CN112111063A - Polysiloxane-containing oxetane monomer and preparation and application thereof - Google Patents

Polysiloxane-containing oxetane monomer and preparation and application thereof Download PDF

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CN112111063A
CN112111063A CN201910543103.5A CN201910543103A CN112111063A CN 112111063 A CN112111063 A CN 112111063A CN 201910543103 A CN201910543103 A CN 201910543103A CN 112111063 A CN112111063 A CN 112111063A
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孙芳
马浩钦
邹应全
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HUBEI GURUN TECHNOLOGY CO LTD
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Abstract

The application relates to polysiloxane-containing oxetane monomers and their preparation and use. The invention relates to compounds of formula (I), wherein the variables n, m, p, R1、R2、R3、R4、R5、R6、R7And R8As defined in the specification. The compound of the formula (I) can be polymerized by light, and has the advantages of good tensile property, excellent hydrophobic property, contamination resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance and the like after photocuring. The invention also relates to the preparation of the compound of formula (I), to a photocurable composition comprising the compound of formula (I) and to a photocurable material obtained by photocuring of the photocurable composition.

Description

Polysiloxane-containing oxetane monomer and preparation and application thereof
Technical Field
The invention belongs to the technical field of photocuring materials, and particularly relates to an oxetane monomer containing polysilicon. The present invention also relates to a process for preparing the monomer, a photocurable composition comprising the monomer and a photocurable material obtained by photocuring the photocurable composition.
Background
Ultraviolet curing refers to a process in which a photoinitiator is excited to become a radical or a cation under the irradiation of ultraviolet rays, thereby initiating a polymerization curing reaction between monomers to form a high molecular polymer. Compared with thermal curing, the ultraviolet curing technology has the advantages of small environmental pollution, high coating quality, low energy consumption and the like, so the ultraviolet curing technology is widely applied to the fields of photo-curing coatings, adhesives, ink printing and the like. And with the stricter emission control of the organic volatile components, the ultraviolet curing technology has wider development prospect.
Compared with free radical photopolymerization systems, cationic photopolymerization systems have the advantages of insensitivity to oxygen, small volume shrinkage, strong adhesion, post-curing capability and the like, so that the cationic photopolymerization systems occupy irreplaceable important positions in the field of photopolymerization. The oxirane monomer belongs to a cationic photocuring system. The oxirane monomer is the main raw material of a high-end cation photocuring product, and the system has low viscosity, low toxicity, high polymerization speed, excellent thermal stability and excellent mechanical properties. 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. 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 situation in the prior art, the present inventors have conducted extensive and intensive studies on oxetane-based cationically photopolymerizable monomers, and have found a novel oxetane-based cationically photopolymerizable monomer which has advantages of good tensile properties, excellent hydrophobic properties, stain resistance, fingerprint resistance, etc. after photocuring. The inventor finds that the polysiloxane chain is introduced into the oxetane monomer, and the obtained polysiloxane-containing oxetane monomer has the advantages of good tensile property, excellent hydrophobic property, stain resistance, fingerprint resistance and the like after photocuring.
It is therefore an object of the present invention to provide a polysiloxane-containing oxetane monomer which contains not only cationically photocurable oxetane groups but also polysiloxane chains. The oxetane monomer with the structure has good tensile property after photocuring, excellent hydrophobic property, contamination resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance and good heat resistance.
It is another object of the present invention to provide a process for preparing the polysiloxane-containing oxetane monomer of the present invention. The preparation process is simple and feasible, the conditions are mild, the raw materials are easy to obtain, and the price is low.
It is a further object of the present invention to provide a photocurable composition comprising a polysiloxane-containing oxetane monomer according to the present invention.
It is a final object of the present invention to provide a photocurable material obtained by photocuring the photocurable composition of the present invention.
The technical solution for achieving the above object of the present invention can be summarized as follows:
1. a compound of the formula (I):
Figure BDA0002103171620000021
wherein
n is an integer of 1 to 50;
m is an integer of 0 to 20;
p is an integer of 1 to 6;
R1is C1-C12Alkyl or C1-C12An alkoxy group;
R2、R3、R4、R5、R6、R7are the same or different and are independently C6-C10Aryl radical, C1-C12Alkyl radical, C1-C12Alkoxy or two carbon atoms between which one or more are independently selected from NRaO, S C of hetero atom1-C12Alkyl radical, wherein RaIs H or C1-C4An alkyl group; and
R8is 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
n is an integer of 1 to 20, preferably an integer of 2 to 15; and/or
m is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3; and/or
p is an integer from 1 to 4, for example 1,2 or 3; and/or
R1Is C1-C6Alkyl or C1-C6An alkoxy group; r1Preferably C1-C4Alkyl or C1-C4An alkoxy group; and/or
R2、R3、R4、R5、R6、R7Are the same or different and are independently C6-C10Aryl radical, C1-C6Alkyl radical, C1-C6Alkoxy or two carbon atoms between which one or more members selected from NRaO, S C of hetero atom1-C6Alkyl radical, wherein RaIs H or C1-C4An alkyl group; preferably, R is2、R3、R4、R5、R6、R7Identical or different and independently of one another are phenyl, C1-C4Alkyl radical, C1-C4Alkoxy or two carbon atoms between which one or more are independently selected from NRaO, S C of hetero atom1-C4Alkyl radical, wherein RaIs H or C1-C4An alkyl group; and/or
R8Is H, halogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Hydroxyalkyl radical, C1-C4Alkoxy or C1-C4A haloalkoxy group.
3. The compound according to item 1, wherein
n is an integer of 1 to 9;
m is an integer of 1 to 5;
p is 1,2 or 3;
R1is C1-C4Alkyl or C1-C4An alkoxy group;
R2、R3、R4、R5、R6、R7identical or different and independently of one another are phenyl, C1-C4Alkyl radical, C1-C4Alkoxy or two carbon atoms between which one or more members selected from NRaO, S C of hetero atom1-C4Alkyl radical, wherein RaIs H or C1-C4An alkyl group; and
R8is H, halogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Hydroxyalkyl radical, C1-C4Alkoxy or C1-C4A haloalkoxy group;
it is preferable that the first and second liquid crystal layers are formed of,
n is an integer of 3 to 15;
m is an integer of 1 to 5;
p is 1;
R1is C1-C4An alkyl group;
R2、R3、R4、R5、R6、R7are the same or different and are independently C1-C4An alkyl group; and
R8is H or C1-C4An alkyl group.
4. The compound according to item 1, which is one or more compounds selected from the group consisting of:
Figure BDA0002103171620000041
Figure BDA0002103171620000051
5. a process for the preparation of a compound of formula (I) according to any one of items 1 to 4, comprising reacting a compound of formula (II):
Figure BDA0002103171620000052
wherein n and R1、R2、R3、R4、R5、R6And R7As defined in any one of items 1 to 4,
with a compound of the formula (III),
Figure BDA0002103171620000053
wherein m, p and R8As defined in any one of items 1 to 4,
to obtain the compound of formula (I).
6. The method according to item 5, wherein
The reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of Karstedt's catalyst or Speier's catalyst, preferably in an amount of 2 to 100ppm, based on the weight of the hydrogen-containing silicone oil; and/or
The molar ratio of the compound of the formula (II) to the compound of the formula (III) is 1:1-1: 1.5; and/or
The reaction between the compound of formula (II) and the compound of formula (III) is carried out at 80-110 ℃, preferably 85-100 ℃; and/or
The reaction between the compound of formula (II) and the compound of formula (III) is carried out for 3 to 6 hours, preferably 3.5 to 5.5 hours.
7. The method according to item 5 or 6, further comprising: reacting a compound of formula (IV)
Figure BDA0002103171620000061
Wherein p and R8As defined in any one of items 1 to 4,
with a compound of the formula (V),
Figure BDA0002103171620000062
wherein m is as defined in any of claims 1 to 4, X is halogen, for example fluorine, chlorine, bromine or iodine,
to obtain the compound of formula (III).
8. The method according to item 7, wherein
The reaction of the compound of formula (IV) with the compound of formula (V) is carried out in the presence of a basic catalyst, preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably the molar ratio of the compound of formula (IV) to the basic catalyst is 1:1 to 1: 3; and/or
The molar ratio of the compound of the formula (IV) to the compound of the formula (V) is 1:1-1: 1.2; and/or
The reaction between the compound of the formula (IV) and the compound of the formula (V) is carried out at from 80 to 120 ℃, preferably at from 100 to 120 ℃; and/or the presence of a gas in the gas,
the reaction between the compound of formula (IV) and the compound of formula (V) is carried out for 6 to 12 hours, preferably 8 to 10 hours.
9. A photocurable composition comprising a compound of formula (I) according to any one of items 1 to 4 as polymerized monomer.
10. A photocurable material obtained by photocuring the photocurable composition according to item 9.
Drawings
FIG. 1 is a graph of the oxetane ring conversion of Compound 1 prepared in example 1 as a function of irradiation time.
FIG. 2 is a graph of the oxetane ring conversion of Compound 2 prepared in example 2 as a function of irradiation time.
FIG. 3 is a graph of the oxetane ring conversion of Compound 3 prepared in example 3 as a function of irradiation time.
Fig. 4 is a contact angle diagram for a blank E4221 cured film and cured films of compounds 1-3 prepared in examples 1-3, respectively.
FIG. 5 is a thermogravimetric plot of a blank E4221 cured film and cured films of compounds 1-3 prepared for each of examples 1-3.
FIG. 6 is a graph of the mechanical properties of a blank E4221 cured film and the cured films of compounds 1-3 prepared in examples 1-3, respectively.
Detailed Description
According to one aspect of the present invention, there is provided a compound of formula (I):
Figure BDA0002103171620000071
wherein
n is an integer of 1 to 50;
m is an integer of 0 to 20;
p is an integer of 1 to 6;
R1is C1-C12Alkyl or C1-C12An alkoxy group;
R2、R3、R4、R5、R6、R7are the same or different and are independently C6-C10Aryl radical, C1-C12Alkyl radical, C1-C12Alkoxy radicalOr two carbon atoms interrupted by one or more independently selected from NRaO, S C of hetero atom1-C12Alkyl radical, wherein RaIs H or C1-C4An alkyl group; and
R8is H, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Hydroxyalkyl radical, C1-C6Alkoxy or C1-C6A haloalkoxy group.
In the present invention, the compounds of formula (I) comprise an oxetane structure and also a polysiloxane moiety. The compound with the structure can be cured by cationic light, and has the advantages of good tensile property, excellent hydrophobic property, stain resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance and good heat resistance after being cured by light.
In the present invention, the prefix "Cn-Cm"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 hereinn-CmAlkyl "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, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, and isomers thereof.
The term "C" as used herein6-CmAryl "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-CmAs 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 hereinn-CmAlkoxy "means at Cn-CmOpen chain C corresponding to alkyln-CmC having an oxygen atom as a linking group bonded to any carbon atom of the alkanen-CmAlkyl 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 hereinn-CmHaloalkyl "means C substituted with one or more halogen atoms which may be the same or differentn-CmAlkyl radicals, e.g. C1-C12Haloalkyl, preferably C1-C6Haloalkyl, particularly preferably C1-C4A haloalkyl group. As Cn-CmExamples of haloalkyl radicals which may be mentioned are the monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, 1-chloromethyl radicalsEthyl, chlorobutyl, 1-chloromethylpropyl, 2-chloromethylpropyl, 1-dichloromethylethyl, chloropentyl, 1-chloromethylbutyl, 2-chloromethylbutyl, 3-chloromethylbutyl, 2-dichloromethylpropyl, 1-chloroethylpropyl, monochlorohexyl, 1-dichloromethylpropyl, 1, 2-dichloromethylpropyl, 1-chloromethylpentyl, 2-chloromethylpentyl, 3-chloromethylpentyl, 4-chloromethylpentyl, 1-dichloromethylbutyl, 1, 2-dichloromethylbutyl, 1, 3-dichloromethylbutyl, 2-dichloromethylbutyl, 2, 3-dichloromethylbutyl, 3-dichloromethylbutyl, 1-chloroethylbutyl, 1-dichloromethylethyl, 1-dichloromethylethyl, 2-dichloromethylpropyl, 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 hereinn-CmHaloalkoxy "means C substituted by one or more of the same or different halogen atomsn-CmAlkoxy radicals, e.g. C1-C12Haloalkoxy, more preferably C1-C6Haloalkoxy, particularly preferably C1-C4A haloalkoxy group. As Cn-CmAs 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 hereinn-CmHydroxyalkyl "means at Cn-CmOpen chain C corresponding to alkyln-CmC having a hydroxy group bonded to any carbon atom of the alkanen-CmAlkyl radicals, e.g. C1-C6Hydroxyalkyl, particularly preferably C1-C4Hydroxyalkyl radicals, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl and isomers thereof.
In the compounds of the invention, n is generally an integer from 1 to 50, preferably from 1 to 20, particularly preferably from 2 to 15, in particular from 3 to 15, for example 3,4, 5, 6, 7, 8 or 9.
In the compounds of the invention, m is generally an integer from 0 to 20, preferably an integer from 1 to 8, particularly preferably an integer from 1 to 5 or from 1 to 3, for example 1,2, 3,4 or 5.
In the compounds of the invention, p is generally an integer from 1 to 6, preferably an integer from 1 to 4, for example 1,2 or 3.
In the compounds 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.
In the compounds of the invention, R2、R3、R4、R5、R6、R7Are identical or different and are usually independently C6-C10Aryl radical, C1-C12Alkyl radical, C1-C12Alkoxy or two carbon atoms between which one or more are independently selected from NRaO, S C of hetero atom1-C12Alkyl radical, wherein RaIs H or C1-C4An alkyl group. Preferably, R is2、R3、R4、R5、R6、R7Are the same or different and are independently C6-C10Aryl radical, C1-C6Alkyl radical, C1-C6Alkoxy or two carbon atoms between which one or more members selected from NRaO, S C of hetero atom1-C6Alkyl radical, wherein RaIs H or C1-C4An alkyl group. It is particularly preferred that R2、R3、R4、R5、R6、R7Identical or different and independently of one another are phenyl, C1-C4Alkyl radical, C1-C4Alkoxy or two carbon atoms between which one or more are independently selected from NRaO, S C of hetero atom1-C4Alkyl radical, wherein RaIs H or C1-C4An alkyl group. Especially R2、R3、R4、R5、R6、R7Are the same or different and are independently C1-C4An alkyl group. For example, R2、R3、R4、R5、R6、R7The 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.
In the compounds of the invention, R8Usually H, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Hydroxyalkyl radical, C1-C6Alkoxy or C1-C6A haloalkoxy group. Preferably, R is8Is H, halogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Hydroxyalkyl radical, C1-C4Alkoxy or C1-C4A haloalkoxy group. It is particularly preferred that R8Is H or C1-C4An alkyl group. For example, R8Can 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.
In some preferred embodiments of the present invention,
n is an integer of 1 to 9;
m is an integer of 1 to 5;
p is 1,2 or 3;
R1is C1-C4Alkyl or C1-C4An alkoxy group;
R2、R3、R4、R5、R6、R7identical or different and independently of one another are phenyl, C1-C4Alkyl radical, C1-C4Alkoxy or two carbon atoms between which one or more members selected from NRaO, S C of hetero atom1-C4Alkyl radical, wherein RaIs H or C1-C4An alkyl group; and
R8is H, halogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Hydroxyalkyl radical, C1-C4Alkoxy or C1-C4A haloalkoxy group.
In another embodiment of the invention, the compound of formula (I) is a compound selected from the group consisting of:
Figure BDA0002103171620000111
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 present invention, which comprises reacting a compound of formula (II):
Figure BDA0002103171620000112
wherein n and R1、R2、R3、R4、R5、R6And R7As defined for the compounds of formula (I),
with a compound of the formula (III),
Figure BDA0002103171620000121
wherein m, p and R8As defined for the compounds of formula (I),
to obtain the compound of formula (I).
The compound of formula (II) contains a hydrogen atom on the silicon atom, and therefore, the compound of formula (II) can be referred to as a hydrogen-containing silicone oil. The addition reaction of a silicon atom-bonded hydrogen atom in the compound of formula (II) with an unsaturated carbon-carbon double bond in the compound of formula (III) is of a type known in the art. Generally, the reaction is carried out in the presence of a catalyst. As a catalyst suitable for this reaction, Karstedt's catalyst or Speier's catalyst is generally used. The amount of catalyst used is also conventional. In general, the catalyst is used in an amount of 2 to 100ppm by weight based on the weight of the hydrogen-containing silicone oil. The reaction of the compound of formula (II) with the compound of formula (III) is generally carried out in a solvent. As the type of the solvent, there is no particular limitation as long as the compound of formula (II), the compound of formula (III) and the 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 (I). As the solvent, an organic solvent is generally used, and petroleum ether, dichloromethane, toluene or any mixture thereof is preferably used. The amount of solvent is also conventional, and in general, the amount of solvent is 1.5 to 3 times the total weight of the compound of formula (II) and the compound of formula (III). The compounds of the formula (II) and of the formula (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 ranging from 1:1 to 1: 1.5. To achieve the above reaction, the compound of formula (II) and the catalyst are usually dissolved in a solvent, aged for a certain period of time, then contacted with the compound of formula (III), and then heated to the reaction temperature for a certain 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 formula (II) and the compound of formula (III) is generally from 80 to 110 ℃ and preferably from 85 to 100 ℃. The reaction between the compound of the formula (II) and the compound of the formula (III) is maintained at the reaction temperature for a period of usually 3 to 6 hours, preferably 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.
In another embodiment of the method of the present invention, further comprising: reacting a compound of formula (IV)
Figure BDA0002103171620000131
Wherein p and R8As defined for the compound of formula (III),
with a compound of the formula (V),
Figure BDA0002103171620000132
wherein m is as defined for the compound of formula (III), X is halogen, such as fluorine, chlorine, bromine or iodine,
to obtain the compound of formula (III).
The reaction of the hydroxyl group in the compound of formula (IV) with the halogen in the compound of formula (V) 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, mention may be made, for example, of sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof. The amount of catalyst used is also conventional. Generally, the molar ratio of the compound of formula (IV) to the basic catalyst is from 1:1 to 1: 3. The reaction of the compound of formula (IV) with the compound of formula (V) is generally carried out in a solvent. As the type of the solvent, there is no particular limitation as long as the compound of formula (IV), the compound of formula (V) and the corresponding basic 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 (III). 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 0.5 to 3 times the total weight of the compound of formula (IV) and the compound of formula (V). The compounds of formula (IV) and (V) are generally used in approximately equimolar amounts. Advantageously, the compound of formula (IV) and the compound of formula (V) are used in a molar ratio of from 1:1 to 1: 1.2. To achieve the above reaction, the compound of formula (IV), the compound of formula (V) and the catalyst are typically dissolved in a solvent and then heated to the reaction temperature for a period of time to give the compound of formula (III). The reaction temperature between the compound of the formula (IV) and the compound of the formula (V) is generally from 80 to 120 ℃ and preferably 100-120 ℃. The reaction between the compound of the formula (IV) and the compound of the formula (V) is maintained at the reaction temperature for a period of usually 6 to 12 hours, preferably 8 to 10 hours. The reaction is, of course, advantageously carried out with stirring. After the reaction is finished, the compound of the formula (III) is obtained through conventional post-treatment. This work-up generally comprises 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. Recrystallization is also possible if a higher purity product is to be obtained.
The compound of formula (I) is a cationic photocuring monomer, and has the advantages of good tensile property, excellent hydrophobic property, stain resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance and good heat resistance after photocuring polymerization.
Thus, according to a third aspect of the present invention, there is provided a photocurable composition comprising as polymerized monomers a compound of formula (I) according to the invention. The photocurable composition may contain, in addition to the compound of formula (I) of the present invention, a ring-opening polymerizable cationic photoinitiator (a photoinitiator capable of initiating cationic polymerization) and optionally other monomers and oligomers having a cationically photocurable group such as a vinyl ether double bond, an alicyclic epoxy group, an oxirane group or an oxetane group, for example, 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate (E4221). 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 the advantages of 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
Figure BDA0002103171620000141
Wherein
Ra、Rb、Rc、Rd、ReEach 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 with alkyl and substituted phenyl substituents, wherein the substituted phenyl comprises one or more substituents selected from halogen, nitro, 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 from 0.5 to 5% by weight, preferably from 1 to 3% by weight, based on the total weight of the photocurable composition of the present invention.
According to a final aspect of the present invention, there is provided a photocurable material obtained by photocuring the photocurable composition of the present invention. The photocuring material has the advantages of better tensile property, excellent hydrophobic property, stain resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance and good heat resistance due to the fact that the photocuring material contains the compound shown in the formula (I) as the photocuring monomer.
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
In a three-necked flask equipped with a temperature probe and a reflux condenser, 11.6g (0.1mol) of 3-hydroxymethyl-3-ethyl-oxetane, 14.40g (0.12mol) of 3-bromopropene, 30mL of toluene and 11.2(0.2mol) of potassium hydroxide were charged, the temperature was raised to 110 ℃ and the reaction was carried out for 10 hours under a stirring rate of 500r/min, followed by terminating the reaction. Washing the obtained reaction solution with distilled water for three times, taking supernatant, centrifuging to remove solid impurities, performing rotary evaporation at 45 ℃ and 0.1MPa by using a rotary evaporator, and performing reduced pressure distillation at 300Pa and 40 ℃ to obtain a compound 1a with the yield of 50%.
Figure BDA0002103171620000161
In a three-necked flask equipped with a temperature probe and a reflux condenser, 41.2g (0.1mol) of hydrogen-containing silicone oil (corresponding to a compound of formula (II) wherein n is 3, R1Is n-butylAnd R2、R3、R4、R5、R6And R7Methyl) and 8.24g 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, 18.72g (0.12mol) of Compound 1a 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. Characterized by nuclear magnetic hydrogen spectrum, the compound is determined as compound 1, which is sometimes called MOSi-3 hereinafter.
[MOSi-3]:1H NMR(400MHz,CDCl3)0.16-0.04(m,30H),0.56(m,4H),0.92(td,J＝7.4,5.8Hz,6H),1.34(m,4H),1.61(m,2H),1.78(d,J＝7.5Hz,2H),3.44(t,J＝6.8Hz,2H),3.57(d,J＝9.8Hz,2H),4.51-4.37(m,4H).
Figure BDA0002103171620000162
Example 2
In a three-necked flask equipped with a temperature probe and a reflux condenser, 63.4g (0.1mol) of hydrogen-containing silicone oil (corresponding to a compound of formula (II) wherein n is 6, R1Is n-butyl, and R2、R3、R4、R5、R6And R7Methyl) and 12.68g of Karstedt's catalyst (Karstedt's catalyst, ansamitra chemical) at a concentration of 100ppm were dissolved in the solvent anhydrous toluene and then heated to 60 ℃ for 40 min. Thereafter, 18.72g (0.12mol) of Compound 1a 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. Characterized by nuclear magnetic hydrogen spectrum, determined as compound 2, hereinafter sometimes referred to as MOSi-6.
[MOSi-6]:1H NMR(400MHz,CDCl3)0.14-0.04(m,48H),0.56(m,4H),0.92(td,J＝7.4,5.8Hz,6H),1.34(m,4H),1.61(m,2H),1.78(d,J＝7.5Hz,2H),3.44(t,J＝6.8Hz,2H),3.57(d,J＝9.8Hz,2H),4.51-4.37(m,4H).
Figure BDA0002103171620000171
Example 3
In a three-necked flask equipped with a temperature probe and a reflux condenser, 85.6g (0.1mol) of hydrogen-containing silicone oil (corresponding to a compound of formula (II) wherein n is 9, R1Is n-butyl, and R2、R3、R4、R5、R6And R7Methyl) and 17.12g 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, 18.72g (0.12mol) of Compound 1a 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. Characterized by nuclear magnetic hydrogen spectrum, determined as compound 3, hereinafter sometimes referred to as MOSi-9.
[MOSi-9]:1H NMR(400MHz,CDCl3)0.16-0.04(m,66H),0.56(m,4H),0.92(td,J＝7.4,5.8Hz,6H),1.34(m,4H),1.61(m,2H),1.78(d,J＝7.5Hz,2H),3.44(t,J＝6.8Hz,2H),3.57(d,J＝9.8Hz,2H),4.51-4.37(m,4H).
Figure BDA0002103171620000172
Example 4
In a three-necked flask equipped with a temperature probe and a reflux condenser, 130g (0.1mol) of hydrogen-containing silicone oil (corresponding to a compound of formula (II) wherein n is 15, R1Is n-butyl, and R2、R3、R4、R5、R6And R7Methyl) and 26g 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. Then, 18.72g (0.12mol) of Compound 1a was added dropwise to the three-necked flask, the temperature was raised to 90 ℃ and the mixture was heatedKept under stirring for 4 h. 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. Characterized by nuclear magnetic hydrogen spectrum, identified as compound 4, sometimes referred to hereinafter as MOSi-15.
[MOSi-15]:1H NMR(400MHz,CDCl3)0.16-0.04(m,102H),0.56(m,4H),0.92(td,J＝7.4,5.8Hz,6H),1.34(m,4H),1.61(m,2H),1.78(d,J＝7.5Hz,2H),3.44(t,J＝6.8Hz,2H),3.57(d,J＝9.8Hz,2H),4.51-4.37(m,4H).
Figure BDA0002103171620000181
Example 5
In a three-necked flask equipped with a temperature probe and a reflux condenser, 5.8g (0.05mol) of 3-hydroxymethyl-3-ethyl-oxetane, 10.62g (0.06mol) of 7-bromo-1-heptene, 20mL of toluene and 5.6g (0.1mol) of potassium hydroxide were charged, the temperature was raised to 110 ℃ and the reaction was carried out for 10 hours under a stirring rate of 500r/min, and then the reaction was terminated. Washing the obtained reaction solution with distilled water for three times, taking supernatant, centrifuging to remove solid impurities, performing rotary evaporation at 45 ℃ and 0.1MPa by using a rotary evaporator, and performing reduced pressure distillation at 300Pa and 40 ℃ to obtain a compound 5a with the yield of 50%.
Figure BDA0002103171620000182
In a three-necked flask equipped with a temperature probe and a reflux condenser, 41.2g (0.1mol) of hydrogen-containing silicone oil (corresponding to a compound of formula (II) wherein n is 3, R1Is n-butyl, and R2、R3、R4、R5、R6And R7Methyl) and 8.24g 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. Then, 25.46g (0.12mol) of Compound 5a was added dropwise to the three-necked flask, and the temperature was raised to 90 ℃ and maintained for 4 hours under stirring. Removing solid impurities by centrifugation, rotatingThe evaporator is used for rotary evaporation at the temperature of 45 ℃ and the pressure of 0.1MPa, and the obtained solution is subjected to reduced pressure distillation at the temperature of 300Pa and the temperature of 40 ℃ to obtain the product. And the compound is determined to be the compound 5 by nuclear magnetic hydrogen spectrum characterization.
1H NMR(400MHz,CDCl3)0.16-0.04(m,30H),0.56(m,4H),0.92(td,J＝7.4,5.8Hz,6H),1.34(m,2H),1.43-1.50(m,4H),1.23-1.29(m,6H),1.61(m,2H),1.78(d,J＝7.5Hz,2H),3.44(t,J＝6.8Hz,2H),3.57(d,J＝9.8Hz,2H),4.51-4.37(m,4H).
Figure BDA0002103171620000191
Example 6
In a three-necked flask equipped with a temperature probe and a reflux condenser, 8.8g (0.1mol) of 3-hydroxymethyloxetane, 14.40g (0.12mol) of 3-bromopropene, 20mL of toluene and 11.2(0.2mol) of potassium hydroxide were charged, the temperature was raised to 110 ℃ and the reaction was carried out for 10 hours under a stirring rate of 500r/min, followed by terminating the reaction. Washing the obtained reaction solution with distilled water for three times, taking supernatant, centrifuging to remove solid impurities, performing rotary evaporation at the temperature of 45 ℃ and the pressure of 0.1MPa by using a rotary evaporator, and performing reduced pressure distillation on the obtained solution at the temperature of 300Pa and the temperature of 40 ℃ to obtain a compound 6a with the yield of 50%.
Figure BDA0002103171620000192
In a three-necked flask equipped with a temperature probe and a reflux condenser, 41.2g (0.1mol) of hydrogen-containing silicone oil (corresponding to a compound of formula (II) wherein n is 3, R1Is n-butyl, and R2、R3、R4、R5、R6And R7Methyl) and 8.24g 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. Then, 15.36g (0.12mol) of Compound 6a was added dropwise to the three-necked flask, and the mixture was heated to 90 ℃ and kept for 4 hours under stirring. Centrifuging to remove solid impurities, rotary evaporating at 45 deg.C and 0.1MPa with rotary evaporator, and collecting the obtained solutionDistilling under reduced pressure at 300Pa and 40 ℃ to obtain the product. And the compound is identified as a compound 6 by nuclear magnetic hydrogen spectrum characterization.
1H NMR(400MHz,CDCl3)0.16-0.04(m,30H),0.56(m,4H),0.92(td,J＝7.4,5.8Hz,3H),1.34(m,4H),1.78(d,J＝7.5Hz,2H),2.92(m,1H)3.44(t,J＝6.8Hz,2H),3.57(d,J＝9.8Hz,2H),4.51-4.37(m,4H).
Figure BDA0002103171620000193
Example 7
This example is intended to illustrate the photopolymerizability of the compounds of the invention.
A mixture of a photoinitiator diphenyl iodonium hexafluorophosphate (810) and 2-isopropyl thioxanthone (ITX, sensitizer) in a mass ratio of 2:1 is used as a photoinitiation system, and the real-time infrared (RT-IR) method is adopted to test the photopolymerization performance of each of the compounds 1-6 under different initiator concentrations. The peak of the absorption of the C-O-C bond asymmetric deformation vibration of the oxetanyl group was found to be 980cm-1As the curing reaction proceeds, the C-O-C bond is broken by ring opening, and the absorption peak area at the corresponding position is reduced. The conversion rate of the quaternary oxygen heterocyclic ring can be respectively calculated by monitoring the change of the area size of the infrared absorption peak through RT-IR. The light source is a high-pressure mercury lamp, the emission wavelength is 365nm, and the light intensity is 60mW/cm2. Wherein the results for each of compounds 1-3 are shown in FIGS. 1-3, respectively. The results show that the compounds 1 to 3 have good photopolymerization properties. In addition, each of the compounds 4-6 has four initiating systems of 0.75% 810+ 0.38% ITX, 1.50% 810+ 0.75% ITX, 3.00% 810+ 1.50% ITX, 4.50% 810+ 2.25% ITX, and after 600 seconds of high-pressure mercury lamp irradiation, the conversion rate of the monomer of the quaternary oxygen heterocycle increases with the increase of the initiator concentration, and the maximum conversion rate of the quaternary oxygen heterocycle reaches at least 50%. Wherein the respective concentrations of 810 and ITX are based on the respective weights of compounds 1-6. Therefore, the compound of the invention has good photopolymerization performance.
Example 8
The present example is intended to demonstrate that the compounds of the present invention can improve the surface hydrophobicity of a photocurable film.
Reacting each of compounds 1-6 with 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate (E4221) epoxy monomer at a molar ratio of 5: 95, and uniformly mixing 3.0 wt% of 810 and 1.5 wt% of ITX which are respectively based on the total weight of the E4221 and the epoxy monomer and are used as initiators to obtain the photosensitive solution. Uniformly spreading the obtained photosensitive solution in a silica gel mold with the thickness of 70mm multiplied by 8mm multiplied by 6mm at the concentration of 60mW/cm2The film was exposed to light for 900 seconds under a high-pressure mercury lamp to obtain a completely cured film. Then, the surface hydrophobicity of each cured film was measured by using a water contact angle measuring instrument model OCA20 (model OCA20, daphysics, germany) at a measurement temperature of 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. 4.
As can be seen from FIG. 4, when the compound of the present invention is not added to the E4221 polymerization system, the water contact angle of the cured film is 62.5 °, and the water contact angles of the cured film are significantly increased to 84.2 °, 87.6 ° and 91.7 ° after the compounds 1-3 are additionally added. In addition, the contact angles of the cured films obtained by additionally adding one of the compounds 4 to 6 were all over 85 ° (93.5 °, 85.6 °, 86.0 °, respectively). Therefore, the compound of the invention can remarkably improve the surface hydrophobicity of the cured film, thereby resisting contamination and fingerprints.
Example 9
The present example is intended to demonstrate that the compounds of the present invention are capable of improving the heat resistance of cured films.
Cured films of each of the compounds 1 to 3 were obtained in the same manner as described in example 8. Then, the heat resistance of each photocurable film was measured by a thermal gravimetric analyzer model TGA 550 (TGA 550, watt & ltd., usa). The test conditions were: under the protection of nitrogen, the temperature range is 25-800 ℃, 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. 5 and Table 1.
As can be seen from Table 1 and FIG. 5, the initial decomposition temperature (T) of the cured film after addition of any of the compounds 1 to 35％) And maximum temperature T of thermal weight lossmax1And Tmax2Is obviously improved, thereby having high durabilityThe heat is significantly improved.
TABLE 1
Figure BDA0002103171620000211
Example 10
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 8. Tensile properties of the photocured films were then tested using an Instron-1211 type electronic tensile machine (Instron-1211 type, Instron corporation, USA). The test temperature was 25 ℃ and the test speed was 50 mm/min. Meanwhile, a blank E4221 cured film was prepared as a reference using the same method. The results are shown in FIG. 6.
As can be seen from FIG. 6, the tensile strength of the pure E4221 photocured film is 7.02MPa, and the tensile strength and elongation at break of the photocured film are gradually increased after the compound 1-3 monomer is additionally added. Therefore, the compound of the present invention can significantly improve the tensile properties of the cured film.

Claims (10)

1. A compound of the formula (I):
Figure FDA0002103171610000011
wherein
n is an integer of 1 to 50;
m is an integer of 0 to 20;
p is an integer of 1 to 6;
R1is C1-C12Alkyl or C1-C12An alkoxy group;
R2、R3、R4、R5、R6、R7are the same or different and are independently C6-C10Aryl radical, C1-C12Alkyl radical, C1-C12Alkoxy or having a number one interposed between two carbon atomsOne or more are independently selected from NRaO, S C of hetero atom1-C12Alkyl radical, wherein RaIs H or C1-C4An alkyl group; and
R8is 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
n is an integer of 1 to 20, preferably an integer of 2 to 15; and/or
m is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3; and/or
p is an integer from 1 to 4, for example 1,2 or 3; and/or
R1Is C1-C6Alkyl or C1-C6An alkoxy group; r1Preferably C1-C4Alkyl or C1-C4An alkoxy group; and/or
R2、R3、R4、R5、R6、R7Are the same or different and are independently C6-C10Aryl radical, C1-C6Alkyl radical, C1-C6Alkoxy or two carbon atoms between which one or more members selected from NRaO, S C of hetero atom1-C6Alkyl radical, wherein RaIs H or C1-C4An alkyl group; preferably, R is2、R3、R4、R5、R6、R7Identical or different and independently of one another are phenyl, C1-C4Alkyl radical, C1-C4Alkoxy or two carbon atoms between which one or more are independently selected from NRaO, S C of hetero atom1-C4Alkyl radical, wherein RaIs H or C1-C4An alkyl group; and/or
R8Is H, halogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Hydroxyalkyl radical, C1-C4Alkoxy or C1-C4A haloalkoxy group.
3. A compound according to claim 1, wherein
n is an integer of 2 to 15;
m is an integer of 1 to 5;
p is 1,2 or 3;
R1is C1-C4Alkyl or C1-C4An alkoxy group;
R2、R3、R4、R5、R6、R7identical or different and independently of one another are phenyl, C1-C4Alkyl radical, C1-C4Alkoxy or two carbon atoms between which one or more members selected from NRaO, S C of hetero atom1-C4Alkyl radical, wherein RaIs H or C1-C4An alkyl group; and
R8is H, halogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Hydroxyalkyl radical, C1-C4Alkoxy or C1-C4A haloalkoxy group;
it is preferable that the first and second liquid crystal layers are formed of,
n is an integer of 3 to 15;
m is an integer of 1 to 5;
p is 1;
R1is C1-C4An alkyl group;
R2、R3、R4、R5、R6、R7are the same or different and are independently C1-C4An alkyl group; and
R8is H or C1-C4An alkyl group.
4. The compound according to claim 1, which is one or more compounds selected from the group consisting of:
Figure FDA0002103171610000021
Figure FDA0002103171610000031
5. a process for the preparation of a compound of formula (I) according to any one of claims 1 to 4, comprising reacting a compound of formula (II):
Figure FDA0002103171610000032
wherein n and R1、R2、R3、R4、R5、R6And R7As defined in any of claims 1 to 4, with a compound of the formula (III),
Figure FDA0002103171610000033
wherein m, p and R8As defined in any one of claims 1 to 4,
to obtain the compound of formula (I).
6. A method according to claim 5, wherein
The reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of Karstedt's catalyst or Speier's catalyst, preferably in an amount of 2 to 100ppm, based on the weight of the hydrogen-containing silicone oil; and/or
The molar ratio of the compound of the formula (II) to the compound of the formula (III) is 1:1-1: 1.5; and/or
The reaction between the compound of formula (II) and the compound of formula (III) is carried out at 80-110 ℃, preferably 85-100 ℃; and/or
The reaction between the compound of formula (II) and the compound of formula (III) is carried out for 3 to 6 hours, preferably 3.5 to 5.5 hours.
7. The method according to claim 5 or 6, further comprising: reacting a compound of formula (IV)
Figure FDA0002103171610000041
Wherein p and R8As defined in any one of claims 1 to 4,
with a compound of the formula (V),
Figure FDA0002103171610000042
wherein m is as defined in any of claims 1 to 4 and X is halogen, such as fluorine, chlorine, bromine or iodine, to give compounds of formula (III).
8. The method according to claim 7, wherein
The reaction of the compound of formula (IV) with the compound of formula (V) is carried out in the presence of a basic catalyst, preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably the molar ratio of the compound of formula (IV) to the basic catalyst is 1:1 to 1: 3; and/or
The molar ratio of the compound of the formula (IV) to the compound of the formula (V) is 1:1-1: 1.2; and/or
The reaction between the compound of the formula (IV) and the compound of the formula (V) is carried out at from 80 to 120 ℃, preferably at from 100 to 120 ℃; and/or the presence of a gas in the gas,
the reaction between the compound of formula (IV) and the compound of formula (V) is carried out for 6 to 12 hours, preferably 8 to 10 hours.
9. A photocurable composition comprising a compound of formula (I) according to any one of claims 1 to 4 as polymerized monomer.
10. A photocurable material obtained by photocuring the photocurable composition according to claim 9.
CN201910543103.5A 2019-06-21 2019-06-21 Polysiloxane-containing oxetane monomer and preparation and application thereof Pending CN112111063A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113336946A (en) * 2021-06-21 2021-09-03 湖北固润科技股份有限公司 Nopol bio-based silicon-containing oxetane monomer and preparation method thereof
CN113416208A (en) * 2021-06-21 2021-09-21 湖北固润科技股份有限公司 Eugenol bio-based silicon-containing oxetane monomer and preparation method thereof
CN113620985A (en) * 2021-08-13 2021-11-09 合肥工业大学 Silicon-containing oxetane derivative and preparation method and application thereof
CN115521460A (en) * 2022-09-30 2022-12-27 湖北固润科技股份有限公司 Trifluoromethyl organosilicon oxacycloalkane monomer, and preparation and application thereof
CN115521463A (en) * 2022-09-30 2022-12-27 湖北固润科技股份有限公司 Trifluoromethyl organosilicon alicyclic epoxy monomer and preparation and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10316757A (en) * 1997-05-14 1998-12-02 Toagosei Co Ltd Cationically photopolymerizable organosilicon compound and its production
JP2000264969A (en) * 1999-03-16 2000-09-26 Ge Toshiba Silicones Co Ltd Condensed-type silicone composition, cured product, surface modification thereof, and lithography
CN1416447A (en) * 2000-02-18 2003-05-07 罗狄亚化学公司 Plastic material surface treatment with polymerisable and/or crosslinkable organic compsn. having reactive functions
JP2004043609A (en) * 2002-07-10 2004-02-12 Toagosei Co Ltd Oxetane ring-containing siloxane derivative
KR20090081880A (en) * 2008-01-25 2009-07-29 삼성에스디아이 주식회사 Additive for electrolyte of lithium secondary battery, organic electrolytic solution comprising the same and Lithium battery using the solution
CN102395622A (en) * 2009-04-14 2012-03-28 Jnc株式会社 Glass fiber-silsesquioxane composite molded article and method for producing same
CN106188548A (en) * 2016-07-16 2016-12-07 北京化工大学 A kind of organosilicon cationic light-cured resin of oxygen heterocycle butane structure and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10316757A (en) * 1997-05-14 1998-12-02 Toagosei Co Ltd Cationically photopolymerizable organosilicon compound and its production
JP2000264969A (en) * 1999-03-16 2000-09-26 Ge Toshiba Silicones Co Ltd Condensed-type silicone composition, cured product, surface modification thereof, and lithography
CN1416447A (en) * 2000-02-18 2003-05-07 罗狄亚化学公司 Plastic material surface treatment with polymerisable and/or crosslinkable organic compsn. having reactive functions
JP2004043609A (en) * 2002-07-10 2004-02-12 Toagosei Co Ltd Oxetane ring-containing siloxane derivative
KR20090081880A (en) * 2008-01-25 2009-07-29 삼성에스디아이 주식회사 Additive for electrolyte of lithium secondary battery, organic electrolytic solution comprising the same and Lithium battery using the solution
CN102395622A (en) * 2009-04-14 2012-03-28 Jnc株式会社 Glass fiber-silsesquioxane composite molded article and method for producing same
CN106188548A (en) * 2016-07-16 2016-12-07 北京化工大学 A kind of organosilicon cationic light-cured resin of oxygen heterocycle butane structure and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113336946A (en) * 2021-06-21 2021-09-03 湖北固润科技股份有限公司 Nopol bio-based silicon-containing oxetane monomer and preparation method thereof
CN113416208A (en) * 2021-06-21 2021-09-21 湖北固润科技股份有限公司 Eugenol bio-based silicon-containing oxetane monomer and preparation method thereof
WO2022267990A1 (en) * 2021-06-21 2022-12-29 湖北固润科技股份有限公司 Nopol bio-based silicon-containing oxetane monomer and method for preparing same
WO2022267989A1 (en) * 2021-06-21 2022-12-29 湖北固润科技股份有限公司 Eugenol bio-based silicon-containing oxetane monomer and preparation method therefor
CN113620985A (en) * 2021-08-13 2021-11-09 合肥工业大学 Silicon-containing oxetane derivative and preparation method and application thereof
CN115521460A (en) * 2022-09-30 2022-12-27 湖北固润科技股份有限公司 Trifluoromethyl organosilicon oxacycloalkane monomer, and preparation and application thereof
CN115521463A (en) * 2022-09-30 2022-12-27 湖北固润科技股份有限公司 Trifluoromethyl organosilicon alicyclic epoxy monomer and preparation and application thereof
WO2024067719A1 (en) * 2022-09-30 2024-04-04 湖北固润科技股份有限公司 Trifluoromethyl organosilicon oxacycloalkane monomer, and preparation and use thereof

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