5	5
			Auxiliary agent	5	5
Filler material	18	18
			Solvent(s)	0	25

The energy curable inks obtained in the above examples and comparative examples were uniformly coated on PET, which was then placed in a Dymax curing apparatus and cured for 60s (3.3J/cm) with a medium pressure mercury lamp²UVA), and the cured product is subjected to performance tests, the adhesion, flexibility and VOC emission tests are the same as those in the above, and the test results are shown in Table 7.

TABLE 7

As can be seen from Table 7 above, the energy curable ink provided by the present invention has good adhesion, good flexibility, and no VOC emissions.

< energy curable adhesive >

Epoxy graft modified organic silicon resin (product 15) or organic silicon resin (SI-MQ 102, St. Laiyang chemical Co., Ltd.), phenolic resin (DKSH Co., 2402) and photoinitiator (triarylsulfonium salt, manufactured by CURREASE, Easepi6976) are added into a stirring tank, stirred at normal temperature and high speed until being uniformly mixed, then filler (talcum powder) is added and stirred for 4 hours, then auxiliary agents (BYK, BYK349) are added, stirred for 2 hours, and defoamed after being uniformly ground to prepare the energy-curable adhesive. The component contents of the above examples and comparative examples are shown in Table 8 (parts by weight).

TABLE 8

Components	Examples	Comparative example
			Product 15	50	0
Silicone resin	0	50
			Phenolic resin	20	20
Photoinitiator	5	5
			Auxiliary agent	5	5
Filler material	20	20
			Solvent(s)	0	25

The energy curable adhesives prepared in the above examples and comparative examples were uniformly coated on PET, which was then placed in a Dymax curing apparatus and cured for 60s (3.3J/cm) with a medium pressure mercury lamp²UVA) and curing, and then carrying out performance test on the cured product, wherein the adhesive force test method is the same as the above method, the tensile shear strength is tested according to GB/T7124-2008, and the test results are shown in Table 9.

TABLE 9

As can be seen from the above Table 9, the energy curable adhesive provided by the invention has good adhesion, strong tensile shear force and no VOC emission.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. An energy-curable epoxy graft modified silicone resin, wherein one or more oxetane groups are grafted to a side chain of at least one repeating unit in the epoxy graft modified silicone resin, and each oxetane group has a structure represented by general formula (I) or general formula (II):

wherein, R is₁Is represented by C₁～C₄₀Linear or branched n-valent alkyl of (2), C₂～C₃₀N-valent alkenyl or C₆～C₄₀N-valent aryl of (A), said R₁Any one of-CH₂May be substituted by oxygen atoms, ester groups or

Substituted and two oxygen atoms are not directly connected, the R₁Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro; n is an integer of 1-12;

the R is₂And said R₄Each independently represents hydrogen, halogen, nitro, C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₅Alkenyl or C₆～C₃₀Aryl of (a), said R₂And said R₄Any one of-CH₂-may be substituted by an oxygen atom or-COO-, and two oxygen atoms are not directly connected, said R₂And said R₄Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

the R is₃And said R₅Each independently represents C₁～C₄₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₂Linear or branched alkenyl of (C)₆～C₃₆Aryl of (a), said R₃And said R₅Any one of-CH₂-may be substituted by an oxygen atom or-COO-, said R₃And said R₅Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

a represents C₁～C₂₀A straight or branched alkylene of (A), any one of the groups-CH₂Can be oxidized by oxygenAtom or-COO-, two oxygen atoms are not directly connected, and any one hydrogen atom in A can be substituted by alkyl, halogen or nitro;

said M and said Q each independently represent C₁～C₂₀Wherein any one of said M and said Q is-CH₂May be substituted by oxygen atoms, -COO-or

And two oxygen atoms are not directly connected, and any one hydrogen atom in the M and the Q can be substituted by alkyl, halogen or nitro.

2. The epoxy graft modified silicone resin according to claim 1, wherein R is₃And said R₅Each independently represent

The R is₆Is represented by C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₈Linear or branched alkenyl or C₆～C₃₀Aryl of (a); the R is₇Represents C₁～C₂₀Linear or branched alkylene of (a); the R is₈Represents hydrogen, halogen, nitro, C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₅Alkenyl of (C)₆～C₃₀Wherein R is₆The R is₇And said R₈Any one of-CH₂-may be substituted by an oxygen atom or-COO-, said R₆The R is₇And said R₈Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

preferably, said R is₆Is represented by C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₈Linear or branched alkenyl of (C)₆～C₂₄Aryl of (a); the R is₇Is represented by C₁～C₁₅Linear or branched alkylene of (a); the R is₈Represents hydrogen, halogen, nitro, C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl of (C)₆～C₂₄₂Wherein R is₆The R is₇And said R₈Any one of-CH₂-may be substituted by an oxygen atom or-COO-with two oxygen atoms not directly connected, said R₆The R is₇And said R₈Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

3. The epoxy graft-modified silicone resin according to claim 1 or 2, wherein R is₁Is represented by C₁～C₃₀Linear or branched n-valent alkyl of (2), C₂～C₂₀N-valent alkenyl of, C₆～C₃₀N-valent aryl of (A), said R₁Any one of-CH₂May be substituted by oxygen atoms, -COO-orSubstituted and two oxygen atoms are not directly connected, the R₁Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

preferably, said R is₁Is represented by C₁～C₂₀Linear or branched n-valent alkyl of (2), C₂～C₁₅N-valent alkenyl of, C₆～C₂₄N-valent aryl of (A), said R₁Any one of-CH₂May be substituted by oxygen atoms, -COO-or

Substituted and two oxygen atoms are not directly connected, the R₁Any one hydrogen atom in (1) may be replaced byAlkyl, halogen or nitro.

4. The epoxy graft-modified silicone resin according to any one of claims 1 to 3, wherein R is the same as R₂And said R₄Each independently represents hydrogen, halogen, nitro, C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl or C₆～C₂₄Aryl of (a), said R₂And said R₄Any one of-CH₂-may be substituted by an oxygen atom or-COO-with two oxygen atoms not directly connected, said R₂And said R₄Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

preferably, said R is₂And said R₄Each independently represents hydrogen, halogen, nitro, C₁～C₁₅Straight or branched alkyl of (2), C₃～C₁₅Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl or C₆～C₁₂Aryl of (a), said R₂And said R₄Any one of-CH₂-may be substituted by an oxygen atom or-COO-, said R₂And said R₄Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

5. The epoxy graft-modified silicone resin according to any one of claims 1 to 3, wherein A represents C₁～C₁₅Any one of the above-mentioned groups-CH₂-may be substituted by oxygen or-COO-with two oxygen atoms not directly connected, any one hydrogen atom of said a being substituted by alkyl, halogen or nitro.

6. The epoxy graft-modified silicone resin according to any one of claims 1 to 3, wherein M and Q each independently represent C₁～C₁₅Said M and saidAny one CH in Q₂May be substituted by oxygen atoms, -COO-or

Substituted and two oxygen atoms are not directly connected, and any one hydrogen atom in the M and the Q can be substituted by alkyl, halogen or nitro.

7. The epoxy graft modified silicone resin according to any one of claims 1 to 3, wherein n is an integer selected from 1 to 6.

8. An energy curable composition containing an energy curable epoxy graft modified silicone resin, characterized in that the energy curable composition comprises the epoxy graft modified silicone resin of any one of claims 1 to 7, and further comprises a resin and an auxiliary agent.

9. The energy curable composition according to claim 8, wherein the resin is one or more selected from the group consisting of an amino resin, a rosin resin, an alkyd resin, a phenolic resin, a saturated polyester resin, a polyurethane resin, a polyurea resin, a chlorinated polyethylene resin, a silicone resin, a fluorocarbon resin, an epoxy resin, a hyperbranched resin, and an acrylic resin, or a modified product of the resin;

preferably, the resin is selected from one or more of the group consisting of epoxy resin, hyperbranched resin, and epoxy graft-modified amino resin, rosin resin, alkyd resin, phenolic resin, saturated polyester resin, polyurethane resin, polyurea resin, silicone resin, fluorocarbon resin, and acrylic resin.

10. The energy curable composition according to claim 8 or 9, wherein the auxiliaries are selected from one or more of the group consisting of flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, heat stabilizers, antioxidants, light stabilizers, compatibilizers, colorants, stabilizers, release agents, antistatic agents, pigments, dyes and flame retardants.

11. The energy curable composition according to any one of claims 8 to 10, further comprising an initiator; preferably, the initiator is a cationic initiator.

12. The energy curable composition according to claim 11, wherein the cationic initiator is selected from one or more of diazonium salts, onium salts and organometallic complexes capable of forming strong acids upon application of an external energy source;

13. The energy curable composition according to any one of claims 8 to 12, wherein the energy curable composition is curable by at least one of light, heat or electron radiation; preferably, the composition is cured by UV light.

14. Use of an energy curable composition containing an energy curable epoxy graft modified silicone resin according to any one of claims 8 to 13 in an energy curable article.

15. Use of an energy curable composition comprising an epoxy graft modified silicone resin in an energy curable article according to claim 14, wherein the energy curable article comprises inks, coatings and adhesives.