CN112111062A - Silicon-containing monomer containing dioxygen heterocycle and preparation and application thereof - Google Patents

Silicon-containing monomer containing dioxygen heterocycle and preparation and application thereof Download PDF

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CN112111062A
CN112111062A CN201910544043.9A CN201910544043A CN112111062A CN 112111062 A CN112111062 A CN 112111062A CN 201910544043 A CN201910544043 A CN 201910544043A CN 112111062 A CN112111062 A CN 112111062A
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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 a silicon-containing monomer containing a dioxygen heterocycle, and preparation and application thereof. The invention relates to compounds of the formulae (I) and (II), where the variables n, m, z, p', R2、R3、R4、R5、R6、R7And R8As defined in the specification. The compound of the formula (I) has the advantages of good tensile property after photocuring, excellent hydrophobic property, stain resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance, good heat resistance, high curing speed and easy adjustment of performance, thereby widening the application range of a photocuring system. The invention also relates to the preparation of compounds of formulae (I) and (II), to photocurable compositions comprising compounds of formulae (I) and/or (II) and to photocurable materials obtained by photocuring of the photocurable compositions.

Description

Silicon-containing monomer containing dioxygen heterocycle and preparation and application thereof
Technical Field
The invention belongs to the technical field of photocuring materials, and particularly relates to a silicon-containing monomer containing a dioxygen heterocycle. 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 can be used for cationic photocuring and is a main raw material of a cationic photocuring product, and the system has the advantages of low viscosity, low toxicity, high polymerization speed, and excellent thermal stability and 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 inventors of the present invention conducted extensive and intensive studies on an oxacyclic cationically photopolymerizable monomer to find a novel oxacyclic cationically photocurable monomer which has advantages of fast photocuring speed, good tensile properties after curing, excellent hydrophobic properties, stain resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance, and the like. The present inventors have found that the silicon-containing monomer containing a dioxyheterocycle obtained by introducing an oxirane group into both ends of a polysiloxane chain has the aforementioned advantages.
Accordingly, it is an object of the present invention to provide a silicon-containing dioxyheterocycle-containing monomer which contains not only a cationically photocurable oxacycloalkyl group but also a polysiloxane chain. The oxacyclic monomer with the structure has the advantages of high photocuring speed, good tensile property after curing, excellent hydrophobic property, stain resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance and good heat resistance.
Another object of the present invention is to provide a method for preparing the silicon-containing dioxyheterocycle-containing 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 dioxyheterocycle-containing silicon-containing 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. compounds of the following formulae (I) and/or (II):
Figure BDA0002103446880000021
wherein
n is an integer of 1 to 50;
m is an integer of 1 to 10;
z is an integer from 0 to 10;
p and p' are the same or different and are integers from 1 to 6;
R2、R3、R4、R5、R6、R7are the same or different and are independently C6-C10Aryl radical, C1-C12Alkyl radical, C1-C12Alkoxy or C having two carbon atoms interrupted by one or more heteroatoms independently selected from N, O, S1-C12An 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 15, preferably an integer of 1 to 12; and/or
m is an integer of 1 to 6, preferably an integer of 2 to 4; and/or
z is an integer from 1 to 6, preferably an integer from 0 to 3; and/or
p and p' are the same or different and are each independently an integer of 1 to 4, preferably 1 to 3; 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 NRbO, S C of hetero atom1-C6Alkyl radical, wherein RbIs H or C1-C4Alkyl, preferably, 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 NRbO, S C of hetero atom1-C4Alkyl radical, wherein RbIs 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; preferably R8Is H or C1-C4An alkyl group.
3. The compound according to item 1, wherein
n is an integer of 1 to 12;
m is 2,3 or 4;
z is 0, 1,2 or 3;
p and p' are the same and are 1,2 or 3;
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 compounds 1 to 5.
5. A process for the preparation of a compound of formula (I) according to any one of items 1 to 4, comprising:
(1) reacting a compound of formula (III)
Figure BDA0002103446880000041
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for any one of items 1 to 4,
with a compound of formula (IV) to give a compound of formula (I)
Figure BDA0002103446880000042
Wherein p and R8As defined for any one of items 1 to 4, and X is halogen, for example chlorine, bromine or iodine.
6. The method according to item 5, wherein in step (1),
the reaction of the compound of formula (III) with the compound of formula (IV) 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 (III) to the basic catalyst is from 1:2 to 1: 10; and/or
The molar ratio of the compound of formula (III) to the compound of formula (IV) is 1:2 to 1: 2.4; and/or
The reaction between the compound of formula (III) and the compound of formula (IV) is firstly carried out at the freezing point temperature, and then the temperature is raised to 25-60 ℃, preferably to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
7. A process for the preparation of a compound of formula (II) according to any one of items 1 to 4, comprising:
(a) reacting a compound of formula (III)
Figure BDA0002103446880000043
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for any one of items 1 to 4,
with a compound of the formula (IV),
Figure BDA0002103446880000051
wherein p and R8As defined for any one of items 1 to 4 and X is halogen, for example chlorine, bromine or iodine, to give a compound of formula (V),
Figure BDA0002103446880000052
wherein n, m, z, R2、R3、R4、R5、R6、R7And R8As defined for any one of items 1 to 4; and
(b) reacting a compound of formula (V) with a compound of formula (VI) to give a compound of formula (II)
Figure BDA0002103446880000053
Wherein p' is as defined for any one of items 1 to 4 and Y is halogen, for example chlorine, bromine or iodine.
8. The method according to item 7, wherein in step (a),
the reaction of the compound of formula (III) with the compound of formula (IV) 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 (III) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (III) to the compound of formula (IV) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (III) and the compound of formula (IV) is firstly carried out at the freezing point temperature, and then the temperature is raised to 25-60 ℃, preferably to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
9. The method according to item 7 or 8, wherein in step (b),
the reaction of the compound of formula (V) with the compound of formula (VI) 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 (V) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (V) and the compound of formula (VI) is firstly carried out at the freezing temperature, and then the temperature is raised to 25-60 ℃, preferably 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
10. A process for the preparation of a compound of formula (II) according to any one of items 1 to 4, comprising:
(i) reacting a compound of formula (III)
Figure BDA0002103446880000061
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for any one of items 1 to 4,
with a compound of the formula (VI),
Figure BDA0002103446880000062
wherein p' is as defined for any one of items 1 to 4 and Y is halogen, for example chlorine, bromine or iodine,
to obtain the compound of the formula (V-a),
Figure BDA0002103446880000063
wherein n, m, z, p', R2、R3、R4、R5、R6And R7As defined for any one of items 1 to 4;
and
(ii) reacting a compound of formula (V-a) with a compound of formula (IV) to give a compound of formula (II)
Figure BDA0002103446880000064
Wherein p and R8As defined for any one of items 1 to 4, and X is halogen, for example chlorine, bromine or iodine.
11. The method according to item 10, wherein in step (i),
the reaction of the compound of formula (III) with the compound of formula (VI) 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 (III) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (III) to the compound of formula (VI) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (III) and the compound of formula (VI) is firstly carried out at the freezing point temperature, and then the temperature is raised to 25-60 ℃, preferably to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
12. The method according to item 10 or 11, wherein in step (ii),
the reaction of the compound of formula (V-a) with the compound of formula (IV) 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 (V-a) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (V-a) to the compound of formula (IV) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (V-a) and the compound of formula (IV) is firstly carried out at the freezing temperature, then the temperature is raised to 25-60 ℃, and preferably the temperature is raised to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
13. Any one of claims 5-12, wherein X is chlorine and Y is bromine.
14. A photocurable composition comprising a compound of formula (I) and/or (II) according to any one of items 1 to 4 as polymerized monomer.
15. A photocurable material obtained by photocuring the photocurable composition according to item 14.
Drawings
FIG. 1 is a graph of quaternary oxirane conversion versus exposure time for compound 1 prepared in example 1.
FIG. 2 is a graph of quaternary oxirane conversion versus exposure time for Compound 2 prepared in example 2.
FIG. 3 is a graph of ternary oxirane conversion versus exposure time for Compound 2 prepared in example 2.
Detailed Description
According to one aspect of the present invention, there is provided a compound of the following formula (I) and/or (II):
Figure BDA0002103446880000081
wherein
n is an integer of 1 to 50;
m is an integer of 1 to 10;
z is an integer from 0 to 10;
p and p' are the same or different and are integers from 1 to 6; r2、R3、R4、R5、R6、R7Are the same or different and are independently C6-C10Aryl radical, C1-C12Alkyl radical, C1-C12Alkoxy or C having two carbon atoms interrupted by one or more heteroatoms independently selected from N, O, S1-C12An 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 the formulae (I) and (II) contain both a cationically photocurable oxygen heterocyclic structure and a polysiloxane moiety. The compound with the structure can be subjected to cationic photocuring, and has the advantages of high photocuring speed, good tensile property after curing, excellent hydrophobic property, contamination resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance and the like. In addition, the compounds of the formulae (I) and (II) according to the invention have less volume shrinkage, better adhesion and faster polymerization rates than compounds which contain oxirane rings at both ends.
In the present invention, the prefix "Cn-Cm"in each case tableThe number of carbon atoms contained in the group is shown to be n-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 monovalent branched or unbranched saturated hydrocarbon radical having n to m, for example 1 to 12, preferably 1 to 6, particularly preferably 1 to 4, carbon atoms. As Cn-CmAs examples of alkyl groups, there may be mentioned 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-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, hexyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-dimethylbutyl, 1, 3-dimethylbutyl, 3-ethylbutyl, 1,1, 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.
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. AsCn-CmAs examples of the alkoxy group, there may be mentioned methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy and isomers thereof.
The term "C" as used hereinn-CmHaloalkyl "means C substituted by 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 examples of the haloalkyl group herein, mention may be made of monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, 1-chloromethylethyl, monochlorobutyl, 1-chloromethylpropyl, 2-chloromethylpropyl, 1-dichloromethylethyl, monochloropentyl, 1-chloromethylbutyl, 2-chloromethylbutyl, 3-chloromethylbutyl, 2-dichloromethylpropyl, 1-chloroethylpropyl, monochlorohexyl, 1-dichloromethylpropyl, 1, 2-dichloromethylpropyl, 1-chloromethylpentyl, 2-chloromethylpentyl, 3-chloromethylpentyl, 4-chloromethylpentyl, 1-dichloromethylbutyl, 1, 2-dichloromethylbutyl, 1, 3-dichloromethylbutyl, dichloromethylbutyl, 2, 2-dichloromethylbutyl, 2, 3-dichloromethylbutyl, 3-dichloromethylbutyl, 1-chloroethylbutyl, 2-chloroethylbutyl, 1, 2-trichloromethylpropyl, 1,2, 2-trichloromethylpropyl, 1-chloroethyl-1-methylpropyl, 1-ethyl-2-chloromethylpropyl and isomers thereof.
The term "C" as used 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 an integer from 1 to 15, particularly preferably an integer from 1 to 12, for example 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11 or 12.
In the compounds of the invention, m is generally an integer from 1 to 10, preferably an integer from 1 to 6, particularly preferably an integer from 2 to 4, for example 2,3 or 4, in particular 2.
In the compounds of the invention, z is generally an integer from 0 to 10, preferably an integer from 1 to 6, particularly preferably an integer from 0 to 3, for example 0, 1,2 or 3, in particular 1.
In the compounds of the invention, p and p' are identical or different and are each independently of the other usually an integer from 1 to 6, preferably an integer from 1 to 4, particularly preferably an integer from 1 to 3, for example 1,2 or 3, in particular 1.
In the compounds of the formulae (I) and (II) according to 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 NRbO, S C of hetero atom1-C12Alkyl radical, wherein RbIs 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 NRbO, S C of hetero atom1-C6Alkyl radical, wherein RbIs 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 NRbO, S C of hetero atom1-C4Alkyl radical, wherein RbIs 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 formulae (I) and (II) according to 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 compounds of formulae (I) and (II) of the present invention,
n is an integer of 1 to 12;
m is 2,3 or 4;
z is 0, 1,2 or 3;
p and p' are the same and are 1,2 or 3;
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.
In another embodiment of the present invention, the compounds of formula (I) and formula (II) are compounds selected from the group consisting of:
Figure BDA0002103446880000111
according to a second aspect of the present invention there is provided a process for the preparation of a compound of formula (I) according to the invention which comprises:
(1) reacting a compound of formula (III)
Figure BDA0002103446880000121
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for the compounds of formula (I),
with a compound of formula (IV) to give a compound of formula (I)
Figure BDA0002103446880000122
Wherein p and R8As defined for compounds of formula (I) and X is halogen, for example chlorine, bromine or iodine.
In step (1), the reaction of the terminal hydroxyl group in the compound of formula (III) with the halogen in the compound of formula (IV) is of a type known in the art, and the reaction produces a hydrogen halide. Generally, the reaction is carried out in the presence of a basic catalyst. As basic catalysts suitable for this reaction, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof may be mentioned. The amount of catalyst used is also conventional. Generally, the molar ratio of the compound of formula (III) to the basic catalyst is from 1:2 to 1: 10. The reaction of the compound of formula (III) with the compound of formula (IV) 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 (III), the compound of formula (IV) and the corresponding basic catalyst can be dissolved and do not participate in the reaction between the compound of formula (III) and the compound of formula (IV), 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 toluene, acetone, butanone, toluene, tetrahydrofuran, cyclohexane, 1, 4-dioxane, dichloromethane, acetonitrile, or any mixture thereof is preferably used. The amount of solvent is also conventional, and in general, the amount of solvent is 0.5 to 3 times the total weight of the compound of formula (III) and the compound of formula (IV). The compound of formula (IV) and the compound of formula (III) are generally used in a molar ratio of about twice the molar amount. Advantageously, the compound of formula (III) and the compound of formula (IV) are used in a molar ratio of from 1:2 to 1: 2.4. To achieve the above reaction, the compound of formula (III) and the basic catalyst are generally dissolved in a solvent, the temperature is reduced to the freezing point (about 0 ℃), then the compound of formula (IV) is added, and after the addition is completed, the resulting reaction mixture is stirred at the freezing point (about 0 ℃) for 0.5 to 3 hours, preferably 0.5 to 1 hour, then heated to 25 to 60 ℃, preferably 35 to 60 ℃, and the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours. The reaction is, of course, advantageously carried out with stirring. After the reaction is finished, the compound of the formula (I) is obtained through conventional post-treatment. This work-up generally comprises extraction or washing (for example with water, which is then advantageously freed from water using an absorbent compound such as magnesium sulfate or sodium sulfate), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and distillation under reduced pressure to further remove the solvent. If a higher purity product is to be obtained, impurities may also be isolated by recrystallization or column chromatography.
According to a third aspect of the present invention there is provided a process for the preparation of a compound of formula (II) of the present invention comprising:
(a) reacting a compound of formula (III)
Figure BDA0002103446880000131
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for the compound of formula (II),
with a compound of the formula (IV),
Figure BDA0002103446880000132
wherein p and R8As defined for the compounds of formula (II) and X is halogen, for example chlorine, bromine or iodine,
to obtain the compound of the formula (V),
Figure BDA0002103446880000133
wherein n, m, z, R2、R3、R4、R5、R6、R7And R8As defined for compounds of formula (II); and
(b) reacting a compound of formula (V) with a compound of formula (VI) to give a compound of formula (II)
Figure BDA0002103446880000134
Wherein p' is as defined for the compound of formula (II) and Y is halogen, for example chlorine, bromine or iodine.
In step (a), the reaction of the terminal hydroxyl group in the compound of formula (III) with the halogen in the compound of formula (IV) is of a type known in the art, and the reaction produces a hydrogen halide. Generally, the reaction is carried out in the presence of a basic catalyst. As basic catalysts suitable for this reaction, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof may be mentioned. The amount of catalyst used is also conventional. Generally, the molar ratio of the compound of formula (III) to the basic catalyst is from 1:1 to 1: 5. The reaction of the compound of formula (III) with the compound of formula (IV) 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 (III), the compound of formula (IV) and the corresponding basic catalyst can be dissolved and do not participate in the reaction between the compound of formula (III) and the compound of formula (IV), and it is preferable that the solvent also contributes to precipitation of the product, i.e., the compound of formula (V). As the solvent, an organic solvent is generally used, and toluene, acetone, butanone, toluene, tetrahydrofuran, cyclohexane, 1, 4-dioxane, dichloromethane, acetonitrile, or any mixture thereof is preferably used. The amount of solvent is also conventional, and in general, the amount of solvent is 0.5 to 3 times the total weight of the compound of formula (III) and the compound of formula (IV). The molar ratio of the compound of the formula (IV) to the compound of the formula (III) is generally approximately equimolar. Advantageously, the compound of formula (III) and the compound of formula (IV) are used in a molar ratio of from 1:1 to 1: 1.2. To achieve the above reaction, the compound of formula (III) and the basic catalyst are generally dissolved in a solvent, the temperature is reduced to the freezing point (about 0 ℃), then the compound of formula (IV) is added, and after the addition is completed, the resulting reaction mixture is stirred at the freezing point (about 0 ℃) for 0.5 to 3 hours, preferably 0.5 to 1 hour, then heated to 25 to 60 ℃, preferably 35 to 60 ℃, and the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours. The reaction is, of course, advantageously carried out with stirring. After the reaction is finished, the compound of the formula (V) is obtained through conventional post-treatment. This work-up generally comprises extraction or washing (for example with water, which is then advantageously freed from water using an absorbent compound such as magnesium sulfate or sodium sulfate), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and distillation under reduced pressure to further remove the solvent. If a higher purity product is to be obtained, impurities may also be isolated by recrystallization or column chromatography.
In step (b), the reaction of the terminal hydroxyl group in the compound of formula (V) with the halogen in the compound of formula (VI) is of a type known in the art, and the reaction produces a hydrogen halide. Generally, the reaction is carried out in the presence of a basic catalyst. As basic catalysts suitable for this reaction, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof may be mentioned. The amount of catalyst used is also conventional. Generally, the molar ratio of the compound of formula (V) to the basic catalyst is from 1:1 to 1: 5. The reaction of the compound of formula (V) with the compound of formula (VI) is generally carried out in a solvent. As the type of the solvent, there is no particular limitation as long as the compound of formula (V), the compound of formula (VI) and the corresponding basic catalyst can be dissolved and do not participate in the reaction between the compound of formula (V) and the compound of formula (VI), and it is preferable that the solvent also contributes to precipitation of the product, i.e., the compound of formula (II). 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 (V) and the compound of formula (VI). The molar ratio of the compound of the formula (VI) to the compound of the formula (V) is generally approximately equimolar. Advantageously, the compound of formula (V) and the compound of formula (VI) are used in a molar ratio of from 1:1 to 1: 1.2. To achieve the above reaction, the compound of formula (V) and the basic catalyst are generally dissolved in a solvent, the temperature is reduced to the freezing point (about 0 ℃), then the compound of formula (VI) is added, and after the addition is completed, the resulting reaction mixture is stirred at the freezing point (about 0 ℃) for 0.5 to 3 hours, preferably 0.5 to 1 hour, then heated to 25 to 60 ℃, preferably 35 to 60 ℃, and the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours. The reaction is, of course, advantageously carried out with stirring. After the reaction is finished, the compound of the formula (II) is obtained through conventional post-treatment. This work-up generally comprises extraction or washing (for example with water, which is then advantageously freed from water using an absorbent compound such as magnesium sulfate or sodium sulfate), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and distillation under reduced pressure to further remove the solvent. If a higher purity product is to be obtained, impurities may also be isolated by recrystallization or column chromatography.
According to a fourth aspect of the present invention there is provided a process for the preparation of a compound of formula (II) of the present invention comprising:
(i) reacting a compound of formula (III)
Figure BDA0002103446880000151
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for the compound of formula (II),
with a compound of the formula (VI),
Figure BDA0002103446880000152
wherein p' is as defined for the compound of formula (II) and Y is halogen, for example chlorine, bromine or iodine,
to obtain the compound of the formula (V-a),
Figure BDA0002103446880000161
wherein n, m, z, p', R2、R3、R4、R5、R6And R7As defined for compounds of formula (II); and
(ii) reacting a compound of formula (V-a) with a compound of formula (IV) to give a compound of formula (II)
Figure BDA0002103446880000162
Wherein p and R8As defined for compounds of formula (II) and X is halogen, for example chlorine, bromine or iodine.
In step (i), the reaction of the terminal hydroxyl group in the compound of formula (III) with the halogen in the compound of formula (VI) is of a type known in the art, and the reaction produces a hydrogen halide. Generally, the reaction is carried out in the presence of a basic catalyst. As basic catalysts suitable for this reaction, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof may be mentioned. The amount of catalyst used is also conventional. Generally, the molar ratio of the compound of formula (III) to the basic catalyst is from 1:1 to 1: 5. The reaction of the compound of formula (III) with the compound of formula (VI) 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 (III), the compound of formula (VI) and the corresponding basic catalyst can be dissolved and do not participate in the reaction between the compound of formula (III) and the compound of formula (VI), and it is preferable that the solvent also contributes to precipitation of the product, i.e., the compound of formula (V-a). 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 (III) and the compound of formula (VI). The molar ratio of the compound of the formula (VI) to the compound of the formula (III) is generally approximately equimolar. Advantageously, the compound of formula (III) and the compound of formula (VI) are used in a molar ratio of from 1:1 to 1: 1.2. To achieve the above reaction, the compound of formula (III) and the basic catalyst are generally dissolved in a solvent, the temperature is reduced to the freezing point (about 0 ℃), then the compound of formula (VI) is added, and after the addition is completed, the resulting reaction mixture is stirred at the freezing point (about 0 ℃) for 0.5 to 3 hours, preferably 0.5 to 1 hour, then heated to 25 to 60 ℃, preferably 35 to 60 ℃, and the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours. The reaction is, of course, advantageously carried out with stirring. After the reaction is finished, the compound of the formula (V-a) is obtained by conventional post-treatment. This work-up generally comprises extraction or washing (for example with water, which is then advantageously freed from water using an absorbent compound such as magnesium sulfate or sodium sulfate), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and distillation under reduced pressure to further remove the solvent. If a higher purity product is to be obtained, impurities may also be isolated by recrystallization or column chromatography.
In step (ii), the reaction of the terminal hydroxyl group in the compound of formula (V-a) with the halogen in the compound of formula (IV) is of a type known in the art, the reaction producing a hydrogen halide. Generally, the reaction is carried out in the presence of a basic catalyst. As basic catalysts suitable for this reaction, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof may be mentioned. The amount of catalyst used is also conventional. Generally, the molar ratio of the compound of formula (V-a) to the basic catalyst is from 1:1 to 1: 5. The reaction of the compound of formula (V-a) with the compound of formula (IV) is usually carried out in a solvent. As the type of the solvent, there is no particular limitation as long as the compound of the formula (V-a), the compound of the formula (IV) and the corresponding basic catalyst can be dissolved and do not participate in the reaction between the compound of the formula (V-a) and the compound of the formula (IV), and it is preferable that the solvent also contributes to precipitation of the product, i.e., the compound of the formula (II). 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 the solvent is also conventional, and in general, the amount of the solvent is 0.5 to 3 times the total weight of the compound of formula (V-a) and the compound of formula (IV). The compound of the formula (IV) and the compound of the formula (V-a) are usually used in a molar ratio of approximately equimolar amounts. Advantageously, the compound of formula (V-a) and the compound of formula (IV) are used in a molar ratio of from 1:1 to 1: 1.2. To achieve the above reaction, the compound of formula (V-a) and the basic catalyst are generally dissolved in a solvent, the temperature is reduced to the freezing point (about 0 ℃), then the compound of formula (IV) is added, and after the addition is completed, the resulting reaction mixture is stirred at the freezing point (about 0 ℃) for 0.5 to 3 hours, preferably 0.5 to 1 hour, then heated to 25 to 60 ℃, preferably 35 to 60 ℃, and the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours. The reaction is, of course, advantageously carried out with stirring. After the reaction is finished, the compound of the formula (II) is obtained through conventional post-treatment. This work-up generally comprises extraction or washing (for example with water, which is then advantageously freed from water using an absorbent compound such as magnesium sulfate or sodium sulfate), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and distillation under reduced pressure to further remove the solvent. If a higher purity product is to be obtained, impurities may also be isolated by recrystallization or column chromatography.
In some preferred embodiments of the invention, wherein X is chlorine and Y is bromine.
The compound of the formula (I) and the compound of the formula (II) are silicon-containing monomers containing dioxygen heterocycle, the monomers have high curing speed, better stretching performance after curing, excellent hydrophobic performance, stain resistance, fingerprint resistance, chemical corrosion resistance and strong aging resistance. The synthesis method is simple and easy, and the conditions are mild; the raw materials are easy to obtain and the price is low.
Thus, according to a third aspect of the present invention, there is provided a photocurable composition comprising as polymerized monomers the compounds of formula (I) and/or (II) of the present invention. The photocurable composition may contain, in addition to the compound of formula (I) and the compound of formula (II) of the present invention, a ring-opening polymerization photoinitiator (a photoinitiator capable of initiating cationic polymerization) and 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 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 cationic 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 BDA0002103446880000181
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 said substituted phenyl comprisesThe substituent is one or more selected from halogen, nitro and C1-C6Alkyl and C1-C6A group of alkoxy groups; and
y, Z are non-nucleophilic anions, e.g. triflate, BF4 、ClO4 、PF6 、AsF6 、SbF6
For example, as the photoinitiator, one or more selected from the group consisting of 4- (phenylthio) phenyl diphenylsulfonium hexafluorophosphate, 4- (phenylthio) phenyl diphenylsulfonium hexafluoroantimonate, bis (4- (diphenylsulfonium) phenyl) sulfide bis hexafluorophosphate, bis (4- (diphenylsulfonium) phenyl) sulfide bis hexafluoroantimonate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate (810), 4-octyloxydiphenyliodonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 4-isobutylphenyl 4' -methylphenylidium hexafluorophosphate, and mixtures thereof, 4-isobutylphenyl 4' -methylphenyliodilium hexafluoroantimonate, bis (4-dodecylbenzene) iodonium hexafluorophosphate, bis (4-tert-butylbenzene) iodonium hexafluoroantimonate, 2-Isopropylthioxanthone (ITX).
For the purposes of the present invention, the amounts of photoinitiator are conventional. The photoinitiator is generally present in an amount of 0.5 to 5%, preferably 1 to 3%, based on 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 good tensile property, excellent hydrophobic property, stain resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance, good heat resistance and the like due to the fact that the photocuring material contains the compound shown in the formula (I) and/or (II) 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 with dropping funnel, temperature probe and reflux condenser, 18.6g (20mmol) of bishydroxy silicone oil (corresponding to the compound of formula (III) wherein n is 8, m is 2, z is 1, and R is added2、R3、R4、R5、R6And R7Methyl) and 30mL of toluene, stirring in an ice-water bath at the rotating speed of 300r/min, adding 8.92g (160mmol) of potassium hydroxide, then slowly dropwise adding 5.65g (44mmol) of 3-ethyl-3-chloromethyl oxetane, reacting for 30min at the temperature of the ice-water bath after dropwise adding, then removing the ice-water bath, reacting for 24 h in an oil bath at 60 ℃, and finishing the reaction. The reaction was washed repeatedly with distilled water, and the supernatant was collected and centrifuged to remove solid impurities. Removing most of the solvent by rotary evaporation at 45 deg.C and 0.1MPa with a rotary evaporator, and distilling the solution at 300Pa and 40 deg.C under reduced pressure to obtain the final product. Characterized by nuclear magnetic hydrogen spectroscopy, identified as compound 1 below, which is sometimes referred to as BOSi.1H NMR(400MHz,CDCl3):0.07-0.17(m,60H),0.56(m,4H),0.92(t,J=7.5Hz,6H),1.76-1.50(m,4H),1.87(q,J=7.5Hz,4H),3.46(t,J=7.0Hz,4H),3.58-3.54(m,4H),3.77-3.73(m,4H),3.82(s,4H),4.44(s,8H).
Figure BDA0002103446880000191
Example 2
In a three-necked flask with dropping funnel, temperature probe and reflux condenser, 18.6g (20mmol) of bishydroxy silicone oil (corresponding to the compound of formula (III) wherein n is 8, m is 2, z is 1, and R is added2、R3、R4、R5、R6And R7Methyl) and 30mL of toluene, stirring in an ice-water bath at a rotation speed of 300r/min, adding 4.46g (80mmol) of potassium hydroxide, slowly adding 2.83g (22mmol) of 3-ethyl-3-chloromethyl oxetane dropwise, and finishing dropwise addingAnd then reacting for 30min at the temperature of the ice-water bath, then removing the ice-water bath, carrying out oil bath at 60 ℃ for reacting for 24 hours again, and finishing the reaction. The reaction was washed repeatedly with distilled water, and the supernatant was collected and centrifuged to remove solid impurities. Removing most of the solvent by rotary evaporation at 45 deg.C and 0.1MPa with a rotary evaporator, and distilling the solution at 300Pa and 40 deg.C under reduced pressure to obtain the final product. The compound is characterized by nuclear magnetic hydrogen spectrum and is determined as the following compound 2 a.1H NMR(400MHz,CDCl3):0.07-0.17(m,60H),0.61(t,J=7.0Hz,4H),0.83(t,J=7.5Hz,3H),1.42(m,4H),1.69(q,J=7.5Hz,2H),3.35(m,4H),3.52(m,6H),3.70(m,2H),3.79(s,2H),4.39-4.14(m,1H),5.4(m,1H).
Figure BDA0002103446880000201
20.56g (20mmol) of Compound 2a and 30mL of toluene were put into a three-necked flask equipped with a dropping funnel, a temperature probe and a reflux condenser, stirred in an ice-water bath at a rotation speed of 300r/min, 4.46g (80mmol) of potassium hydroxide powder was added, 3.01g (22mmol) of epibromohydrin was slowly dropped thereinto, and after 30min of reaction, the ice-water bath was removed, and the reaction was carried out in an oil bath at 60 ℃ for 24 hours again to terminate the reaction. The reaction was washed repeatedly with distilled water, and the supernatant was collected and centrifuged to remove solid impurities. Removing most of the solvent by rotary evaporation at 45 deg.C and 0.1MPa with a rotary evaporator, and distilling the solution at 300Pa and 40 deg.C under reduced pressure to obtain the final product. Characterized by nuclear magnetic hydrogen spectroscopy, identified as compound 2 below, which is sometimes designated as BOTSi.1H NMR(400MHz,CDCl3):0.07-0.17(m,60H),0.58(t,J=7.0Hz,4H),0.92(t,J=7.5Hz,3H),1.56(m,4H),1.87(q,J=7.5Hz,2H),2.61-2.38(m,2H),2.74(m,H),3.61-3.36(m,16H),3.79(s,4H),4.44-4.14(m,4H).
Figure BDA0002103446880000202
Example 3
In a three-necked flask equipped with a dropping funnel, a temperature probe and a reflux condenser, 18.6g (20mmol) of bishydroxy silicone oil (corresponding to formula (III))Wherein n-8, m-2, z-1, and R2、R3、R4、R5、R6And R7Methyl) and 30mL of toluene, stirring in an ice-water bath at the rotation speed of 300r/min, adding 4.46g (80mmol) of potassium hydroxide powder, then slowly dropwise adding 3.01g (22mmol) of epoxy bromopropane, reacting at the temperature of the ice-water bath for 30min after the dropwise adding is finished, then removing the ice-water bath, carrying out oil bath at 60 ℃ for reacting for 24 h, and finishing the reaction. The reaction was washed repeatedly with distilled water, and the supernatant was collected and centrifuged to remove solid impurities. Removing most of the solvent by rotary evaporation at 45 deg.C and 0.1MPa with a rotary evaporator, and distilling the solution at 300Pa and 40 deg.C under reduced pressure to obtain the final product. The compound is identified as the following compound 2b by nuclear magnetic hydrogen spectrum characterization.1H NMR(400MHz,CDCl3):0.07-0.17(m,60H),0.61(t,J=7.0Hz,4H),1.56(m,4H),2.61-2.38(m,2H),2.74(m,H),3.70-3.38(m,14H),5.4(m,1H).
Figure BDA0002103446880000211
19.72g (20mmol) of the compound 2b and 30mL of toluene were put into a three-necked flask equipped with a dropping funnel, a temperature probe and a reflux condenser, stirred in an ice-water bath at a rotation speed of 300r/min, 42.23g (40mmol) of potassium hydroxide powder was added, 2.83g (22mmol) of 3-ethyl-3-chloromethyloxetane was slowly dropped thereinto, and after 30 minutes of reaction, the ice-water bath was removed, and the reaction was completed after further 24 hours in an oil bath at 60 ℃. The reaction was washed repeatedly with distilled water, and the supernatant was collected and centrifuged to remove solid impurities. Removing most of the solvent by rotary evaporation at 45 deg.C and 0.1MPa with a rotary evaporator, and distilling the solution at 300Pa and 40 deg.C under reduced pressure to obtain the final product. The compound is determined to be a compound 2 by nuclear magnetic hydrogen spectrum characterization
Example 4
Example 1 was repeated, but the bishydroxy silicone oil in example 1 was replaced by a bishydroxy silicone oil corresponding to a compound of formula (III) wherein n is 1, m is 2, z is 1, and R is2、R3、R4、R5、R6And R7Is methyl. The final product obtained isThe nuclear magnetic hydrogen spectrum is characterized and determined as the following compound 3.1H NMR(400MHz,CDCl3):0.07-0.17(m,12H),0.56(m,4H),0.92(t,J=7.5Hz,6H),1.76-1.50(m,4H),1.87(q,J=7.5Hz,4H),3.46(t,J=7.0Hz,4H),3.58-3.54(m,4H),3.77-3.73(m,4H),3.82(s,4H),4.44(s,8H).
Figure BDA0002103446880000221
Example 5
Example 1 was repeated, but the bishydroxy silicone oil in example 1 was replaced by a bishydroxy silicone oil corresponding to a compound of formula (III) wherein n-15, m-2, z-1, and R2、R3、R4、R5、R6And R7Is methyl. The obtained final product was characterized by nuclear magnetic hydrogen spectrum and identified as the following compound 4.1H NMR(400MHz,CDCl3):0.07-0.17(m,102H),0.56(m,4H),0.92(t,J=7.5Hz,6H),1.76-1.50(m,4H),1.87(q,J=7.5Hz,4H),3.46(t,J=7.0Hz,4H),3.58-3.54(m,4H),3.77-3.73(m,4H),3.82(s,4H),4.44(s,8H).
Figure BDA0002103446880000222
Example 6
In a three-necked flask with dropping funnel, temperature probe and reflux condenser, 18.6g (20mmol) of bishydroxy silicone oil (corresponding to the compound of formula (III) wherein n is 8, m is 2, z is 1, and R is added2、R3、R4、R5、R6And R7Methyl) and 30mL of toluene, stirring in an ice-water bath at the rotating speed of 300r/min, adding 8.92g (160mmol) of potassium hydroxide, then slowly dropwise adding 3.87g (44mmol) of 3-hydroxymethyl oxetane, reacting at the temperature of the ice-water bath for 30min after the dropwise adding is finished, then removing the ice-water bath, carrying out oil bath at 60 ℃ for reacting for 24 h again, and finishing the reaction. The reaction was washed repeatedly with distilled water, and the supernatant was collected and centrifuged to remove solid impurities. Removing most of the solvent by rotary evaporation at 45 deg.C and 0.1MPa with rotary evaporator, and removing the solutionDistilling under reduced pressure at 300Pa and 40 ℃ to obtain the product. The compound is characterized by nuclear magnetic hydrogen spectrum and is determined as the following compound 5.1H NMR(400MHz,CDCl3):0.07-0.17(m,60H),0.56(m,4H),1.76-1.50(m,4H),,2.92(s,2H),3.46(t,J=7.0Hz,4H),3.58-3.54(m,4H),3.77-3.73(m,4H),3.82(s,4H),4.44(s,8H).
Figure BDA0002103446880000223
Example 7
This example is intended to illustrate the photopolymerizability of the compounds 1 and 3 to 5 according to the invention.
The photopolymerization performance of the compounds 1 and 3-5 at different initiator concentrations is tested by a real-time infrared (RT-IR) method by taking a mixture of a photoinitiator diphenyliodonium hexafluorophosphate (810) and 2-Isopropylthioxanthone (ITX) in a mass ratio of 2:1 as a photoinitiation system. 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 calculated by monitoring the change of the area size of an 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. The results for compound 1 are shown in figure 1. FIG. 1 is a graph of oxetane ring conversion as a function of irradiation time. The results show that compound 1 has good photopolymerization performance. In addition, each of the compounds 3-5 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 with the four-membered oxygen heterocycle increases with the increase of the initiator concentration, and the maximum conversion rate of the four-membered oxygen heterocycle reaches at least 53%. Wherein the respective concentrations of 810 and ITX are based on the respective weights of compounds 1 and 3-5. Therefore, the compound of the invention has good photopolymerization performance.
Example 8
This example is intended to illustrate the photopolymerization performance of compound 2 prepared in example 2.
A mixture of a photoinitiator diphenyl iodonium hexafluorophosphate (810) and 2-Isopropyl Thioxanthone (ITX) in a mass ratio of 2:1 is used as a photoinitiation system, and the photopolymerization performance of the compound 2 at different initiator concentrations is tested by a real-time infrared method. The peak of the absorption of the C-O-C bond asymmetric deformation vibration of the oxetanyl group was found to be 980cm-1The vibration absorption peak of the C-O-C bond asymmetric deformation of the three-membered oxygen heterocycle is positioned at 910cm-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 rates of the quaternary oxygen heterocycle and the ternary oxygen heterocycle can be respectively calculated by monitoring the change of the area size of an 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. The results for compound 2 are shown in figures 2 and 3. FIG. 2 is a graph showing the change in the conversion of oxetane ring with irradiation time, and FIG. 3 is a graph showing the change in the conversion of oxirane ring with irradiation time. The result shows that the ternary heterocycle can promote the polymerization of the quaternary oxygen heterocycle, and the compound 2 has good photopolymerization performance.
Example 9
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 1-5 with 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate (E4221) epoxy monomer at a molar ratio of 5: 95, and 3.0 wt% 810 and 1.5 wt% ITX based on the total weight of the compounds 1 to 5 and E44221, respectively, as an initiator, and uniformly mixing 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 show that when the E4221 polymerization system is not added with the compound of the present invention, the water contact angle of the cured film is 62.5 °, and the contact angles reach 81.5 ° and 87.4 ° after the additional addition of compound 1 or 2, respectively. In addition, the contact angles of the cured films obtained by additionally adding one of the compounds 3 to 5 were each over 78.6 °. Therefore, the compound of the invention can remarkably improve the surface hydrophobicity of the cured film, thereby resisting contamination and fingerprints.
Example 10
The purpose of this example is to demonstrate that each of the compounds 1 and 2 prepared in examples 1-2 can improve the heat resistance of the cured film.
Each of the cured films of the compounds 1 to 2 was obtained in the same manner as described in example 9. 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 Table 1.
The results show that, after addition of the compounds 1 or 2, the initial decomposition temperature (T) of the cured film5%) And maximum temperature T of thermal weight lossmax1And Tmax2The heat resistance is improved remarkably.
TABLE 1
Figure BDA0002103446880000241

Claims (15)

1. Compounds of the following formulae (I) and/or (II):
Figure FDA0002103446870000011
wherein
n is an integer of 1 to 50;
m is an integer of 1 to 10;
z is an integer from 0 to 10;
p and p' are the same or different and are integers from 1 to 6;
R2、R3、R4、R5、R6、R7are the same or different and are independently C6-C10Aryl radical, C1-C12Alkyl radical, C1-C12Alkoxy or C having two carbon atoms interrupted by one or more heteroatoms independently selected from N, O, S1-C12An 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 15, preferably an integer of 1 to 12; and/or
m is an integer of 1 to 6, preferably an integer of 2 to 4; and/or
z is an integer from 1 to 6, preferably an integer from 0 to 3; and/or
p and p' are the same or different and are each independently an integer of 1 to 4, preferably 1 to 3; 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 NRbO, S C of hetero atom1-C6Alkyl radical, wherein RbIs H or C1-C4Alkyl, preferably, 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 NRbO, S C of hetero atom1-C4Alkyl radical, wherein RbIs H or C1-C4An alkyl group; and/or
R8Is H, halogen,C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Hydroxyalkyl radical, C1-C4Alkoxy or C1-C4Haloalkoxy, preferably R8Is H or C1-C4An alkyl group.
3. A compound according to claim 1, wherein
n is an integer of 1 to 12;
m is 2,3 or 4;
z is 0, 1,2 or 3;
p and p' are the same and are 1,2 or 3;
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 FDA0002103446870000021
Figure FDA0002103446870000031
5. a process for the preparation of a compound of formula (I) according to any one of claims 1 to 4, comprising:
(1) reacting a compound of formula (III)
Figure FDA0002103446870000032
Wherein n, m, z, R2、R3、R4、R5、R6And R7Reaction with a compound of formula (IV) as defined in any one of claims 1 to 4 to give a compound of formula (I)
Figure FDA0002103446870000033
Wherein p and R8As defined for any one of claims 1-4, and X is halogen, such as chlorine, bromine, or iodine.
6. The method according to claim 5, wherein in step (1),
the reaction of the compound of formula (III) with the compound of formula (IV) 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 (III) to the basic catalyst is from 1:2 to 1: 10; and/or
The molar ratio of the compound of formula (III) to the compound of formula (IV) is 1:2 to 1: 2.4; and/or
The reaction between the compound of formula (III) and the compound of formula (IV) is firstly carried out at the freezing point temperature, and then the temperature is raised to 25-60 ℃, preferably to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
7. A process for the preparation of a compound of formula (II) according to any one of claims 1 to 4, comprising:
(a) reacting a compound of formula (III)
Figure FDA0002103446870000041
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for any of claims 1 to 4, with a compound of formula (IV),
Figure FDA0002103446870000042
wherein p and R8As defined for any one of claims 1 to 4 and X is halogen, such as chlorine, bromine or iodine,
to obtain the compound of the formula (V),
Figure FDA0002103446870000043
wherein n, m, z, R2、R3、R4、R5、R6、R7And R8As defined for any one of claims 1-4; and
(b) reacting a compound of formula (V) with a compound of formula (VI) to give a compound of formula (II)
Figure FDA0002103446870000044
Wherein p' is as defined for any one of claims 1 to 4 and Y is halogen, such as chlorine, bromine or iodine.
8. The method according to claim 7, wherein in step (a),
the reaction of the compound of formula (III) with the compound of formula (IV) 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 (III) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (III) to the compound of formula (IV) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (III) and the compound of formula (IV) is firstly carried out at the freezing point temperature, and then the temperature is raised to 25-60 ℃, preferably to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
9. The method according to claim 7 or 8, wherein in step (b),
the reaction of the compound of formula (V) with the compound of formula (VI) 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 (V) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (V) and the compound of formula (VI) is firstly carried out at the freezing temperature, and then the temperature is raised to 25-60 ℃, preferably 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
10. A process for the preparation of a compound of formula (II) according to any one of claims 1 to 4, comprising:
(i) reacting a compound of formula (III)
Figure FDA0002103446870000051
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for any of claims 1 to 4, with a compound of the formula (VI),
Figure FDA0002103446870000052
wherein p' is as defined for any one of claims 1 to 4 and Y is halogen, such as chlorine, bromine or iodine, to give a compound of formula (V-a),
Figure FDA0002103446870000053
wherein n, m, z, p', R2、R3、R4、R5、R6And R7As defined for any one of claims 1-4; and
(ii) reacting a compound of formula (V-a) with a compound of formula (IV) to give a compound of formula (II)
Figure FDA0002103446870000061
Wherein p and R8As defined for any one of claims 1-4, and X is halogen, such as chlorine, bromine, or iodine.
11. The method according to claim 10, wherein in step (i),
the reaction of the compound of formula (III) with the compound of formula (VI) 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 (III) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (III) to the compound of formula (VI) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (III) and the compound of formula (VI) is firstly carried out at the freezing point temperature, and then the temperature is raised to 25-60 ℃, preferably to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
12. The method according to claim 10 or 11, wherein in step (ii),
the reaction of the compound of formula (V-a) with the compound of formula (IV) 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 (V-a) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (V-a) to the compound of formula (IV) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (V-a) and the compound of formula (IV) is firstly carried out at the freezing temperature, then the temperature is raised to 25-60 ℃, and preferably the temperature is raised to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
13. Any of claims 5-12, wherein X is chloro and Y is bromo.
14. Photocurable composition comprising as polymerized monomers compounds of the formula (I) and/or (II) according to any of claims 1 to 4.
15. A photocurable material obtained by photocuring the photocurable composition according to claim 14.
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