CN111057028A - Fluorine-containing cationic polymerization monomer and synthesis and application thereof - Google Patents
Fluorine-containing cationic polymerization monomer and synthesis and application thereof Download PDFInfo
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- CN111057028A CN111057028A CN201811208451.9A CN201811208451A CN111057028A CN 111057028 A CN111057028 A CN 111057028A CN 201811208451 A CN201811208451 A CN 201811208451A CN 111057028 A CN111057028 A CN 111057028A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
- C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
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- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
Abstract
The present invention relates to monomeric compounds of formula (I) wherein the variables are as defined in the specification. The monomer is synthesized rapidly in high yield by a click chemistry reaction between thiol and olefin, and a substantially perfluorinated alkane chain is introduced into an oxirane monomer via a linker group containing a norbornane moiety, so that a photocured film obtained by cationic photocuring of the resulting monomer has high surface hardness, low surface energy, excellent hydrophobic and oleophobic properties, and particularly excellent oil stain resistance. The present invention also relates to a process for preparing the monomer, a polymer obtained by ring-opening polymerization of the monomer, a photocurable composition comprising the monomer and a photocurable material obtained by photocuring the photocurable composition.
Description
Technical Field
The invention relates to a novel fluorine-containing cationic polymerization monomer. The present invention also relates to a process for producing the monomer, a polymer obtained by ring-opening polymerization of the monomer, a photocurable composition comprising the monomer and a photocurable material obtained by photocuring the photocurable composition.
Background
The ultraviolet curing technology refers to a process in which a photoinitiator is excited to become a radical or a cation under the irradiation of ultraviolet light, so that the polymerization between monomers is initiated to form a high molecular polymer. Compared with the traditional thermal curing, the ultraviolet curing technology has the advantages of high speed, low energy consumption, small environmental pollution and the like, so the ultraviolet curing technology has wider application in the fields of coating, adhesive, ink printing and the like. And, with the stricter emission of the organic volatile components, the ultraviolet curing technology will have wider application.
Compared with free radical photocuring, the cationic photocuring system has the advantages of no oxygen inhibition interference, small volume shrinkage of a cured coating, low production cost and the like, so that the cationic photocuring system is widely concerned. In the cationic photocuring system, the products mainly used are monomers and oligomers with cationic photocuring groups such as vinyl ether double bonds, alicyclic epoxy groups, ethylene oxide groups, oxetane groups and the like. With the increasing demands of consumers on the properties of coatings, there is an increasing demand for anti-staining, anti-fingerprint, anti-corrosion and anti-scratch coatings. At present, the types of fluorine-containing photo-curable cationic monomers capable of meeting the requirements are few, and more types of fluorine-containing monomers capable of being cured by cationic light need to be developed.
Disclosure of Invention
In view of the above-mentioned state of the art, the present inventors have conducted extensive and intensive studies on an oxetane cationically polymerizable monomer, and have found a novel cationically photocurable fluorine-containing monomer which is efficient and simple in synthesis process, and gives a photocurable film having low surface energy, good hydrophobic and oleophobic properties, oil stain resistance, fingerprint resistance, chemical corrosion resistance, weather resistance and aging resistance after polymerization. The present inventors have found that a fluorine-containing cationic photocurable monomer can be synthesized rapidly and with high yield by introducing a substantially perfluorinated alkane into an oxirane monomer by a click chemistry reaction between a thiol and an olefin, and that a substantially perfluorinated alkane chain is introduced into the oxirane monomer via a linker group containing a norbornane moiety, so that the resulting photocurable film obtained by cationic photocuring of the monomer has high surface hardness, low surface energy, good hydrophobic and oleophobic properties, and particularly, excellent oil stain resistance.
Accordingly, it is an object of the present invention to provide a novel class of fluorine-containing cationically photocurable monomers which contain not only cationically photocurable oxetanyl groups (e.g., oxirane and oxetane groups) but also substantially perfluorinated alkyl groups. The monomer can be synthesized rapidly in high yield by a click chemistry reaction between thiol and olefin, and a substantially perfluorinated alkane chain is introduced into an oxirane monomer via a linker group containing a norbornane moiety, so that a photocured film obtained by cationic photocuring of the resulting monomer has high surface hardness, low surface energy, excellent hydrophobic and oleophobic properties, and particularly excellent oil stain resistance.
It is another object of the present invention to provide a method for preparing the fluorine-containing cationically photocurable monomer of the present invention. The monomer can be carried out by a click chemistry reaction between mercaptan and olefin, so the reaction is rapid and the yield is high.
It is a further object of the present invention to provide polymers obtained by ring-opening polymerization of the fluorine-containing cationically photocurable monomers of the present invention. The polymer is cured into a film, and has high surface hardness, low surface energy, excellent hydrophobic and oleophobic properties and particularly good oil stain resistance.
It is a further object of the present invention to provide a photocurable composition comprising a compound according to the invention or a mixture thereof.
It is a final object of the present invention to provide a photocurable material obtained by photocuring a photocurable composition comprising 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):
wherein
Y is a linear or branched alkyl group containing from 1 to 10 carbon atoms, preferably from 2 to 8 carbon atoms, the hydrogen atoms of which are substantially completely replaced by fluorine, preferably 80 to 100%, preferably 90 to 100%, of the hydrogen atoms of the alkyl group are replaced by fluorine, more preferably Y is a perfluorinated linear or branched alkyl group containing from 3 to 8 carbon atoms;
z is- (CH)2)p-, where p is 0, 1,2 or 3;
w is- (CH)2)q-, wherein q is 0, 1,2 or 3, with the proviso that p and q cannot both be 0;
(R0)mis W, O, Z m substituents R on the ring formed together with the carbon atom linking Z and W0Wherein m is 0, 1 or 2, and R0Is selected from C1-C6Alkyl and hydroxy C1-C6Alkyl, wherein when m is 2, two R are0May be the same or different;
n1 is 1 or 2;
n3 is 1,2, 3 or 4;
R1and R2Each independently selected from H, C1-C6Alkyl and C1-C6Alkoxy, when n1 is 2, two R1May be the same or different, and two R2May be the same or different;
R5and R6Each independently selected from H and C1-C6Alkyl, wherein when n3 is 2,3 or 4, n 3R5Which may be the same or different, and n 3R6May be the same or different; and
R7、R8、R9、R10and R11Each independently selected from H and C1-C4An alkyl group.
2. The compound according to claim 1, wherein p and q are both 1, or one of p and q is 0 and the other is 1.
3. The method according to claim 1 or 2Wherein m is 0 or 1, and when m is 1, R0Preferably on the carbon atom linking Z and W.
4. A compound according to any one of claims 1 to 3, wherein n1 is 1; and/or n3 is 2.
5. The compound according to any one of items 1 to 4, wherein
R0Is selected from C1-C4Alkyl and hydroxy C1-C4An alkyl group; and/or
R1、R2Each independently selected from H, C1-C4Alkyl and C1-C4Alkoxy, preferably R1、R2Are all H; and/or
R5And R6Each independently selected from H and C1-C4Alkyl, preferably both are H; and/or
R7、R8、R9、R10And R11Each independently selected from H and C1-C2Alkyl groups, preferably both are H.
6. The compound according to item 1, which is a compound selected from the group consisting of:
7. a process for the preparation of a compound of formula (I) as described in any one of items 1 to 6, comprising:
1) reacting a compound of formula (II)
Wherein R is7、R8、R9、R10And R11As defined for compounds of formula (I), and X is halogen, preferably chloro or bromo;
carrying out esterification reaction with the compound of the formula (III),
z, W, R therein0、R1、R2M and n1 are as defined for the compound of formula (I),
to obtain the compound of the formula (IV),
z, W, R therein0、R1、R2、R7、R8、R9、R10、R11M and n1 are as defined for the compound of formula (I); and
2) reacting a compound of formula (IV) with a compound of formula (V),
wherein R is5、R6、n3And Y is as defined for the compound of formula (I),
to obtain the compound of formula (I).
8. The process of claim 7, wherein the reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a fulgide agent, preferably triethylamine, aniline, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or any mixture thereof.
9. The process according to claim 7 or 8, wherein the molar ratio of the compound of formula (III) to the compound of formula (II) is from 1.0 to 2.0, preferably from 1.1 to 1.5; and/or the molar ratio of the fulgide agent to the compound of formula (II) is 1.0 to 2.0, preferably 1.1 to 1.5; and/or the reaction in step 1) is carried out at a temperature of 20 to 30 ℃, preferably at room temperature.
10. The process according to any one of claims 7 to 9, wherein the reaction of step 2) is carried out according to step 2 a): 2a) reacting a compound of formula (IV) with a compound of formula (V) in the presence of a free radical initiator and in the absence of oxygen, preferably
The free radical initiator is selected from azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide or any mixture thereof; and/or the molar ratio of compound of formula (IV) to compound of formula (V) is from 0.8 to 1.5, preferably from 0.9 to 1.1; and/or the reaction of step 2a) is carried out at a temperature of 40 to 110 ℃, preferably 50 to 100 ℃.
11. The process according to any one of claims 7 to 9, wherein the reaction of step 2) is carried out according to step 2 b): 2b) reacting the compound of formula (IV) and the compound of formula (V) under UV irradiation, preferably,
the reaction in the step 2b) is carried out under the irradiation of an ultraviolet lamp with an emission waveband of 300-600 nm; and/or the molar ratio of compound of formula (IV) to compound of formula (V) is from 0.8 to 1.5, preferably from 0.9 to 1.0; and/or the reaction of step 2b) is carried out at room temperature.
12. A polymer obtained by ring-opening polymerization of a compound of formula (I) as described in any one of items 1 to 6, preferably by cationic photocuring, especially uv-curing in the presence of a photoinitiator.
13. A photocurable composition comprising a compound of formula (I) as described in any one of items 1 to 6 as a polymerized monomer.
14. A photocurable material obtained by photocuring the photocurable composition according to item 13.
Detailed Description
According to one aspect of the present invention, there is provided a compound of formula (I):
wherein
Y is a linear or branched alkyl group containing from 1 to 10 carbon atoms, the hydrogen atoms of which are substantially completely replaced by fluorine;
z is- (CH)2)p-, where p is 0, 1,2 or 3;
w is- (CH)2)q-, where q is 0, 1,2 or 3, with the proviso that pAnd q cannot be 0 at the same time;
(R0)mis W, O, Z m substituents R on the ring formed together with the carbon atom linking Z and W0，
Wherein m is 0, 1 or 2, and R0Is selected from C1-C6Alkyl and hydroxy C1-C6Alkyl, wherein when m is
At 2, two R0May be the same or different;
n1 is 1 or 2;
n3 is 1,2, 3 or 4;
R1and R2Each independently selected from H, C1-C6Alkyl and C1-C6Alkoxy, when n1 is 2, two R1May be the same or different, and two R2May be the same or different;
R5and R6Each independently selected from H and C1-C6Alkyl, wherein when n3 is 2,3 or 4, n 3R5Which may be the same or different, and n 3R6May be the same or different; and
R7、R8、R9、R10and R11Each independently selected from H and C1-C4An alkyl group.
In the compounds of the present invention, Y is a substantially perfluorinated linear or branched alkyl group containing 1 to 10 carbon atoms, preferably a substantially perfluorinated linear or branched alkyl group containing 2 to 8 carbon atoms, more preferably a perfluorinated linear or branched alkyl group containing 3 to 8 carbon atoms. In the present invention, "substantially perfluorinated linear or branched alkyl" means that at least 80% of all hydrogen atoms of the linear or branched alkyl group are replaced by fluorine, preferably 80-100%, more preferably 90-100% of the hydrogen atoms of the linear or branched alkyl group are replaced by fluorine, in particular all hydrogen atoms of the linear or branched alkyl group are replaced by fluorine, i.e. Y is a perfluorinated alkyl group. As examples of Y, mention may be made of trifluoromethyl, tetrafluoroethyl, pentafluoroethyl, heptafluoropropyl, 1-trifluoromethyltetrafluoroethyl, nonafluorobutyl, undecafluoropentyl and tridecafluorohexyl.
Z and W arePart of the oxacycloalkane moiety in the compound. Z is- (CH)2)p-, where p is 0, 1,2 or 3. W is- (CH)2)q-, where q is 0, 1,2 or 3, with the proviso that p and q cannot both be 0. Preferably, p and q are both 1, or one of p and q is 0 and the other is 1. That is, it is preferable that the oxacycloalkane moiety in the compound of the present invention is an oxetane or oxirane ring.
(R0)mIs W, O, Z m substituents R on the ring formed together with the carbon atom linking Z and W0Wherein m is 0, 1 or 2, and R0Is selected from C1-C6Alkyl and hydroxy C1-C6Alkyl, wherein when m is 2, two R are0May be the same or different. Preferably, m is 0 or 1. When m is 1, R0Advantageously on the carbon atom linking Z and W. R0Preferably selected from C1-C4Alkyl and hydroxy C1-C4Alkyl groups such as methyl, ethyl, propyl, butyl, hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl.
In the present invention, n1 is 1 or 2, preferably n1 is 1. R1And R2Each independently selected from H, C1-C6Alkyl and C1-C6Alkoxy, preferably each independently selected from H, C1-C4Alkyl and C1-C4Alkoxy groups such as methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy and butoxy. When n1 is 2, two R1May be the same or different, and two R2May be the same or different. Particular preference is given to R1And R2Are all H.
In the present invention, n3 is 1,2, 3 or 4, preferably 2. R5And R6Each independently selected from H and C1-C6Alkyl, preferably each independently selected from H and C1-C4Alkyl radicals, such as methyl, ethyl, propyl, butyl. When n3 is 2,3 or 4, n 3R5Which may be the same or different, and n 3R6May be the same or different. Particular preference is given to R5And R6Are all H.
In the compounds of the invention, R7、R8、R9、R10And R11Each independently selected from H and C1-C4Alkyl radicals, such as methyl, ethyl, propyl, butyl, are preferably each independently selected from H and C1-C2Alkyl, particularly preferably R7、R8、R9、R10And R11Are all H.
The compounds of the present invention contain substantially perfluorinated alkyl groups. Fluorine is the element with the strongest electronegativity, the C-F bond is short, so that the bond angle is reduced, fluorine atoms are spirally distributed along the carbon chain, the polarities of the whole carbon chain are basically counteracted with each other, and therefore the polarity of the whole molecule is low, and the surface energy of the coating prepared by the method is low. The special structure makes the whole molecule very rigid and the molecular rotation barrier is very large, so that the weather resistance and the chemical resistance are good. Since the fluorine-containing species have a very strong mobility and migrate to the interface, the addition of a very small amount of fluorine-containing compound greatly reduces the surface tension of the coating. In addition, because the C-F bond can be highly difficult to break, the coating can be protected from corrosion and oxidation in a complex environment with high temperature and high humidity. The monomer has good application prospect in printing plate imaging materials, anti-fouling and corrosion-resistant photocureable coatings, photocureable printing ink, photoresists and anti-fouling or non-fingerprint coatings. Compared with the photo-curing polymer in the general sense, the fluorine-containing photo-curing polymer has the characteristics of good hydrophobicity, low surface tension and the like, and solves the problems of headache, adhesion, poor spreadability and the like of the material in the application process. The low-adhesion high-spreadability polyurethane coating has a wide application prospect in the fields of microelectronic technology, precision optical instrument manufacturing, precision printing, aerospace, marine antifouling, biochemistry and the like. For example: monomers containing fluorine, silicon and other elements are added in the printing process, so that the spreadability of the surface of the cured film can be enhanced, the surface hydrophobicity is also enhanced, and the printing ink can be conveniently spread; in the nanoimprint process, the material containing fluorine and silicon can be used as a good demolding material due to the lower surface energy of the material, so that the problem that the photoresist is high in viscosity and not easy to separate from a mold is effectively solved.
The compounds of the present invention link a cationically photocurable oxacycloalkyl group to a substantially perfluorinated alkyl group via a linking group containing a norbornane structure. The substantially perfluorinated alkyl group has the ability to migrate to the interface in the curing system, so that a perfluorinated coating layer is formed on the surface of the coating, the surface energy of the whole coating is effectively reduced, meanwhile, the cationic polymerization of the oxacycloalkyl group is not influenced by the norbornane structure, and the cationic polymerization is initiated by ultraviolet light under the action of a cationic initiator. The final polymerization degree is close to one hundred percent, and the curing rate and the curing efficiency are good. In addition, the inventors of the present invention found that norbornane itself has an effect of increasing the hardness of the coating, enabling the coating to have very good wear resistance and oil stain resistance.
In a preferred embodiment of the invention, the compounds of the invention are selected from the group consisting of:
an important feature of the compounds of formula (I) according to the invention is that they can be synthesized in high yields and rapidly by means of a click chemistry reaction between thiol compounds and olefin compounds.
Thus, 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 process comprises:
1) reacting a compound of formula (II)
Wherein R is7、R8、R9、R10And R11As defined for compounds of formula (I), and X is halogen, preferably chloro or bromo;
carrying out esterification reaction with the compound of the formula (III),
z, W, R therein0、R1、R2M and n1 are as defined for the compound of formula (I),
to obtain the compound of the formula (IV),
z, W, R therein0、R1、R2、R7、R8、R9、R10、R11M and n1 are as defined for the compound of formula (I); and
2) reacting a compound of formula (IV) with a compound of formula (V),
wherein R is5、R6、n3And Y is as defined for the compound of formula (I),
to obtain the compound of formula (I).
In the process of the present invention, the compound of formula (IV) is first obtained from the compound of formula (II) and the compound of formula (III) by esterification, and then the compound of formula (I) is obtained from the compound of formula (IV) and the compound of formula (V).
The reaction in step 1) is an esterification reaction. The compound of formula (II) is an acid halide compound, and the compound of formula (III) is an alcohol compound, so the esterification reaction in step 1) is a typical esterification reaction between an acid halide compound and an alcohol compound. The compounds of formula (II) may be obtained commercially directly or by conventional reactions. To obtain the compound of formula (II), the compound of formula (II) wherein X is a hydroxyl group (i.e., a carboxylic acid compound, which may be hereinafter referred to as a compound of formula (IIA)) may be reacted with an acid halide reagent, especially an acid chloride reagent, under anhydrous conditions to obtain an acid halide compound of formula (II). As the acid halide reagent herein, sulfoxide chloride (thionyl chloride), phosphorus oxychloride, phosphorus pentachloride, oxalyl chloride or any mixture thereof can be used. Since the acid halide is liable to react with water to lower the reaction efficiency, the reaction is required to be carried out under anhydrous conditions, and the subsequent reaction of the resulting acid halide compound (II) with the compound of formula (III) is also required to be carried out under anhydrous conditions, since the resulting acid halide compound is also liable to react with water to lower the reaction yield. Therefore, in order to achieve the above-mentioned anhydrous condition, each reaction raw material needs to be dehydrated. It is common practice to add a molecular sieve, such as a 3A molecular sieve, to the feedstock, to stand for a period of time, such as 24 hours, to absorb water, and then to filter off the molecular sieve. If a non-aqueous solvent is required for the reaction, the solvent is usually dehydrated before the reaction, and the common method comprises adding sodium sand and benzophenone as an indicator into the solvent, and heating and refluxing the mixture to be used immediately after steaming. In addition, the reaction vessel such as a glass vessel used also needs to be baked at 110 ℃ for at least half an hour before the reaction.
Considering that a small amount of the acid halogenating agent still reacts with moisture in the air, it is advantageous that the acid halogenating agent is used in an excess amount, i.e., the acid halogenating agent is used in a molar ratio of 1.1 to 10 times, preferably 2 to 5 times, relative to the compound of formula (IIA) to be reacted therewith. For example, when thionyl chloride or oxalyl chloride is used as the acylhalogenation reagent, the thionyl chloride or oxalyl chloride is used in an amount of 2 to 5 times by mole with respect to the compound of the formula (IIA). The reaction of the acid halogenating agent with the compound of formula (IIA) is generally carried out at elevated temperature, and it is therefore advantageous that the reaction of the compound of formula (IIA) with the acid halogenating agent under anhydrous conditions is carried out at a temperature of from 60 to 90 ℃ and preferably at a temperature of from 70 to 80 ℃. The reaction time is usually 2 to 10 hours, preferably 4 to 6 hours. The reaction of the compound of formula (IIA) with the acid acylating agent under anhydrous conditions may be carried out in the presence of a non-aqueous solvent. For this, solvents that may be used include dichloromethane, tetrahydrofuran, n-hexane, petroleum ether, 1, 4-dioxane, acetonitrile or any mixture thereof. The amount of the solvent to be used is not particularly limited as long as each reactant can be sufficiently dissolved. In general, the solvent is used in an amount of 2 to 50 times by weight of the total amount of the reactants.
After the reaction of the compound of formula (IIA) with the acid halogenating agent is completed, the compound of formula (II) is obtained. The compound can be completely separated and then reacted with the compound of the formula (III), or the compound of the formula (III) can be introduced for continuous reaction after the excessive acyl halide reagent is removed by rotary evaporation and reduced pressure distillation. Since the reaction of the compound of formula (II) with the compound of formula (III) generates hydrogen halide as an acidic substance, the reaction of the compound of formula (II) with the compound of formula (III) is generally carried out in the presence of an acid trapping agent in order to prevent side reactions caused by the acidic substance and reduce the final yield. As the fulgide agent, triethylamine, aniline, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, or any mixture thereof may be used. The amount of the fulgide agent is generally such that the molar ratio of the fulgide agent to the compound of formula (II) is from 1.0 to 2.0, preferably from 1.1 to 1.5. For example, when triethylamine or aniline is used as the fulgide agent, the triethylamine or aniline is used in a molar amount of 1.1 to 1.5 times the molar amount relative to the compound of formula (II). The compound of the formula (III) is generally added in such an amount that the molar ratio of the compound of the formula (III) to the compound of the formula (II) is from 1.0 to 2.0, preferably from 1.1 to 1.5. The compound of formula (III) and the acid scavenger may each independently be introduced as such or in solution in a solvent. If both are introduced in solution, it is preferred that the solvents used for both are the same. For this, solvents which can be used include dichloromethane, tetrahydrofuran, n-hexane, petroleum ether, 1, 4-dioxane and acetonitrile. The amount of solvent used is generally 2 to 10 times by weight based on the total amount of the compound of formula (III). The reaction of the compound of the formula (II) with the compound of the formula (III) is generally carried out at a temperature of from 20 to 30 ℃ and preferably at room temperature. The reaction time is usually 10 to 20 hours.
After the reaction in the step 1) is finished, purifying the obtained product to obtain the compound in the formula (IV). To purify the product obtained in step 1), the reaction mixture is usually filtered to remove insoluble materials, the filtrate is washed with deionized water until the pH of the aqueous phase is neutral, the organic phase is dried, for example, over anhydrous magnesium sulfate powder for 10-12h, and finally the excess solvent is removed by rotary evaporation and then distilled under reduced pressure to obtain the compound of formula (IV).
By step 1), a compound of formula (IV) is obtained. The compound contains a cycloolefindouble bond, and the cycloolefindouble bond can perform click chemical reaction with a compound containing sulfhydryl (namely mercaptan), so that the compound of the formula (I) can be quickly and efficiently obtained.
Thus, in step 2) of the process of the invention, the compound of formula (IV) is reacted with a compound of formula (V) to give a compound of formula (I),
wherein R is5、R6N3 and Y are as defined for the compounds of formula (I).
The reaction in step 2) is carried out by a click chemistry reaction of a thiol with an olefin. In order to carry out the reaction in step 2), there are generally two reaction modes, namely step 2a) and step 2 b).
In step 2a), a compound of formula (IV) is reacted with a compound of formula (V) in the presence of a free radical initiator and in the absence of oxygen. The type of radical initiator employed herein is not particularly limited, so long as it decomposes at the reaction temperature to produce radicals. As examples of free-radical initiators here, mention may be made of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide or any mixtures thereof.
In step 2b), the compound of formula (IV) and the compound of formula (V) are reacted under uv irradiation. In order to generate the ultraviolet light required for the reaction, an ultraviolet lamp, for example, an ultraviolet lamp having an emission band of 300-600nm, may be used.
In step 2a), the compound of formula (IV) and the compound of formula (V) are used in such amounts that the molar ratio of the compound of formula (IV) to the compound of formula (V) is generally from 0.8 to 1.5, preferably from 0.9 to 1.1. The reaction temperature in step 2) is generally 40 to 110 ℃ and preferably 50 to 100 ℃. The reaction time is usually 6 to 15 hours, preferably 7 to 11 hours.
The reaction in step 2a) is generally carried out in the presence of an organic solvent. For step 2a), the solvent used must have a high boiling point, since the reaction is carried out at high temperature. As examples of the organic solvent, Dimethylformamide (DMF) and toluene can be used. A single solvent may be used, or a mixture of two or more solvents may be used. The amount of the solvent to be used is not particularly limited as long as each reactant can be sufficiently dissolved. In general, the solvent is used in an amount of 2 to 10 times by weight of the total amount of the reactants.
After the reaction of step 2a) is completed, the resulting product is purified to obtain the compound of formula (I). For the purification of the product obtained in step 2a), the crude product obtained from the reaction is generally purified by rotary evaporation and distillation under reduced pressure to give the compound of formula (I). The yield of the product obtained in step 2a) is generally above 95%.
In step 2b), the compound of formula (IV) and the compound of formula (V) are used in such amounts that the molar ratio of the compound of formula (IV) to the compound of formula (V) is generally from 0.8 to 1.5, preferably from 0.9 to 1.0. The reaction temperature in step 2b) is usually room temperature. The reaction time is generally 20 to 40min, preferably 25 to 35 min. The reaction conversion in step 2b) is very high, with yields typically above 99%. Thus, when the compound of formula (IV) and the compound of formula (V) are used in equimolar amounts, no purification is necessary. Thus, compared with the reaction in step 2a), the reaction in step 2b) is simple and convenient to operate, consumes less time and has higher yield.
According to a third aspect of the present invention, there is provided a polymer obtained by ring-opening polymerization of a compound of formula (I) of the present invention. The ring-opening polymerization is preferably carried out by cationic photocuring ring-opening polymerization. The cationic photocuring ring-opening polymerization is realized by ultraviolet light curing in the presence of a photoinitiator.
As the photoinitiator for ring-opening polymerization, iodonium salts and sulfonium salts are mainly used, such as compound A (diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate, CAS NO: 8945-2-37-9)) of the following formula, compound B ((bis-4, 1-secondary phenyl) -bis (diphenylsulfonium) -bis-hexafluoroantimonate, CAS NO: 71449-78-0) or mixtures thereof. For example, TR-PAG-201, a product of Changzhou powerful New electronic materials, Inc., is an acrylate solution in which the total amount of compound A and compound B is 50%, where the acrylate is 4-methyl-1, 3-dioxolan-2-one (CAS NO: 108-32-7).
The fluorine-containing cationic photocurable monomer compound comprises a photopolymerizable structure part and a basically perfluorinated alkyl structure, and a norbornane structure part is connected between the photopolymerizable structure part and the basically perfluorinated alkyl structure, so that a polymer coating formed by polymerizing the monomer has high surface hardness, extremely low surface energy, excellent hydrophobic and oleophobic performances, and particularly excellent oil stain resistance.
Thus, according to a fourth 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 photoinitiator 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, GR-OXT-1(CAS NO:3047-32-3), GR-OXT-7(CAS NO:483303-25-9) available from Kunststoku scientific Co., Ltd, Hubei. The photocurable composition of the present invention may be a photocurable coating composition, a photocurable ink composition, a photoresist composition, or the like. The composition has high surface hardness after being cured, extremely low surface energy, good hydrophobic and oleophobic properties and particularly good oil stain resistance.
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 photocurable material has high surface hardness, extremely low surface energy, excellent water and oil repellency, and particularly excellent oil stain resistance due to the inclusion of the compound of formula (I) of the present invention as a photocurable monomer.
Examples
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention.
Example 1: synthesis of Compound B-1
13.8g (0.1mol) of 5-norbornene-2-carboxylic acid and 59.5g (0.5mol) of thionyl chloride were mixed uniformly and stirred at 75 ℃ for 6 hours. After removing excess thionyl chloride by rotary evaporation and distillation under reduced pressure, 100mL of dichloromethane was added to the remaining liquid. Then, a mixture of 12.76g (0.11mol) of 3-ethyl-3-hydroxymethyloxetane and 11.11g (0.11mol) of triethylamine was added dropwise thereto under a nitrogen atmosphere. After the dropwise addition, the reaction was continued at room temperature for 12 hours. After the reaction, insoluble substances are filtered, the filtrate is washed by water until the pH value of the water phase is neutral, then the organic phase is dried by anhydrous magnesium sulfate powder for 12 hours, finally, excessive dichloromethane is removed by rotary evaporation, and the reduced pressure distillation is carried out to obtain 19.14g of intermediate product 3-ethyl-3- (5-norbornene-2-carbonyloxymethyl) -1-oxetane with the yield of 81 percent.
2.36g (0.01mol) of 3-ethyl-3- (5-norbornene-2-carbonyloxymethyl) -1-oxetane, 2.80g (0.01mol) of 1H,1H,2H, 2H-perfluorohexanethiol, 0.0496g (0.0002mol) of azobisisoheptonitrile and 10mL of toluene were charged into a three-necked flask and mixed uniformly under a nitrogen atmosphere. The reaction mixture was then warmed to 60 ℃ and stirred for 10 h. After the reaction is finished, cooling the reaction system to room temperature, removing redundant toluene by rotary evaporation, and then carrying out reduced pressure distillation to obtain a final product B-1, wherein the total amount of 4.95g is obtained, and the yield is 96%.
Nuclear magnetic hydrogen spectrum of the obtained product: 1H NMR (400MHz, CDCl3) δ 4.36(d, J ═ 5.9Hz,2H),4.19(d, J ═ 6.0Hz,2H),3.94(s,2H),3.22(ddd, J ═ 12.2,9.5,6.2Hz,1H),2.95(ddd, J ═ 12.3,9.5,6.2Hz,1H),2.56(q, J ═ 7.0Hz,1H), 2.44-2.33 (m,1H), 2.35-2.27 (m,1H), 2.31-2.11 (m,4H),1.82(dt, J ═ 13.0,7.0Hz,1H),1.68(dq, J ═ 13.2,6.8, 3H),1.59 (dt, 1.43, 1.7H), 1.77 (t, 1.7H), 1.7.7H, 1.77 (t ═ 13.13.2, 6H, 3H).
Example 2: synthesis of Compound B-2
The process of example 1 was repeated except that: 1H,1H,2H, 2H-perfluorohexanethiol is replaced by 1H,1H,2H, 2H-perfluorooctanethiol. The final product B-2 was obtained in a total of 6.07g with a yield of 95%.
Nuclear magnetic hydrogen spectrum of the obtained product:1H NMR(400MHz,CDCl3)δ4.36(d,J＝5.9Hz,2H),4.19(d,J＝6.0Hz,2H),3.94(s,2H),3.22(ddd,J＝12.2,9.5,6.2Hz,1H),2.95(ddd,J＝12.3,9.5,6.2Hz,1H),2.56(q,J＝7.0Hz,1H),2.44–2.33(m,1H),2.35–2.27(m,1H),2.31–2.11(m,4H),1.82(dt,J＝13.0,7.0Hz,1H),1.68(dq,J＝13.2,6.8Hz,3H),1.59–1.43(m,2H),1.18(dt,J＝13.0,7.0Hz,1H),0.77(t,J＝6.7Hz,3H).
example 3: synthesis of Compound B-3
The process of example 1 was repeated except that: 1H,1H,2H, 2H-perfluorohexanethiol is replaced by 1H,1H,2H, 2H-perfluorodecanethiol. The final product B-3 was obtained in a total of 6.87g with a yield of 96%.
Nuclear magnetic hydrogen spectrum of the obtained product:1H NMR(400MHz,CDCl3)δ4.36(d,J＝5.9Hz,2H),4.19(d,J＝6.0Hz,2H),3.94(s,2H),3.22(ddd,J＝12.2,9.5,6.2Hz,1H),2.95(ddd,J＝12.3,9.5,6.2Hz,1H),2.56(q,J＝7.0Hz,1H),2.44–2.33(m,1H),2.35–2.27(m,1H),2.31–2.11(m,4H),1.82(dt,J＝13.0,7.0Hz,1H),1.68(dq,J＝13.2,6.8Hz,3H),1.59–1.43(m,2H),1.18(dt,J＝13.0,7.0Hz,1H),0.77(t,J＝6.7Hz,3H).
example 4: synthesis of Compound B-4
13.8g (0.1mol) of 5-norbornene-2-carboxylic acid and 38.1g (0.3mol) of oxalyl chloride were mixed homogeneously and stirred at 70 ℃ for 5 hours. After subsequent rotary evaporation followed by distillation under reduced pressure to remove excess oxalyl chloride, 100mL of dichloromethane and 11.76g (0.14mol) of solid sodium bicarbonate were added to the remaining liquid. The mixture was cooled to about zero degrees centigrade by an ice bath under nitrogen atmosphere with rapid stirring, and then 8.14g (0.11mol) of glycidol was added dropwise thereto. After the dropwise addition, the reaction is continued for 14 hours under rapid stirring at room temperature. After the reaction is finished, insoluble substances are filtered, filtrate is washed by water until the pH value of a water phase is neutral, then the organic phase is dried by anhydrous magnesium sulfate powder for 12 hours, finally, excessive dichloromethane is removed by rotary evaporation, and the intermediate product 5-norbornene-2-glycidyl formate 15.72g is obtained by reduced pressure distillation, wherein the yield is 81%.
1.94g (0.01mol) of glycidyl 5-norbornene-2-carboxylate, 2.80g (0.01mol) of 1H,1H,2H, 2H-perfluorohexanethiol, 0.0328g (0.0002mol) of azobisisobutyronitrile and 10mL of toluene were added to a three-necked flask and mixed well under a nitrogen atmosphere. The reaction mixture was then warmed to 70 ℃ and stirred for 8 h. After the reaction is finished, cooling the reaction system to room temperature, removing redundant toluene by rotary evaporation, and then carrying out reduced pressure distillation to obtain a final product B-4, wherein the total amount of the product B-4 is 4.55g, and the yield is 96%.
1.94g (0.01mol) of glycidyl 5-norbornene-2-carboxylate and 2.80g (0.01mol) of 1H,1H,2H, 2H-perfluorohexanethiol were added to a single beaker and mixed well. Then it was exposed to an ultraviolet lamp (generating a radiation band of 300-600nm) for 30min to obtain the final product B-4, which amounted to 4.69g and had a yield of 99%.
Nuclear magnetic hydrogen spectrum of the obtained product:1H NMR(400MHz,CDCl3)δ4.54(dd,J＝12.4,7.0Hz, 1H),4.33(dd,J＝12.4,6.9Hz,1H),3.27–3.15(m,1H),3.07(p,J＝7.1Hz,1H),3.00–2.88(m,1H),2.66(dd,J＝7.1,5.0Hz,1H),2.56(q,J＝7.0Hz,1H),2.48–2.21(m,5H),2.13(h,J＝7.0Hz,1H),2.03(dt,J＝12.9,7.0Hz,1H),1.80(dt,J＝13.0,7.0Hz,1H),1.63(ddt,J＝13.0,8.6,7.0Hz,2H),1.47(dt,J＝12.9,6.9Hz,1H),1.20(dt,J＝13.0,7.0Hz,1H)。
example 5: synthesis of Compound B-5
The process of example 4 was repeated except that: 1H,1H,2H, 2H-perfluorohexanethiol is replaced by 1H,1H,2H, 2H-perfluorooctanethiol. The final product B-5 was obtained in a total of 5.51g, 96% yield.
Nuclear magnetic hydrogen spectrum of the obtained product:1H NMR(400MHz,CDCl3)δ4.54(dd,J＝12.4,7.0Hz,1H),4.33(dd,J＝12.4,6.9Hz,1H),3.27–3.15(m,1H),3.07(p,J＝7.1Hz,1H),3.00–2.88(m,1H),2.66(dd,J＝7.1,5.0Hz,1H),2.56(q,J＝7.0Hz,1H),2.48–2.21(m,5H),2.13(h,J＝7.0Hz,1H),2.03(dt,J＝12.9,7.0Hz,1H),1.80(dt,J＝13.0,7.0Hz,1H),1.63(ddt,J＝13.0,8.6,7.0Hz,2H),1.47(dt,J＝12.9,6.9Hz,1H),1.20(dt,J＝13.0,7.0Hz,1H).
example 6: synthesis of Compound B-6
The process of example 4 was repeated except that: 1H,1H,2H, 2H-perfluorohexanethiol is replaced by 1H,1H,2H, 2H-perfluorodecanethiol. The final product B-6 was obtained in a total of 6.47g, 96% yield.
Nuclear magnetic hydrogen spectrum of the obtained product:1H NMR(400MHz,CDCl3)δ4.54(dd,J＝12.4,7.0Hz,1H),4.33(dd,J＝12.4,6.9Hz,1H),3.27–3.15(m,1H),3.07(p,J＝7.1Hz,1H),3.00–2.88(m,1H),2.66(dd,J＝7.1,5.0Hz,1H),2.56(q,J＝7.0Hz,1H),2.48–2.21(m,5H),2.13(h,J＝7.0Hz,1H),2.03(dt,J＝12.9,7.0Hz,1H),1.80(dt,J＝13.0,7.0Hz,1H),1.63(ddt,J＝13.0,8.6,7.0Hz,2H),1.47(dt,J＝12.9,6.9Hz,1H),1.20(dt,J＝13.0,7.0Hz,1H).
example 7: synthesis of Compound B-7
15.2g (0.1mol) of 5-norbornene-3-methyl-2-carboxylic acid and 50.8g (0.4mol) of oxalyl chloride were mixed homogeneously and stirred at 80 ℃ for 4 hours. After removing excess oxalyl chloride by rotary evaporation and distillation under reduced pressure, 100mL of dichloromethane was added to the remaining liquid. The mixture was cooled to about zero degrees centigrade by an ice bath under a nitrogen atmosphere, and a mixture of 12.76g (0.11mol) of 3-ethyl-3-hydroxymethyloxetane and 14.14g (0.14mol) of triethylamine was added dropwise thereto. After the dropwise addition, the reaction was continued at room temperature for 16 hours. After the reaction, insoluble substances are filtered, the filtrate is washed by water until the pH value of the water phase is neutral, then the organic phase is dried by anhydrous magnesium sulfate powder for 12 hours, finally, excessive dichloromethane is removed by rotary evaporation, and the reduced pressure distillation is carried out to obtain 20.27g of intermediate product 5-norbornene-3-methyl-2-glycidyl formate with the yield of 81 percent.
2.50g (0.01mol) of glycidyl 5-norbornene-3-methyl-2-carboxylate, 2.94g (0.01mol) of 1H,1H,1H,2H,2H, 3H-perfluoroheptane-3-thiol, 0.0328g (0.0002mol) of azobisisobutyronitrile and 10mL of toluene were added to a three-necked flask and mixed uniformly under a nitrogen atmosphere. The reaction mixture was then warmed to 90 ℃ and stirred for 9 h. After the reaction is finished, cooling the reaction system to room temperature, removing excessive toluene by rotary evaporation, and then carrying out reduced pressure distillation to obtain a final product B-7, wherein the total amount of the product B-7 is 5.17g, and the yield is 95%.
Nuclear magnetic hydrogen spectrum of the obtained product:1H NMR(400MHz,CDCl3)δ4.36(d,J＝6.0Hz,2H),4.09(d,J＝6.0Hz,2H),3.94(s,2H),2.94(tdd,J＝20.9,5.9,3.3Hz,1H),2.77(q,J＝7.0Hz,1H),2.45(p,J＝7.0Hz,1H),2.33(t,J＝7.0Hz,1H),2.18(h,J＝6.8Hz,1H),2.03–1.93(m,2H),1.83(dt,J＝12.6,6.9Hz,1H),1.76–1.57(m,5H),1.27(dt,J＝12.8,6.9Hz,1H),0.91(t,J＝8.0Hz,3H),0.82(t,J＝6.7Hz,3H),0.76(d,J＝6.8Hz,3H).
example 8: synthesis of Compound B-8
13.8g (0.1mol) of 5-norbornene-2-carboxylic acid and 25.4g (0.2mol) of oxalyl chloride were mixed homogeneously and stirred at 75 ℃ for 6 h. After removing excess oxalyl chloride by rotary evaporation and distillation under reduced pressure, 100mL of dichloromethane was added to the remaining liquid. The mixture was cooled to about zero degrees centigrade by an ice bath under a nitrogen atmosphere, and then a mixture of 11.45g (0.13mol) of 3, 4-epoxy-1-butanol and 14.14g (0.14mol) of triethylamine was added dropwise thereto. After the dropwise addition, the reaction was continued at room temperature for 18 hours. After the reaction is finished, insoluble substances are filtered, filtrate is washed by water until the pH value of a water phase is neutral, then the organic phase is dried by anhydrous magnesium sulfate powder for 12 hours, finally, excessive dichloromethane is removed by rotary evaporation, and the intermediate product 5-norbornene-2-formic acid 3, 4-epoxybutyl ester is obtained by reduced pressure distillation in a yield of 81 percent.
2.08g (0.01mol) of 3, 4-epoxybutyl 5-norbornene-2-carboxylate, 2.80g (0.01mol) of 1H,1H,2H, 2H-perfluorohexanethiol, 0.0328g (0.0002mol) of azobisisobutyronitrile and 10mL of toluene were added to a three-necked flask and mixed well under a nitrogen atmosphere. The reaction mixture was then warmed to 85 ℃ and stirred for 9 h. After the reaction is finished, cooling the reaction system to room temperature, removing redundant toluene by rotary evaporation, and then carrying out reduced pressure distillation to obtain a final product B-8, wherein the total amount of the product B-8 is 4.64g, and the yield is 95%.
Nuclear magnetic hydrogen spectrum of the obtained product:1H NMR(400MHz,CDCl3)δ4.03(pd,J＝12.4,3.7Hz,2H),3.22(ddd,J＝12.5,9.5,6.2Hz,1H),2.95(ddd,J＝12.3,9.5,6.2Hz,1H),2.71–2.60(m,3H),2.57(p,J＝6.9Hz,1H),2.42–2.17(m,6H),1.93–1.78(m,2H),1.71–1.55(m,2H),1.55–1.42(m,2H),1.17(dt,J＝13.4,6.8Hz,1H).
example 9: synthesis of Compound B-9
13.8g (0.1mol) of 5-norbornene-2-carboxylic acid and 35.7g (0.3mol) of thionyl chloride were mixed uniformly and stirred at 80 ℃ for 5 hours. After removing the excess thionyl chloride by rotary evaporation and then distillation under reduced pressure, 100mL of dichloromethane was added to the remaining liquid. The mixture was cooled to about zero degrees centigrade by an ice bath under a nitrogen atmosphere, and a mixture of 12.26g (0.12mol) of 1, 2-epoxy-3-hydroxypentane and 14.14g (0.14mol) of triethylamine was added dropwise thereto. After the dropwise addition, the reaction was continued at room temperature for 20 hours. After the reaction, insoluble substances are filtered, filtrate is washed by water until the pH value of a water phase is neutral, then the organic phase is dried by anhydrous magnesium sulfate powder for 12 hours, finally, excessive dichloromethane is removed by rotary evaporation, and the reduced pressure distillation is carried out to obtain 17.99g of intermediate product 5-norbornene-2-formic acid 1, 2-epoxy-3-ethyl-3-propyl ester, wherein the yield is 81%.
2.22g (0.01mol) of 1, 2-epoxy-3-ethyl-3-propyl 5-norbornene-2-carboxylate, 2.80g (0.01mol) of 1H,1H,2H, 2H-perfluorohexanethiol, 0.0328g (0.0002mol) of azobisisobutyronitrile and 10mL of toluene were added to a three-necked flask and mixed uniformly under a nitrogen atmosphere. The reaction mixture was then warmed to 90 ℃ and stirred for 9 h. After the reaction is finished, cooling the reaction system to room temperature, removing excessive toluene by rotary evaporation, and then carrying out reduced pressure distillation to obtain a final product B-9, wherein the total amount of the product B-9 is 4.77g, and the yield is 95%.
Nuclear magnetic hydrogen spectrum of the obtained product:1H NMR(400MHz,CDCl3)δ4.72(q,J＝7.0Hz,1H),3.27–3.14(m,1H),3.00(q,J＝7.0Hz,1H),2.93(ddd,J＝12.4,9.7,6.0Hz,1H),2.64(dq,J＝22.1,7.0Hz,2H),2.48(dd,J＝7.0,4.9Hz,1H),2.40–2.17(m,5H),2.04(dt,J＝12.9,6.9Hz,1H),1.83(dt,J＝13.5,6.9Hz,1H),1.73(ddt,J＝15.1,12.5,8.0Hz,1H),1.66–1.55(m,2H),1.47(dt,J＝13.6,6.9Hz,1H),1.24(ddt,J＝19.7,13.0,7.0Hz,2H),0.75(t,J＝8.0Hz,3H).
example 10: synthesis of Compound B-10
13.8g (0.1mol) of 5-norbornene-2-carboxylic acid and 35.7g (0.3mol) of thionyl chloride were mixed uniformly and stirred at 70 ℃ for 5 hours. After removing the excess thionyl chloride by rotary evaporation and then distillation under reduced pressure, 100mL of dichloromethane was added to the remaining liquid. The mixture was cooled to about zero degrees centigrade by an ice bath under a nitrogen atmosphere, and then a mixture of 14.16g (0.12mol) of 3, 3-bis (hydroxymethyl) -1-oxetane and 14.14g (0.14mol) of triethylamine was added dropwise thereto. After the dropwise addition, the reaction was continued at room temperature for 10 hours. After the reaction, insoluble substances were filtered off, the filtrate was washed with water until the pH of the aqueous phase became neutral, and then the organic phase was dried over anhydrous magnesium sulfate powder for 12 hours, and finally, excess dichloromethane was removed by rotary evaporation, and the intermediate product, 3-hydroxymethyl-3- (5-norbornene-2-carbonyloxymethyl) -1-oxetane, was obtained by distillation under reduced pressure in an amount of 19.29g in a yield of 81%.
2.38g (0.01mol) of 3-hydroxymethyl-3- (5-norbornene-2-carbonyloxymethyl) -1-oxetane, 2.80g (0.01mol) of 1H,1H,2H, 2H-perfluorohexanethiol, 0.0328g (0.0002mol) of azobisisobutyronitrile and 10mL of toluene were charged into a three-necked flask and mixed uniformly under a nitrogen atmosphere. The reaction mixture was then warmed to 90 ℃ and stirred for 8 h. After the reaction is finished, cooling the reaction system to room temperature, removing redundant toluene by rotary evaporation, and then carrying out reduced pressure distillation to obtain a final product B-10, wherein the total amount of the product B-10 is 4.92g, and the yield is 95%.
Nuclear magnetic hydrogen spectrum of the obtained product:1H NMR(400MHz,CDCl3)δ4.59(d,J＝5.9Hz,2H),4.41(d,J＝6.0Hz,2H),3.94(s,2H),3.39(d,J＝4.9Hz,2H),3.21(ddd,J＝12.5,9.5,6.3Hz,1H),2.95(ddd,J＝12.4,9.7,6.4Hz,1H),2.67(q,J＝7.0Hz,1H),2.54(p,J＝6.9Hz,1H),2.42–2.17(m,6H),1.83(dt,J＝13.5,6.9Hz,1H),1.65–1.55(m,1H),1.54–1.41(m,2H),1.19(dt,J＝13.4,6.9Hz,1H).
example 11: synthesis of Compound B-11
13.8g (0.1mol) of 5-norbornene-2-carboxylic acid and 59.5g (0.5mol) of thionyl chloride were mixed uniformly and stirred at 70 ℃ for 6 hours. After removing excess thionyl chloride by rotary evaporation and distillation under reduced pressure, 100mL of dichloromethane was added to the remaining liquid. Then, a mixture of 12.76g (0.11mol) of 3-ethyl-3-hydroxymethyloxetane and 11.11g (0.11mol) of triethylamine was added dropwise thereto under a nitrogen atmosphere. After the dropwise addition, the reaction was continued at room temperature for 12 hours. After the reaction, insoluble substances were filtered off, the filtrate was washed with water until the pH of the aqueous phase became neutral, and then the organic phase was dried over anhydrous magnesium sulfate powder for 12 hours, and finally, excess dichloromethane was removed by rotary evaporation, and the intermediate product, 3-ethyl-3- (5-norbornene-2-carbonyloxymethyl) -1-oxetane, was obtained by distillation under reduced pressure, in an amount of 19.14g, in a yield of 81%.
2.36g (0.01mol) of 3-ethyl-3- (5-norbornene-2-carbonyloxymethyl) -1-oxetane, 1.48g (0.01mol) of 2,2,3, 3-tetrafluoropropanethiol, 0.0328g (0.0002mol) of azobisisobutyronitrile and 10mL of toluene were added to a three-necked flask and mixed well under a nitrogen atmosphere. The reaction mixture was then warmed to 85 ℃ and stirred for 8 h. After the reaction is finished, cooling the reaction system to room temperature, removing redundant toluene by rotary evaporation, and then carrying out reduced pressure distillation to obtain a final product B-11, wherein the total amount of the product B-11 is 3.69g, and the yield is 96%.
Nuclear magnetic hydrogen spectrum of the obtained product:1H NMR(400MHz,CDCl3)δ4.36(d,J＝6.0Hz,2H),4.18(d,J＝6.0Hz,2H),3.94(s,2H),3.58(td,J＝20.9,12.4Hz,1H),3.38(td,J＝20.9,12.5Hz,1H),2.76–2.66(m,2H),2.51(q,J＝6.9Hz,1H),2.34(hept,J＝7.0Hz,1H),1.99(dt,J＝13.0,7.0Hz,1H),1.89(dt,J＝13.4,6.8Hz,1H),1.73–1.59(m,3H),1.56–1.47(m,1H),1.37(dt,J＝13.7,6.9Hz,1H),1.24–1.15(m,1H), 0.80(t,J＝8.0Hz,3H).
example 12: synthesis of Compound B-12
13.8g (0.1mol) of 5-norbornene-2-carboxylic acid and 59.5g (0.5mol) of thionyl chloride were mixed uniformly and stirred at 70 ℃ for 6 hours. After removing excess thionyl chloride by rotary evaporation and distillation under reduced pressure, 100mL of dichloromethane was added to the remaining liquid. Then, a mixture of 12.76g (0.11mol) of 3-ethyl-3-hydroxymethyloxetane and 11.11g (0.11mol) of triethylamine was added dropwise thereto under a nitrogen atmosphere. After the dropwise addition, the reaction was continued at room temperature for 12 hours. After the reaction, insoluble substances were filtered off, the filtrate was washed with water until the pH of the aqueous phase became neutral, and then the organic phase was dried over anhydrous magnesium sulfate powder for 12 hours, and finally, excess dichloromethane was removed by rotary evaporation, and the intermediate product, 3-ethyl-3- (5-norbornene-2-carbonyloxymethyl) -1-oxetane, was obtained by distillation under reduced pressure, in an amount of 19.14g, in a yield of 81%.
2.36g (0.01mol) of 3-ethyl-3- (5-norbornene-2-carbonyloxymethyl) -1-oxetane, 4.52g (0.01mol) of 1H,1H,2H, 2H-3-trifluoromethyl-perfluoro-1-butanethiol, 0.0328g (0.0002mol) of azobisisobutyronitrile and 10mL of toluene were added to a three-necked flask under a nitrogen atmosphere and mixed well. The reaction mixture was then warmed to 85 ℃ and stirred for 10 h. After the reaction is finished, cooling the reaction system to room temperature, removing redundant toluene by rotary evaporation, and then carrying out reduced pressure distillation to obtain a final product B-12 with 6.60g in total and 96% of yield.
2.36g (0.01mol) of 3-ethyl-3- (5-norbornene-2-carbonyloxymethyl) -1-oxetane and 4.52g (0.01mol) of 1H,1H,2H, 2H-3-trifluoromethyl-perfluoro-1-butanethiol are added to a single-neck beaker and mixed homogeneously. Then it was exposed to an ultraviolet lamp (generating a radiation band of 300-600nm) for 30min to obtain the final product B-12 in a total of 6.81g with a yield of 99%.
Nuclear magnetic hydrogen spectrum of the obtained product:1H NMR(400MHz,CDCl3)δ4.38(d,J＝5.9Hz,2H),4.17(d,J＝5.9Hz,2H),3.94(s,2H),3.35(td,J＝12.5,2.3Hz,1H),3.01(td,J＝12.3,4.0Hz,1H),2.84(dtd,J＝24.8,12.3,2.2Hz,1H),2.76–2.60(m,3H),2.41–2.24(m,2H),2.07(dt,J＝13.0,7.0Hz,1H),1.88–1.79(m,1H),1.69(q,J＝6.7Hz,2H),1.59(ddt,J＝14.1,12.9,6.9Hz,2H),1.47(dt,J＝12.8,6.8Hz,1H),1.21(dt,J ＝13.4,6.8Hz,1H),0.81(t,J＝6.7Hz,3H).
the inventive compounds cure to form a film:
1g of the compound of the invention was mixed with 0.01g of a photoinitiator (compound A below). The resulting mixture was mixed at 0.5g/cm2Spin-coating on a glass plate without drying, and placing the glass plate in a low-pressure mercury lamp (with a light intensity P of 30mW/cm at λ 365 nm)2) Then, the film was cured by light for 10min to form a film.
To verify the cured film properties of the monomeric compounds, the pencil hardness of the film was measured and the following tests were performed: fingerprint resistance test of coating film surface
The characterization method of the fingerprint resistance of the coating surface comprises 2 methods of contact angle and oil resistance pen tests. The contact angle is measured by a static drop angulometer, the test temperature is 25 ℃, and the humidity is 50%. Testing the oil resistance pen, namely symmetrically marking 2 points in the middle of a sampling plate, wherein the distance between the 2 points is 5 cm; drawing a straight line between 2 points by using an oil pen, wiping by using dust-free cloth, and recording the number of times as 1; and then linearly wiping the oil-based handwriting at the same position by using a dust-free cloth, repeating the steps until the oil-based handwriting cannot be wiped cleanly by using the dust-free cloth, and counting the number of times to be N, wherein the number of times of the oil-resistant pen is (N-1).
Measurement of surface energy
The surface tension between the solid and liquid contacting phases can be expressed as follows:
in the formula (1), the reaction mixture is,
γSLis the surface tension between the solid and the liquid, and the unit is N/m;
γS、
respectively representing the total surface energy of the solid, the dispersion component of the surface energy of the solid and the polar component of the surface energy of the solid, wherein the unit is N/m; and
γL、
respectively represent the total surface energy, the dispersive component of the surface energy and the polar component of the surface energy of the tested liquid, and the unit is N/m.
The total surface energy of the solid and the liquid to be tested and the dispersion component and the polar component of the surface energy satisfy the following two equations, respectively:
the formula (1) is substituted into the Young's equation to obtain the following formula (4)
According to the formula (4), the contact angle theta of two known liquids on the surface of the solid coating is measured, and the gamma of each of the two known liquids is reusedL、
(Total surface energy of the liquid to be tested, dispersion component of surface energy, polar component of surface energy) data, from which the surface of the solid coating can be solved
(dispersion component of solid surface energy, polar component of solid surface energy).
Finally, the total surface energy of the solid coating is solved according to the formula (2).
Two specific test solutions and related data are shown in the following table:
corrosion resistance test of coating film surface
The characterization method of the corrosion resistance of the surface of the coating film is mainly an alkali resistance test, because the photo-cured coating has outstanding acid resistance and generally has poor alkali resistance.
Alkali resistance test: a20% NaOH aqueous solution is dropped on the surface of the coating by a dropper 1, and the time for which the coating turns white is observed.
However, the numbers of times of oil resistance pens of coating films obtained by curing each of the compounds A-1 to A-14, the compounds B-1 to B-7, the compounds C-1 to C-4 and the compounds D-1 to D-7 in CN 106187953A did not exceed 40 times, which is far lower than that of the present invention.
Claims (14)
1. A compound of the formula (I):
wherein
Y is a linear or branched alkyl group containing from 1 to 10 carbon atoms, preferably from 2 to 8 carbon atoms, the hydrogen atoms of which are substantially completely replaced by fluorine, preferably 80 to 100%, preferably 90 to 100%, of the hydrogen atoms of the alkyl group are replaced by fluorine, more preferably Y is a perfluorinated linear or branched alkyl group containing from 3 to 8 carbon atoms;
z is- (CH)2)p-, where p is 0, 1,2 or 3;
w is- (CH)2)q-, wherein q is 0, 1,2 or 3, with the proviso that p and q cannot both be 0;
(R0)mis W, O, Z m substituents R on the ring formed together with the carbon atom linking Z and W0Wherein m is 0, 1 or 2, and R0Is selected from C1-C6Alkyl and hydroxy C1-C6Alkyl, wherein when m is 2, two R are0May be the same or different;
n1 is 1 or 2;
n3 is 1,2, 3 or 4;
R1and R2Each independently selected from H, C1-C6Alkyl and C1-C6Alkoxy, when n1 is 2, two R1May be the same or different, and two R2May be the same or different;
R5and R6Each independently selected from H and C1-C6Alkyl, wherein when n3 is 2,3 or 4, n 3R5Which may be the same or different, and n 3R6May be the same or different; and
R7、R8、R9、R10and R11Each independently selected from H and C1-C4An alkyl group.
2. The compound of claim 1, wherein p and q are both 1, or one of p and q is 0 and the other is 1.
3. The compound of claim 1 or 2, wherein m is 0 or 1, and when m is 1, R is0Preferably on the carbon atom linking Z and W.
4. The compound of any one of claims 1-3, wherein n1 is 1; and/or n3 is 2.
5. A compound according to any one of claims 1 to 4, wherein
R0Is selected from C1-C4Alkyl and hydroxy C1-C4An alkyl group; and/or
R1、R2Each independently selected from H, C1-C4Alkyl and C1-C4Alkoxy, preferably R1、R2Are all H; and/or
R5And R6Each independently selected from H and C1-C4Alkyl, preferably both are H; and/or
R7、R8、R9、R10And R11Each independently selected from H and C1-C2Alkyl groups, preferably both are H.
6. The compound of claim 1, which is a compound selected from the group consisting of:
7. a process for the preparation of a compound of formula (I) as defined in any one of claims 1 to 6, comprising:
1) reacting a compound of formula (II)
Wherein R is7、R8、R9、R10And R11As defined for compounds of formula (I), and X is halogen, preferably chloro or bromo;
carrying out esterification reaction with the compound of the formula (III),
z, W, R therein0、R1、R2M and n1 are as defined for the compound of formula (I),
to obtain the compound of the formula (IV),
z, W, R therein0、R1、R2、R7、R8、R9、R10、R11M and n1 are as defined for the compound of formula (I); and
2) reacting a compound of formula (IV) with a compound of formula (V),
wherein R is5、R6、n3And Y is as defined for the compound of formula (I),
to obtain the compound of formula (I).
8. The method of claim 7, wherein the reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a fulgide agent, preferably a triethylamine, aniline, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or any mixture thereof.
9. The process according to claim 7 or 8, wherein the molar ratio of compound of formula (III) to compound of formula (II) is from 1.0 to 2.0, preferably from 1.1 to 1.5; and/or the molar ratio of the fulgide agent to the compound of formula (II) is 1.0 to 2.0, preferably 1.1 to 1.5; and/or the reaction in step 1) is carried out at a temperature of 20 to 30 ℃, preferably at room temperature.
10. The process according to any one of claims 7 to 9, wherein the reaction of step 2) is carried out according to step 2 a): 2a) reacting a compound of formula (IV) with a compound of formula (V) in the presence of a free radical initiator and in the absence of oxygen, preferably
The free radical initiator is selected from azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide or any mixture thereof; and/or the molar ratio of compound of formula (IV) to compound of formula (V) is from 0.8 to 1.5, preferably from 0.9 to 1.1; and/or the reaction of step 2a) is carried out at a temperature of 40 to 110 ℃, preferably 50 to 100 ℃.
11. The process according to any one of claims 7 to 9, wherein the reaction of step 2) is carried out according to step 2 b): 2b) reacting the compound of formula (IV) and the compound of formula (V) under UV irradiation, preferably,
the reaction in the step 2b) is carried out under the irradiation of an ultraviolet lamp with an emission waveband of 300-600 nm; and/or the molar ratio of compound of formula (IV) to compound of formula (V) is from 0.8 to 1.5, preferably from 0.9 to 1.0; and/or the reaction of step 2b) is carried out at room temperature.
12. A polymer obtained by ring-opening polymerization of a compound of formula (I) according to any one of claims 1 to 6, preferably by cationic photocuring, especially uv-curing in the presence of a photoinitiator.
13. A photocurable composition comprising a compound of formula (I) as defined in any one of claims 1 to 6 as polymerized monomer.
14. A photocurable material obtained by photocuring the photocurable composition according to claim 13.
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| US3989725A (en) * | 1975-08-29 | 1976-11-02 | Ciba-Geigy Corporation | Perfluoroalkylthio norbornane 2,3-dicarboxylic acid compounds |
| CN106187953A (en) * | 2016-07-29 | 2016-12-07 | 湖北固润科技股份有限公司 | A kind of cationic polymerization monomer and synthesis and application |
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| CN101759670B (en) * | 2010-01-07 | 2012-02-08 | 浙江大学 | Perfluoroalkoxy epoxy compound, preparation method and purpose thereof |
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| US3989725A (en) * | 1975-08-29 | 1976-11-02 | Ciba-Geigy Corporation | Perfluoroalkylthio norbornane 2,3-dicarboxylic acid compounds |
| CN106187953A (en) * | 2016-07-29 | 2016-12-07 | 湖北固润科技股份有限公司 | A kind of cationic polymerization monomer and synthesis and application |
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