WO2020253839A1 - Mixable photocurable polysilicon-containing oxetane monomer and preparation and application thereof - Google Patents

Mixable photocurable polysilicon-containing oxetane monomer and preparation and application thereof Download PDF

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WO2020253839A1
WO2020253839A1 PCT/CN2020/097175 CN2020097175W WO2020253839A1 WO 2020253839 A1 WO2020253839 A1 WO 2020253839A1 CN 2020097175 W CN2020097175 W CN 2020097175W WO 2020253839 A1 WO2020253839 A1 WO 2020253839A1
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compound
formula
alkyl
integer
reaction
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French (fr)
Chinese (zh)
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孙芳
马浩钦
邹应全
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湖北固润科技股份有限公司
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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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment

Definitions

  • the technical field of the present invention is the field of light-curable materials, and specifically relates to a polysilicon-containing oxetane monomer that can be mixed with light-curable.
  • the invention also relates to a preparation method of the monomer, a photocurable composition containing the monomer and a photocurable material obtained by photocuring the photocurable composition.
  • Ultraviolet curing refers to the process in which a photoinitiator is excited to become free radicals or cations under ultraviolet radiation, thereby initiating polymerization and curing reactions between monomers to form high molecular polymers.
  • ultraviolet light curing technology Compared with thermal curing, ultraviolet light curing technology has the advantages of low environmental pollution, high film quality, and low energy consumption. Therefore, it is widely used in light-curing coatings, adhesives, and ink printing. Moreover, as the emission control of organic volatile components becomes stricter, UV curing technology will have a broader development prospect.
  • the free radical light curing system has the advantages of fast curing speed and easy adjustment of performance, but also has the problems of serious shrinkage, low precision, and poor adhesion.
  • the development of cationic curing system is relatively late. It has the advantages of small volume shrinkage, strong adhesion, wear resistance, high hardness, etc. It is especially suitable for laser rapid prototyping technology (stereolithography) that requires high precision and optical discs that require strong adhesion and wear resistance. It also has the disadvantages of slow curing speed, few types of oligomers and reactive diluents, high price, and difficult adjustment of cured product performance, which limits its practical application.
  • Oxycycloalkane monomers belong to cationic light curing system monomers. Oxycycloalkane monomers are the main raw materials for high-end cationic light curing products. This system not only has low viscosity, low toxicity, and fast polymerization speed, but also has excellent thermal stability and mechanical properties. However, while UV curing has developed rapidly with the advantages of energy saving, environmental protection and high efficiency, people have proposed higher standards for the heat resistance, water repellency, surface stain resistance, corrosion resistance and fingerprint resistance of photocurable materials. Claim. Consumers are increasingly demanding the appearance of products.
  • the surface is also required to have anti-fingerprint and stain-resistant performance, that is, it is not easy to leave fingerprints and other traces on the surface of the product during use, or it is easy to leave traces Be wiped clean.
  • photocurable monomers that can meet the aforementioned requirements, have fast curing speed and easily adjustable performance, and there is no such photocurable monomer on the market, so development is urgently needed.
  • the inventors of the present invention have conducted extensive and in-depth research on oxetane cationic photopolymerizable monomers in order to discover a new type of photocurable monomers.
  • the body After curing, the body not only has the advantages of good tensile properties, excellent hydrophobic properties, anti-staining, anti-fingerprint, anti-chemical corrosion, and strong anti-aging properties, but also has fast curing speed and easy adjustment of performance.
  • the present inventors discovered that the hybrid light-curable monomer compound obtained by combining the organosiloxane with the oxetane moiety and the acrylate group has the aforementioned advantages.
  • one object of the present invention is to provide a hybrid photocurable polysilicon-containing oxetane monomer, which not only contains cationic photocurable oxetane groups, but also contains polysilicon Siloxane chain and free radical light-curable acrylate group.
  • the monomer with such a structure not only has good tensile properties after light curing, excellent hydrophobic properties, anti-staining, anti-fingerprint, anti-chemical corrosion, strong anti-aging properties, good heat resistance, but also has fast curing speed and easy adjustment of performance. This broadens the application range of the light curing system.
  • Another object of the present invention is to provide a method for preparing the hybrid light-curable polysilicon-containing oxetane monomer of the present invention.
  • the preparation process is simple and feasible, the conditions are mild, the raw materials are readily available, and the price is low.
  • Another object of the present invention is to provide a photocurable composition comprising the hybrid photocurable polysilicon-containing oxetane monomer according to the present invention.
  • the last object of the present invention is to provide a photocurable material which is obtained by photocuring the photocurable composition of the present invention.
  • n is an integer from 1-50;
  • n is an integer of 1-10;
  • z is an integer of 0-10;
  • p is an integer of 1-6;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy or A C 1 -C 12 alkyl group with one or more heteroatoms independently selected from N, O and S inserted between two carbon atoms;
  • R 8 is H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy; as well as
  • R 9 is H or C 1 -C 12 alkyl.
  • n is an integer of 1-15, preferably an integer of 1-12;
  • n is an integer of 1-6, preferably an integer of 2-4;
  • z is an integer of 1-6, preferably an integer of 0-3;
  • p is an integer of 1-4, preferably an integer of 1-3;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or A C 1 -C 6 alkyl group with one or more heteroatoms selected from NR b , O, and S inserted between two carbon atoms, wherein R b is H or C 1 -C 4 alkyl, preferably R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are the same or different and are independently a phenyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or one interposed between two carbon atoms Or more C 1 -C 4 alkyl groups independently selected from heteroatoms of NR b , O, and S, wherein R b is H or C 1 -C 4 alkyl; and/or
  • R 8 is H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy, Preferably H or C 1 -C 4 alkyl; and/or
  • R 9 is H or C 1 -C 6 alkyl, preferably H or C 1 -C 4 alkyl.
  • n is an integer from 1-12;
  • n 2, 3 or 4;
  • z 0, 1, 2 or 3;
  • p 1, 2 or 3;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 1 -C 4 alkyl groups; and/or
  • R 8 is H or C 1 -C 4 alkyl
  • R 9 is H or C 1 -C 4 alkyl, especially H or methyl.
  • n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined in any one of items 1-4,
  • p and R 8 are as defined in any one of items 1 to 4, and X is halogen, such as fluorine, chlorine, bromine or iodine,
  • n, m, z, p, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are defined in any one of items 1-4;
  • R 9 is as defined in any one of items 1-4, and Y is halogen, such as fluorine, chlorine, bromine or iodine.
  • the reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a basic catalyst.
  • the basic catalyst is preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably ,
  • the molar ratio of the compound of formula (II) to the basic catalyst is 1:1-1:5; and/or
  • the molar ratio of the compound of formula (II) to the compound of formula (III) is 1:1-1:1.5; and/or
  • the reaction between the compound of formula (II) and the compound of formula (III) is first carried out at the freezing temperature, and then the temperature is increased to 25-60°C, preferably to 35-60°C; preferably, the reaction at the freezing temperature proceeds to 0.5 -3 hours, preferably 0.5-1 hour; and/or, continue the reaction for 6-24 hours after raising the temperature, preferably 8-24 hours.
  • the reaction between the compound of formula (IV) and the compound of formula (V) is carried out in the presence of a basic catalyst.
  • the basic catalyst is preferably triethylamine, potassium carbonate or any mixture thereof, and more preferably, the compound of formula (IV) and the catalyst
  • the molar ratio of is 1:1-1:3 (the example does not use a basic catalyst); and/or
  • the molar ratio of the compound of formula (IV) to the compound of formula (IV) is 1:1-1:1.2; and/or
  • the reaction between the compound of formula (IV) and the compound of formula (IV) is first carried out at freezing temperature, and then the temperature is raised to 25-60°C, preferably to 25-35°C; preferably, the reaction at the freezing point temperature is carried out 0.5 -3 hours, preferably 0.5-1 hour; and/or continue the reaction for 6-24 hours, preferably 8-12 hours after raising the temperature.
  • a photocurable composition comprising the compound of formula (I) according to any one of items 1 to 4 as a polymerizable monomer.
  • Fig. 1 is a graph showing the change of double bond conversion rate of compound 1 prepared in Example 1 with irradiation time.
  • Example 2 is a graph showing the change of the oxetane ring conversion rate of Compound 1 prepared in Example 1 with the irradiation time.
  • n is an integer from 1-50;
  • n is an integer of 1-10;
  • z is an integer of 0-10;
  • p is an integer of 1-6;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy or A C 1 -C 12 alkyl group with one or more heteroatoms independently selected from N, O and S inserted between two carbon atoms;
  • R 8 is H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy; as well as
  • R 9 is H or C 1 -C 12 alkyl.
  • the compound of formula (I) contains both a cationic photocurable oxetane structure, a radical photocurable acrylate structure part, and a polysiloxane structure part.
  • the compound with such a structure has the advantages of both cationic curing and free radical curing. It not only has fast curing speed and easy adjustment of performance, but also has the advantages of small volume shrinkage, strong adhesion, wear resistance and high hardness. In addition, it has tensile properties after light curing. Good, excellent hydrophobic performance, stain resistance, fingerprint resistance, chemical corrosion resistance, strong anti-aging performance, and good heat resistance.
  • C n -C m indicates that the number of carbon atoms contained in the group is nm.
  • Halogen refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferable that the halogen includes fluorine, chlorine or a combination thereof.
  • C n -C m alkyl group refers to a monovalent branched or unbranched saturated hydrocarbon group having nm, for example 1-12, preferably 1-6, particularly preferably 1-4 carbon atoms .
  • C n -C m alkyl groups mention may be made of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1 -Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,
  • C 6 -C m aryl group refers to a monocyclic, bicyclic or multicyclic aromatic hydrocarbon group containing 6 to m carbon atoms, for example, 6 to 10 carbon atoms.
  • C 6 -C m aryl groups mention may be made of phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methyl ethyl phenyl, diethyl phenyl, Methyl ⁇ propylphenyl, naphthyl, etc.; preferably phenyl or naphthyl, especially phenyl.
  • C n -C m alkoxy refers to a C n -C m alkyl group corresponding to any carbon atom of the open chain C n -C m alkane bonded with an oxygen atom as a linking group C n -C m alkyl, for example C 1 -C 12 alkoxy, more preferably C 1 -C 6 alkoxy, especially preferably C 1 -C 4 alkoxy.
  • C n -C m alkoxy groups mention may be made of methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy Group, isopentyloxy, hexyloxy and its isomers.
  • C n -C m haloalkyl refers to a C n -C m alkyl group substituted with one or more identical or different halogen atoms, such as C 1 -C 12 haloalkyl, preferably C 1 -C 6 haloalkyl, C 1 -C 4 haloalkyl is particularly preferred.
  • haloalkyl groups here, mention may be made of monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, 1-chloromethylethyl, monochlorobutyl, 1 -Chloromethylpropyl, 2-chloromethylpropyl, 1,1-dichloromethylethyl, monochloropentyl, 1-chloromethylbutyl, 2-chloromethylbutyl, 3-chloro Methylbutyl, 2,2-dichloromethylpropyl, 1-chloroethylpropyl, monochlorohexyl, 1,1-dichloromethylpropyl, 1,2-dichloromethylpropyl, 1-chloromethylpentyl, 2-chloromethylpentyl, 3-chloromethylpentyl, 4-chloromethylpentyl, 1,1-dichloromethylbutyl, 1,
  • C n -C m haloalkoxy refers to a C n -C m alkoxy group substituted by one or more identical or different halogen atoms, such as C 1 -C 12 haloalkoxy, more preferably C 1 -C 6 haloalkoxy, especially C 1 -C 4 haloalkoxy.
  • C n -C m halogenated alkoxy groups mention may be made of monochloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 2-chloroisopropoxy, 4-chloro-n-butoxy , 3-chloro-sec-butoxy, 2-chloro-tert-butoxy, 5-chloropentyloxy, 4-chloroisopentyloxy, 6-chlorohexyloxy and its isomers.
  • hydroxyalkyl C n -C m alkyl means any carbon atom in the C n -C m alkyl corresponding open-chain alkanes C n -C m hydroxyl group bonded to a C n -C m Alkyl groups, such as C 1 -C 6 hydroxyalkyl groups, particularly preferably C 1 -C 4 hydroxyalkyl groups, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, hydroxybutyl, hydroxypentyl, Hydroxyhexyl and its isomers.
  • n is usually an integer of 1-50, preferably an integer of 1-15, and particularly preferably an integer of 1-12, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
  • m is usually an integer of 1-10, preferably an integer of 1-6, particularly preferably an integer of 2-4, such as 2, 3, or 4.
  • z is usually an integer of 0-10, preferably an integer of 1-6, and particularly preferably an integer of 0-3, such as 0, 1, 2 or 3.
  • p is usually an integer of 1-6, preferably an integer of 1-4, particularly preferably an integer of 1-3, such as 1, 2, or 3.
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are the same or different, and are usually independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy or C 1 -C 12 alkyl with one or more heteroatoms independently selected from NR b , O, S inserted between two carbon atoms, wherein R b is H or C 1- C 4 alkyl.
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different and are independently C 6 -C 10 aryl, C 1 -C 6 alkyl, C 1 -C 6 An alkoxy group or a C 1 -C 6 alkyl group with one or more heteroatoms selected from NR b , O, and S inserted between two carbon atoms, wherein R b is H or a C 1 -C 4 alkyl group.
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different, and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or A C 1 -C 4 alkyl group with one or more heteroatoms independently selected from NR b , O, and S inserted between two carbon atoms, wherein R b is H or a C 1 -C 4 alkyl group.
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 1 -C 4 alkyl groups.
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently H, phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, S-butyl, t-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s-butoxy or t-butoxy.
  • R 8 is usually H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy.
  • R 8 is H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkoxy or C 1 -C 4 Haloalkoxy. It is particularly preferred that R 8 is H or C 1 -C 4 alkyl.
  • R 8 can 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.
  • R 9 is usually H or C 1 -C 12 alkyl.
  • R 9 is H or C 1 -C 6 alkyl. It is particularly preferred that R 9 is H or C 1 -C 4 alkyl.
  • R 9 can be H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, especially H or methyl.
  • n is an integer of 1-12;
  • n 2, 3 or 4;
  • z 0, 1, 2 or 3;
  • p 1, 2 or 3;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 1 -C 4 alkyl groups;
  • R 8 is H or C 1 -C 4 alkyl
  • R 9 is H or C 1 -C 4 alkyl, especially H or methyl.
  • the compound of formula (I) is one or more compounds selected from the following group:
  • n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined for the compound of formula (I),
  • p and R 8 are as defined for the compound of formula (I), and X is halogen, such as fluorine, chlorine, bromine or iodine,
  • n, m, z, p, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are as defined for the compound of formula (I);
  • R 9 is as defined for the compound of formula (I), and Y is halogen, such as fluorine, chlorine, bromine or iodine.
  • step (1) the reaction between the terminal hydroxyl group in the compound of formula (II) and the halogen in the compound of formula (III) belongs to a type of reaction known in the art, and the reaction produces hydrogen halide.
  • this reaction is carried out in the presence of a basic catalyst.
  • a basic catalyst suitable for this reaction sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof can be mentioned.
  • the amount of catalyst is also conventional.
  • the molar ratio of the compound of formula (II) to the basic catalyst is 1:1 to 1:5.
  • the reaction of the compound of formula (II) with the compound of formula (III) is usually carried out in a solvent.
  • the type of solvent is not particularly limited, as long as it can dissolve the compound of formula (II), the compound of formula (III) and the corresponding basic catalyst and does not participate in the reaction between the compound of formula (II) and the compound of formula (III).
  • the solvent also facilitates the precipitation of the product, that is, the compound of formula (IV).
  • an organic solvent is generally used, and toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile, or any mixtures thereof are preferably used.
  • the amount of solvent is also conventional.
  • the amount of solvent is 1.0 to 3 times the total weight of the compound of formula (II) and compound of formula (III).
  • the amount of the compound of formula (II) and the compound of formula (III) is usually used in approximately equimolar amounts.
  • the molar ratio of the compound of formula (II) to the compound of formula (III) is 1:1-1:1.2.
  • the compound of formula (II) and a basic catalyst are dissolved in a solvent, the temperature is lowered to the freezing point (about 0°C), and then the compound of formula (III) is added.
  • the resulting reaction mixture is first heated to the freezing temperature ( (Approximately 0°C) the reaction is stirred for 0.5-3 hours, preferably 0.5-1 hour, and then the temperature is increased to 25-60°C, preferably to 35-60°C. After the temperature is raised, the reaction is usually continued for 6-24 hours, preferably for 8-24 hours. Of course, the reaction is advantageously carried out under stirring. After the reaction is completed, the compound of formula (IV) can be obtained through conventional post-treatment.
  • This post-treatment usually includes extraction or washing (for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and vacuum distillation to further remove the solvent. If you want to obtain a higher purity product, you can also recrystallization or column chromatography to separate impurities.
  • extraction or washing for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water
  • filtration or centrifugation to remove solid impurities
  • rotary evaporation to remove the solvent
  • vacuum distillation to further remove the solvent.
  • step (2) the reaction between the terminal hydroxyl group in the compound of formula (IV) and the acid halide in the compound of formula (V) belongs to a type of reaction known in the art, and the reaction produces hydrogen halide.
  • the reaction is carried out in the presence of a catalyst.
  • a catalyst suitable for this reaction triethylamine, potassium carbonate or any mixture thereof can be mentioned.
  • the amount of catalyst is also conventional.
  • the molar ratio of the compound of formula (IV) to the catalyst is 1:1 to 1:3.
  • the reaction of the compound of formula (IV) with the compound of formula (V) is usually carried out in a solvent.
  • the type of solvent is not particularly limited, as long as it can dissolve the compound of formula (IV), the compound of formula (V) and the corresponding catalyst and does not participate in the reaction between the compound of formula (IV) and the compound of formula (V), preferably
  • the solvent also facilitates the precipitation of the product, that is, the compound of formula (I).
  • an organic solvent is generally used, and toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile, or any mixtures thereof are preferably used.
  • the amount of solvent is also conventional.
  • the amount of solvent is 1.0 to 3 times the total weight of the compound of formula (IV) and compound of formula (V).
  • the amount of the compound of formula (IV) and the compound of formula (V) is usually used in approximately equimolar amounts.
  • the molar ratio of the compound of formula (IV) to the compound of formula (IV) is 1:1-1:1.2.
  • the compound of formula (IV) and the catalyst are dissolved in a solvent, the temperature is lowered to the freezing point (about 0°C), and then a solution of the compound of formula (V) in the solvent is added.
  • the resulting reaction mixture is stirred at freezing temperature (about 0°C) for 0.5-3 hours, preferably 0.5-1 hour, then the temperature is raised to 25-60°C, preferably to 25-35°C, and the reaction is continued for 6-24 hours, preferably 8-12 hours.
  • the reaction is advantageously carried out under stirring.
  • the compound of formula (I) can be obtained through conventional post-treatment.
  • This post-treatment usually includes extraction or washing (for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and vacuum distillation to further remove the solvent. If you want to obtain a higher purity product, you can also recrystallization or column chromatography to separate impurities.
  • the compound of formula (I) of the present invention is a polysilicon-containing oxetane monomer that can be mixed with light curing. It has a fast curing speed, good tensile properties after light curing, excellent hydrophobic properties, stain resistance, and Fingerprint, chemical corrosion resistance, strong anti-aging performance, good heat resistance.
  • the synthetic method is simple and feasible, and the conditions are mild; the raw materials are easily available and the price is low.
  • a photocurable composition comprising the compound of formula (I) of the present invention as a polymerizable monomer.
  • the photocurable composition usually contains a cationic photoinitiator for ring-opening polymerization (a photoinitiator that can initiate cationic polymerization) and a free radical photoinitiator (which can initiate free radicals). Photoinitiator for polymerization).
  • the cationic photoinitiator for ring-opening polymerization initiates the ring-opening polymerization of the oxetane structure in the compound of formula (I) under ultraviolet light irradiation, and the free radical photoinitiator initiates the formula (I) under ultraviolet light irradiation Polymerization of olefinic double bonds in compounds.
  • the photocurable composition can also contain other monomers containing vinyl ether double bonds, alicyclic epoxy groups, oxiranyl groups or oxetanyl groups and other cationic photocurable groups, low Polymers, such as 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221).
  • the photocurable composition of the present invention may be a photocurable coating composition, a photocurable ink composition, a photoresist composition, and the like. After the composition is cured, the resulting cured product has good tensile properties, excellent hydrophobic properties, anti-staining, anti-fingerprint, anti-chemical corrosion, and strong anti-aging properties.
  • iodonium salts and sulfonium salts are commonly used.
  • the iodonium salt photoinitiator and the sulfonium salt photoinitiator have the following general formulas (A) and (B), respectively
  • R a , R b , R c , R d , R e are each independently an unsubstituted C 6 -C 10 aryl group, or are selected from halogen, nitro, carbonyl, C 1 -C 12 alkyl, C 1 C 6 -C 10 aryl substituted with substituents of -C 12 alkoxy, thiophenyl, phenyl and substituted phenyl, preferably phenyl or naphthyl, or selected from halogen, nitro, C 1- C 6 alkyl and substituted phenyl substituted phenyl or naphthyl, wherein the substituted phenyl contains one or more substituents selected from halogen, nitro, C 1 -C 6 alkyl and C 1- C 6 alkoxy group; and
  • Y and Z are non-nucleophilic anions, such as trifluoromethanesulfonate, BF 4 — , ClO 4 — , PF 6 — , AsF 6 — , SbF 6 — .
  • one or more selected from the following group can be used: 4-(phenylthio)phenyl ⁇ diphenylsulfonium hexafluorophosphate, 4-(phenylthio)phenyl ⁇ Diphenylsulfonium hexafluoroantimonate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexa Fluorantimonate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone Ketone-10-sulfonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate (8
  • free radical photoinitiators there are usually 2-isopropylthioxanthone (ITX), 2-hydroxy-2-methyl-1-phenylacetone (1173), 1-hydroxycyclohexylphenyl ketone ( 184), 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone (907), 2,4,6-trimethylbenzyl Acyl-diphenylphosphine oxide (TPO), 2,4,6-trimethylbenzoylphenyl phosphonate (TPO-L), 2-dimethylamino-2-benzyl-1-[4 -(4-morpholinyl)phenyl]-1-butanone (IHT-PI 910), 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1 -Acetone (659), methyl benzoylformate (MBF), etc.
  • IHT-PI 910 2-isopropylthioxanthone
  • the amount of photoinitiator is conventional.
  • the content of the cationic photoinitiator for ring-opening polymerization is usually 0.5-5%, preferably 1-3%.
  • the content of the free radical photoinitiator is usually 0.5-3%, preferably 1-2%.
  • a photocurable material is provided, which is obtained by photocuring the photocurable composition of the present invention. Because the photocurable material contains the compound of formula (I) of the present invention as a photocurable monomer, the curing speed is fast, the performance is easy to adjust, and after curing, it has good tensile properties, excellent hydrophobic properties, stain resistance, and fingerprint resistance. , Anti-chemical corrosion, strong anti-aging performance, good heat resistance.
  • Example 1 was repeated, but 22 mmol of acryloyl chloride was replaced by 22 mmol of methacryloyl chloride.
  • the resulting final product was characterized by hydrogen nuclear magnetic spectroscopy and silicon spectroscopy and identified as compound 2, sometimes referred to as BODSi-2 hereinafter.
  • the purpose of this example is to illustrate the photopolymerization properties of the compounds of the present invention.
  • the asymmetric deformation vibration absorption peak of the COC bond of the oxetanyl group is located at 980 cm -1
  • Fig. 1 is a graph showing the change of double bond conversion rate with irradiation time
  • Fig. 2 is a graph showing the change of double bond conversion rate with irradiation time
  • each of the compounds 2-6 has an initiation system with four concentrations of 0.75% 810+0.38% ITX, 1.50% 810+0.75% ITX, 3.00% 810+1.50% ITX, and 4.50% 810+2.25% ITX.
  • the conversion rate of the quaternary oxygen heterocyclic ring of the monomer will increase with the increase of the initiator concentration, and the maximum conversion rate of the quaternary oxygen heterocyclic ring of the monomer has reached at least 60%.
  • the maximum conversion rate of carbon double bonds reached at least 75%.
  • the respective concentrations of 810 and ITX are based on the respective weight of compound 1-6. Therefore, the compound of the present invention has good photopolymerization performance.
  • the purpose of this example is to show that the compound of the present invention can improve the surface hydrophobicity of the photocurable film.
  • Compounds 1-6 were each mixed with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221) epoxy monomer in a mass ratio of 15:85, based on E4221 and compound 1
  • the total weight of each of -6 is 3.0wt% 810 and 1.5wt% ITX as initiators, and they are mixed uniformly to obtain a photosensitive liquid.
  • OCA20 German dataphysics company
  • the purpose of this example is to show that the compound of the present invention can improve the tensile properties of the photocurable film.
  • the cured film of compound 1-6 was prepared in exactly the same way as described in Example 8. Then, an Instron-1211 electronic tensile machine (Instron-1211, Instron, USA) was used to test the tensile properties of the light-cured film at a test temperature of 25°C and a test speed of 50 mm/min. At the same time, use the same method to prepare a blank E4221 cured film as a reference.
  • Instron-1211 electronic tensile machine Instron-1211, Instron, USA
  • the tensile strength of the pure E4221 light-cured film is 7.02MPa, and the elongation at break is 7.5%; and after adding 15% of compound 1, the tensile strength of the cured film of E4221 reaches 11.9MPa and the elongation at break is 15.7. %.
  • the tensile strength of the cured film obtained by additionally adding one of the compounds 2-6 all exceeded 11.0 MPa, and the elongation at break all exceeded 15.2%. Therefore, the compound of the present invention can significantly improve the tensile properties of the cured film.

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Abstract

The present invention relates to a compound represented by formula (I), wherein variables n, m, z, p, R2, R3, R4, R5, R6, R7, R8 and R9 are as defined in the description. The compound represented by formula (I) not only has, after photocuring, good tensile properties, excellent hydrophobic properties, anti-staining, anti-fingerprint and anti-chemical corrosion properties, strong anti-aging properties, and good heat resistance, but also has a fast curing speed and easy performance adjustment, thus broadening the application range of a photocuring system. The present invention further relates to the preparation of the compound represented by formula (I), a photocurable composition containing the compound represented by formula (I), and a photocured material obtained by photocuring the photocurable composition.

Description

一种可混杂光固化的含多硅的氧杂环丁烷类单体及其制备和应用Hybrid light-curable oxetane monomer containing polysilicon and preparation and application thereof 技术领域Technical field
本发明所属技术领域为光固化材料领域，具体来说涉及一种可混杂光固化的含多硅的氧杂环丁烷类单体。本发明还涉及该单体的制备方法，包含该单体的可光固化组合物和由该可光固化组合物光固化得到的光固化材料。The technical field of the present invention is the field of light-curable materials, and specifically relates to a polysilicon-containing oxetane monomer that can be mixed with light-curable. The invention also relates to a preparation method of the monomer, a photocurable composition containing the monomer and a photocurable material obtained by photocuring the photocurable composition.
背景技术Background technique
紫外光固化是指在紫外线的辐照下，光引发剂受激发变为自由基或阳离子，从而引发单体间发生聚合固化反应形成高分子聚合物的过程。与热固化相比，紫外光固化技术具有环境污染小、涂膜质量高、能量消耗低等优点，因而在光固化涂料、粘合剂和油墨印刷等领域应用广泛。并且，随着对有机挥发组分排放控制日益严格，紫外光固化技术将具有更广阔的发展前景。Ultraviolet curing refers to the process in which a photoinitiator is excited to become free radicals or cations under ultraviolet radiation, thereby initiating polymerization and curing reactions between monomers to form high molecular polymers. Compared with thermal curing, ultraviolet light curing technology has the advantages of low environmental pollution, high film quality, and low energy consumption. Therefore, it is widely used in light-curing coatings, adhesives, and ink printing. Moreover, as the emission control of organic volatile components becomes stricter, UV curing technology will have a broader development prospect.
自由基光固化体系具有固化速度快、性能易于调节的优点，但也有收缩严重、精度不高、附着力差等问题。阳离子固化体系发展较晚，它具有体积收缩小、附着力强、耐磨、硬度高等优点，特别适用于需要高精度的激光快速成型技术(立体光刻)和需要附着力强、耐磨的光盘和光纤涂层等方面，但它也有固化速度慢、低聚物和活性稀释剂种类少、价格高、固化产物性能不易调节等缺点，从而限制了其实际应用。The free radical light curing system has the advantages of fast curing speed and easy adjustment of performance, but also has the problems of serious shrinkage, low precision, and poor adhesion. The development of cationic curing system is relatively late. It has the advantages of small volume shrinkage, strong adhesion, wear resistance, high hardness, etc. It is especially suitable for laser rapid prototyping technology (stereolithography) that requires high precision and optical discs that require strong adhesion and wear resistance. It also has the disadvantages of slow curing speed, few types of oligomers and reactive diluents, high price, and difficult adjustment of cured product performance, which limits its practical application.
氧杂环烷烃类单体属阳离子光固化体系单体。氧杂环烷烃类单体是高端阳离子光固化产品的主要原料，这种体系不仅粘度低、毒性低、聚合速度快，还具有优异的热稳定性及机械性能。然而，在紫外光固化以节能、环保、高效等优点迅速发展的同时，对于光固化材料的耐热性、拒水性、表面的抗沾污、耐腐蚀及抗指纹等方面人们提出了更高的要求。消费者对产品外观的要求日益提高，除了色彩美观以及手感舒适外，还要求表面具有抗指纹、耐沾污的性能，即使用时产品表面不易留下指纹等痕迹，或者即使留下痕迹也很容易被擦净。目前，能够满足前述要求并且固化速度快、性能易于调节的光固化单体的种类非常少，市场上更是没有这类光固化单体，因此亟需开发。Oxycycloalkane monomers belong to cationic light curing system monomers. Oxycycloalkane monomers are the main raw materials for high-end cationic light curing products. This system not only has low viscosity, low toxicity, and fast polymerization speed, but also has excellent thermal stability and mechanical properties. However, while UV curing has developed rapidly with the advantages of energy saving, environmental protection and high efficiency, people have proposed higher standards for the heat resistance, water repellency, surface stain resistance, corrosion resistance and fingerprint resistance of photocurable materials. Claim. Consumers are increasingly demanding the appearance of products. In addition to beautiful colors and comfortable feel, the surface is also required to have anti-fingerprint and stain-resistant performance, that is, it is not easy to leave fingerprints and other traces on the surface of the product during use, or it is easy to leave traces Be wiped clean. At present, there are very few types of photocurable monomers that can meet the aforementioned requirements, have fast curing speed and easily adjustable performance, and there is no such photocurable monomer on the market, so development is urgently needed.
发明内容Summary of the invention
鉴于现有技术的上述状况，本发明的发明人在氧杂环丁烷类可阳离子光聚合单体方面进行了广泛而又深入的研究，以期发现一类新型的可光固化单体，该单体不仅固化后具有拉伸性能好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强等优点，而且固化速度快、性能易于调节。本发明人发现，将有机硅氧烷与氧杂环丁烷结构部分及丙烯酸酯基相结合得到的可混杂光固化单体化合物即具有前述优点。In view of the above-mentioned state of the art, the inventors of the present invention have conducted extensive and in-depth research on oxetane cationic photopolymerizable monomers in order to discover a new type of photocurable monomers. After curing, the body not only has the advantages of good tensile properties, excellent hydrophobic properties, anti-staining, anti-fingerprint, anti-chemical corrosion, and strong anti-aging properties, but also has fast curing speed and easy adjustment of performance. The present inventors discovered that the hybrid light-curable monomer compound obtained by combining the organosiloxane with the oxetane moiety and the acrylate group has the aforementioned advantages.
因此，本发明的一个目的是提供一种可混杂光固化的含多硅的氧杂环丁烷单体，该单体不仅含有可阳离子光固化的氧杂环丁烷基团，而且还含有聚硅氧烷链和可自由基光固化的丙烯酸酯基。具有如此结构的单体不仅光固化后拉伸性能好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强，耐热性好，而且固化速度快、性能易于调节，从而拓宽了光固化体系的应用范围。Therefore, one object of the present invention is to provide a hybrid photocurable polysilicon-containing oxetane monomer, which not only contains cationic photocurable oxetane groups, but also contains polysilicon Siloxane chain and free radical light-curable acrylate group. The monomer with such a structure not only has good tensile properties after light curing, excellent hydrophobic properties, anti-staining, anti-fingerprint, anti-chemical corrosion, strong anti-aging properties, good heat resistance, but also has fast curing speed and easy adjustment of performance. This broadens the application range of the light curing system.
本发明的另一目的是提供一种制备本发明可混杂光固化的含多硅的氧杂环丁烷单体的方法。该制备过程简单易行，条件温和，原料易得，价格低廉。Another object of the present invention is to provide a method for preparing the hybrid light-curable polysilicon-containing oxetane monomer of the present invention. The preparation process is simple and feasible, the conditions are mild, the raw materials are readily available, and the price is low.
本发明的再一个目的是提供一种可光固化组合物，该组合物包含根据本发明的可混杂光固化的含多硅的氧杂环丁烷单体。Another object of the present invention is to provide a photocurable composition comprising the hybrid photocurable polysilicon-containing oxetane monomer according to the present invention.
本发明的最后一个目的是提供一种光固化材料，该材料通过将本发明的可光固化组合物光固化而获得。The last object of the present invention is to provide a photocurable material which is obtained by photocuring the photocurable composition of the present invention.
实现本发明上述目的的技术方案可以概括如下：The technical solutions for achieving the above-mentioned objects of the present invention can be summarized as follows:
1.下式(I)化合物：1. The compound of the following formula (I):
Figure PCTCN2020097175-appb-000001
Figure PCTCN2020097175-appb-000001
其中among them
n为1-50的整数；n is an integer from 1-50;
m为1-10的整数；m is an integer of 1-10;
z为0-10的整数；z is an integer of 0-10;
p为1-6的整数；p is an integer of 1-6;
R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 6-C 10芳基、C 1-C 12烷基、C 1-C 12烷氧基或者两个碳原子之间插有一个或多个独立地选自N、O、S的杂原子的C 1-C 12烷基； R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy or A C 1 -C 12 alkyl group with one or more heteroatoms independently selected from N, O and S inserted between two carbon atoms;
R 8为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基；以及 R 8 is H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy; as well as
R 9为H或C 1-C 12烷基。 R 9 is H or C 1 -C 12 alkyl.
2.根据第1项的化合物，其中2. The compound according to item 1, wherein
n为1-15的整数，优选为1-12的整数；和/或n is an integer of 1-15, preferably an integer of 1-12; and/or
m为1-6的整数，优选为2-4的整数；和/或m is an integer of 1-6, preferably an integer of 2-4; and/or
z为1-6的整数，优选为0-3的整数；和/或z is an integer of 1-6, preferably an integer of 0-3; and/or
p为1-4的整数，优选为1-3的整数；和/或p is an integer of 1-4, preferably an integer of 1-3; and/or
R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 6-C 10芳基、C 1-C 6烷基、C 1-C 6烷氧基或者两个碳原子之间插有一个或多个选自NR b、O、S的杂原子的C 1-C 6烷基，其中R b为H或C 1-C 4烷基，优选R 2、R 3、R 4、R 5、R 6、R 7相同或不同并独立地为苯基、C 1-C 4烷基、C 1-C 4烷氧基或者两个碳原子之间插有一个或多个独立地选自NR b、O、S的杂原子的C 1-C 4烷基，其中R b为H或C 1-C 4烷基；和/或 R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or A C 1 -C 6 alkyl group with one or more heteroatoms selected from NR b , O, and S inserted between two carbon atoms, wherein R b is H or C 1 -C 4 alkyl, preferably R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are the same or different and are independently a phenyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or one interposed between two carbon atoms Or more C 1 -C 4 alkyl groups independently selected from heteroatoms of NR b , O, and S, wherein R b is H or C 1 -C 4 alkyl; and/or
R 8为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基，优选为H或C 1-C 4烷基；和/或 R 8 is H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy, Preferably H or C 1 -C 4 alkyl; and/or
R 9为H或C 1-C 6烷基，优选为H或C 1-C 4烷基。 R 9 is H or C 1 -C 6 alkyl, preferably H or C 1 -C 4 alkyl.
3.根据第1项的化合物，其中3. The compound according to item 1, wherein
n为1-12的整数；和/或n is an integer from 1-12; and/or
m为2、3或4；和/或m is 2, 3 or 4; and/or
z为0、1、2或3；和/或z is 0, 1, 2 or 3; and/or
p为1、2或3；和/或p is 1, 2 or 3; and/or
R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 1-C 4烷基；和/或 R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 1 -C 4 alkyl groups; and/or
R 8为H或C 1-C 4烷基；和/或 R 8 is H or C 1 -C 4 alkyl; and/or
R 9为H或C 1-C 4烷基，尤其是H或甲基。 R 9 is H or C 1 -C 4 alkyl, especially H or methyl.
4.根据第1项的化合物，其为一种或多种选自下组的化合物：4. The compound according to item 1, which is one or more compounds selected from the following group:
Figure PCTCN2020097175-appb-000002
Figure PCTCN2020097175-appb-000002
5.一种制备根据第1-4项中任一项的式(I)化合物的方法，包括：5. A method for preparing a compound of formula (I) according to any one of items 1 to 4, comprising:
(1)使式(II)化合物(1) Make the compound of formula (II)
Figure PCTCN2020097175-appb-000003
Figure PCTCN2020097175-appb-000003
其中n、m、z、R 2、R 3、R 4、R 5、R 6和R 7如第1-4项中任一项所定义， Wherein n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined in any one of items 1-4,
与式(III)化合物反应，React with the compound of formula (III),
Figure PCTCN2020097175-appb-000004
Figure PCTCN2020097175-appb-000004
其中p和R 8如第1-4项中任一项所定义，并且X为卤素，例如氟、氯、溴或碘， Wherein p and R 8 are as defined in any one of items 1 to 4, and X is halogen, such as fluorine, chlorine, bromine or iodine,
得到式(IV)化合物，To obtain the compound of formula (IV),
Figure PCTCN2020097175-appb-000005
Figure PCTCN2020097175-appb-000005
其中n、m、z、p、R 2、R 3、R 4、R 5、R 6、R 7和R 8第1-4项中任一项所定义；以及 Wherein n, m, z, p, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are defined in any one of items 1-4; and
(2)使式(IV)化合物与式(V)化合物反应，得到式(I)化合物，(2) reacting the compound of formula (IV) with the compound of formula (V) to obtain the compound of formula (I),
Figure PCTCN2020097175-appb-000006
Figure PCTCN2020097175-appb-000006
其中R 9如第1-4项中任一项所定义，并且Y为卤素，例如氟、氯、溴或碘。 Wherein R 9 is as defined in any one of items 1-4, and Y is halogen, such as fluorine, chlorine, bromine or iodine.
6.根据第5项的方法，其中在步骤(1)中，6. The method according to item 5, wherein in step (1),
式(II)化合物与式(III)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选是氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物，更优选的是，式(II)化合物与碱性催化剂的摩尔比为1:1-1:5；和/或The reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a basic catalyst. The basic catalyst is preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably , The molar ratio of the compound of formula (II) to the basic catalyst is 1:1-1:5; and/or
式(II)化合物与式(III)化合物的摩尔比为1:1-1:1.5；和/或The molar ratio of the compound of formula (II) to the compound of formula (III) is 1:1-1:1.5; and/or
式(II)化合物与式(III)化合物之间的反应先在冰点温度下进行，然后升温至25-60℃，优选升温至35-60℃反应；优选的是，冰点温度下的反应进行0.5-3小时，优选0.5-1小时；和/或，升温后继续反应6-24小时，优选8-24小时。The reaction between the compound of formula (II) and the compound of formula (III) is first carried out at the freezing temperature, and then the temperature is increased to 25-60°C, preferably to 35-60°C; preferably, the reaction at the freezing temperature proceeds to 0.5 -3 hours, preferably 0.5-1 hour; and/or, continue the reaction for 6-24 hours after raising the temperature, preferably 8-24 hours.
7.根据第5或6项的方法，其中在步骤(2)中，7. The method according to item 5 or 6, wherein in step (2),
式(IV)化合物与式(V)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选为三乙胺、碳酸钾或其任意混合物，更优选的是，式(IV)化合物与催化剂的摩尔比为1:1-1:3(实施例没有使用碱性催化剂)；和/或The reaction between the compound of formula (IV) and the compound of formula (V) is carried out in the presence of a basic catalyst. The basic catalyst is preferably triethylamine, potassium carbonate or any mixture thereof, and more preferably, the compound of formula (IV) and the catalyst The molar ratio of is 1:1-1:3 (the example does not use a basic catalyst); and/or
式(IV)化合物与式(IV)化合物的摩尔比为1:1-1:1.2；和/或The molar ratio of the compound of formula (IV) to the compound of formula (IV) is 1:1-1:1.2; and/or
式(IV)化合物与式(IV)化合物的反应先在冰点温度下进行，然后升温至25-60℃，优选升温至25-35℃反应；优选的是，所述冰点温度下的反应进行0.5-3小时，优选0.5-1小时；和/或升温后继续反应6-24小时，优选8-12小时。The reaction between the compound of formula (IV) and the compound of formula (IV) is first carried out at freezing temperature, and then the temperature is raised to 25-60°C, preferably to 25-35°C; preferably, the reaction at the freezing point temperature is carried out 0.5 -3 hours, preferably 0.5-1 hour; and/or continue the reaction for 6-24 hours, preferably 8-12 hours after raising the temperature.
8.根据第5-7项中任一项，其中X和Y均为氯。8. According to any one of items 5-7, wherein X and Y are both chlorine.
9.一种可光固化组合物，包含根据第1-4项中任一项的式(I)化合物作为聚合单体。9. A photocurable composition comprising the compound of formula (I) according to any one of items 1 to 4 as a polymerizable monomer.
10.一种光固化材料，该材料通过将根据第9项的可光固化组合物光固化而获得。10. A photocurable material obtained by photocuring the photocurable composition according to item 9.
附图说明Description of the drawings
图1是实施例1所制备的化合物1的双键转化率随辐照时间的变化曲线图。Fig. 1 is a graph showing the change of double bond conversion rate of compound 1 prepared in Example 1 with irradiation time.
图2是实施例1所制备的化合物1的氧杂环丁烷环转化率随辐照时间的变化曲线图。2 is a graph showing the change of the oxetane ring conversion rate of Compound 1 prepared in Example 1 with the irradiation time.
具体实施方式Detailed ways
根据本发明的一个方面，提供了一种下式(I)化合物：According to one aspect of the present invention, there is provided a compound of the following formula (I):
Figure PCTCN2020097175-appb-000007
Figure PCTCN2020097175-appb-000007
其中among them
n为1-50的整数；n is an integer from 1-50;
m为1-10的整数；m is an integer of 1-10;
z为0-10的整数；z is an integer of 0-10;
p为1-6的整数；p is an integer of 1-6;
R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 6-C 10芳基、C 1-C 12烷基、C 1-C 12烷氧基或者两个碳原子之间插有一个或多个独立地选自N、O、S的杂原子的C 1-C 12烷基； R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy or A C 1 -C 12 alkyl group with one or more heteroatoms independently selected from N, O and S inserted between two carbon atoms;
R 8为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基；以及 R 8 is H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy; as well as
R 9为H或C 1-C 12烷基。 R 9 is H or C 1 -C 12 alkyl.
在本发明中，式(I)化合物既包含可阳离子光固化的氧杂环丁烷结构，又包含可自由基光固化的丙烯酸酯结构部分，另外还包含聚硅氧烷结构部分。具有如此结构的化合物兼有阳离子固化和自由基固化的优点，不仅固化速度快、性能易于调节，而且还具有体积收缩小、附着力强、耐磨、硬度高等优点，此外光固化后拉伸性能好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强，耐热性好。In the present invention, the compound of formula (I) contains both a cationic photocurable oxetane structure, a radical photocurable acrylate structure part, and a polysiloxane structure part. The compound with such a structure has the advantages of both cationic curing and free radical curing. It not only has fast curing speed and easy adjustment of performance, but also has the advantages of small volume shrinkage, strong adhesion, wear resistance and high hardness. In addition, it has tensile properties after light curing. Good, excellent hydrophobic performance, stain resistance, fingerprint resistance, chemical corrosion resistance, strong anti-aging performance, and good heat resistance.
在本发明中，前缀“C n-C m”在每种情况下表示该基团中包含的碳原子数为n-m个。 In the present invention, the prefix "C n -C m "in each case indicates that the number of carbon atoms contained in the group is nm.
“卤素”是指氟、氯、溴和碘。在本发明中，优选的是，卤素包括氟、氯或其组合。"Halogen" refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferable that the halogen includes fluorine, chlorine or a combination thereof.
本文所用的术语“C n-C m烷基”是指具有n-m个，例如1-12个，优选1-6个，特别优选1-4个碳原子的一价支化或未支化饱和烃基。作为C n-C m烷基的实例，可以提及甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、己基、1,1-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基、庚基、辛基、2-乙基己基、壬基、癸基、十一烷基、十二烷基及其异构体。 The term "C n -C m alkyl group" as used herein refers to a monovalent branched or unbranched saturated hydrocarbon group having nm, for example 1-12, preferably 1-6, particularly preferably 1-4 carbon atoms . As examples of C n -C m alkyl groups, mention may be made of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1 -Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-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 isopropyl Construct.
本文所用术语“C 6-C m芳基”是指含有6-m个碳原子，例如6-10个碳原子的单环、双环或更多环芳族烃基。作为C 6-C m芳基的实例，可提及苯基、甲苯基、乙苯基、丙苯基、丁苯基、二甲苯基、甲基·乙基苯基、二乙基苯基、甲基·丙基苯基和萘基等；优选苯基或萘基，尤其是苯基。 The term "C 6 -C m aryl group" as used herein refers to a monocyclic, bicyclic or multicyclic aromatic hydrocarbon group containing 6 to m carbon atoms, for example, 6 to 10 carbon atoms. As examples of C 6 -C m aryl groups, mention may be made of phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methyl ethyl phenyl, diethyl phenyl, Methyl·propylphenyl, naphthyl, etc.; preferably phenyl or naphthyl, especially phenyl.
本文所用的术语“C n-C m烷氧基”是指在C n-C m烷基对应的开链C n-C m烷烃的任何碳原子上键合有一个氧原子作为连接基团的C n-C m烷基，例如C 1-C 12烷氧基，更优选C 1-C 6烷氧基，尤其优选C 1-C 4烷氧基。作为C n-C m烷氧基的实例，可以提及甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、2-丁氧基、叔丁氧基、戊氧基、异戊氧基、己氧基及其异构体。 The term "C n -C m alkoxy" as used herein refers to a C n -C m alkyl group corresponding to any carbon atom of the open chain C n -C m alkane bonded with an oxygen atom as a linking group C n -C m alkyl, for example C 1 -C 12 alkoxy, more preferably C 1 -C 6 alkoxy, especially preferably C 1 -C 4 alkoxy. As examples of C n -C m alkoxy groups, mention may be made of methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy Group, isopentyloxy, hexyloxy and its isomers.
本文所用的术语“C n-C m卤代烷基”是指被一个或多个相同或不同的卤素原子取代的C n-C m烷基，例如C 1-C 12卤代烷基，优选C 1-C 6卤代烷基，特别优选C 1-C 4卤代烷基。作为这里的卤代烷基的实例，可以提及一氯甲基、一氯乙基、二氯乙基、三氯乙基、一氯丙基、1-氯甲基乙基、一氯丁基、1-氯甲基丙基、2-氯甲基丙基、1,1-二氯甲基乙基、一氯戊基、1-氯甲基丁基、2-氯甲基丁基、3-氯甲基丁基、2,2-二氯甲基丙基、1-氯乙基丙基、一氯己基、1,1-二氯甲基丙基、1,2-二氯甲基丙基、1-氯甲基戊基、2-氯甲基戊基、3-氯甲基戊基、4-氯甲基戊基、1,1-二氯甲基丁基、1,2-二氯甲基丁基、1,3-二氯甲基丁基、2,2-二氯甲基丁基、2,3-二氯甲基丁基、3,3-二氯甲基丁基、1-氯乙基丁基、2-氯乙基丁基、1,1,2-三氯甲基丙基、1,2,2-三氯甲基丙基、1-氯乙基-1-甲基丙基、1-乙基-2-氯甲基丙基及其异构体。 The term "C n -C m haloalkyl" as used herein refers to a C n -C m alkyl group substituted with one or more identical or different halogen atoms, such as C 1 -C 12 haloalkyl, preferably C 1 -C 6 haloalkyl, C 1 -C 4 haloalkyl is particularly preferred. As examples of haloalkyl groups here, mention may be made of monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, 1-chloromethylethyl, monochlorobutyl, 1 -Chloromethylpropyl, 2-chloromethylpropyl, 1,1-dichloromethylethyl, monochloropentyl, 1-chloromethylbutyl, 2-chloromethylbutyl, 3-chloro Methylbutyl, 2,2-dichloromethylpropyl, 1-chloroethylpropyl, monochlorohexyl, 1,1-dichloromethylpropyl, 1,2-dichloromethylpropyl, 1-chloromethylpentyl, 2-chloromethylpentyl, 3-chloromethylpentyl, 4-chloromethylpentyl, 1,1-dichloromethylbutyl, 1,2-dichloromethyl Butyl, 1,3-dichloromethylbutyl, 2,2-dichloromethylbutyl, 2,3-dichloromethylbutyl, 3,3-dichloromethylbutyl, 1- Chloroethylbutyl, 2-chloroethylbutyl, 1,1,2-trichloromethylpropyl, 1,2,2-trichloromethylpropyl, 1-chloroethyl-1-methyl Propyl, 1-ethyl-2-chloromethylpropyl and its isomers.
本文所用的术语“C n-C m卤代烷氧基”是指被一个或多个相同或不同的卤素原子取代的C n-C m烷氧基，例如C 1-C 12卤代烷氧基，更优选C 1-C 6卤代烷氧基，尤其优选C 1-C 4卤代烷氧基。作为C n-C m卤代烷氧基的实例，可以提及一氯甲氧基、2-氯乙氧基、3-氯丙氧基、2-氯异丙氧基、4-氯正丁氧基、3-氯仲丁氧基、2-氯叔丁氧基、5-氯戊氧基、4-氯异戊氧基、6-氯己氧基及其异构体。 The term "C n -C m haloalkoxy" as used herein refers to a C n -C m alkoxy group substituted by one or more identical or different halogen atoms, such as C 1 -C 12 haloalkoxy, more preferably C 1 -C 6 haloalkoxy, especially C 1 -C 4 haloalkoxy. As examples of C n -C m halogenated alkoxy groups, mention may be made of monochloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 2-chloroisopropoxy, 4-chloro-n-butoxy , 3-chloro-sec-butoxy, 2-chloro-tert-butoxy, 5-chloropentyloxy, 4-chloroisopentyloxy, 6-chlorohexyloxy and its isomers.
本文所用的术语“C n-C m羟烷基”是指在C n-C m烷基对应的开链C n-C m烷烃的任何碳原子上键合有一个羟基的C n-C m烷基，例如C 1-C 6羟烷基，尤其优选C 1-C 4羟烷基，例如羟甲基、羟乙基、羟丙基、羟异丙基、羟丁基、羟戊基、羟己基及其异构体。 As used herein, the term "hydroxyalkyl C n -C m alkyl" means any carbon atom in the C n -C m alkyl corresponding open-chain alkanes C n -C m hydroxyl group bonded to a C n -C m Alkyl groups, such as C 1 -C 6 hydroxyalkyl groups, particularly preferably C 1 -C 4 hydroxyalkyl groups, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, hydroxybutyl, hydroxypentyl, Hydroxyhexyl and its isomers.
在本发明化合物中，n通常为1-50的整数，优选为1-15的整数，特别优选为1-12的整数，例如为1、2、3、4、5、6、7、8、9、10、11或12。In the compound of the present invention, n is usually an integer of 1-50, preferably an integer of 1-15, and particularly preferably an integer of 1-12, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
在本发明化合物中，m通常为1-10的整数，优选为1-6的整数，特别优选为2-4的整数，例如为2、3或4。In the compound of the present invention, m is usually an integer of 1-10, preferably an integer of 1-6, particularly preferably an integer of 2-4, such as 2, 3, or 4.
在本发明化合物中，z通常为0-10的整数，优选为1-6的整数，特别优选为0-3的整数，例如为0、1、2或3。In the compound of the present invention, z is usually an integer of 0-10, preferably an integer of 1-6, and particularly preferably an integer of 0-3, such as 0, 1, 2 or 3.
在本发明化合物中，p通常为1-6的整数，优选为1-4的整数，特别优选为1-3的整数，例如为1、2或3。In the compound of the present invention, p is usually an integer of 1-6, preferably an integer of 1-4, particularly preferably an integer of 1-3, such as 1, 2, or 3.
在本发明化合物中，R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并通常独立地为C 6-C 10芳基、C 1-C 12烷基、C 1-C 12烷氧基或者两个碳原子之间插有一个或多个独立地选自NR b、O、S的杂原子的C 1-C 12烷基，其中R b为H或C 1-C 4烷基。优选的是，R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 6-C 10芳基、C 1-C 6烷基、C 1-C 6烷氧基或者两个碳原子之间插有一个或多个选自NR b、O、S的杂原子的C 1-C 6烷基，其中R b为H或C 1-C 4烷基。特别优选的是，R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为苯基、C 1-C 4烷基、C 1-C 4烷氧基或者两个碳原子之间插有一个或多个独立地选自NR b、O、S的杂原子的C 1-C 4烷基，其中R b为H或C 1-C 4烷基。尤其是R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 1-C 4烷基。例如，R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为H、苯基、甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基或叔丁氧基。 In the compound of the present invention, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are the same or different, and are usually independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy or C 1 -C 12 alkyl with one or more heteroatoms independently selected from NR b , O, S inserted between two carbon atoms, wherein R b is H or C 1- C 4 alkyl. Preferably, R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different and are independently C 6 -C 10 aryl, C 1 -C 6 alkyl, C 1 -C 6 An alkoxy group or a C 1 -C 6 alkyl group with one or more heteroatoms selected from NR b , O, and S inserted between two carbon atoms, wherein R b is H or a C 1 -C 4 alkyl group. Particularly preferably, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different, and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or A C 1 -C 4 alkyl group with one or more heteroatoms independently selected from NR b , O, and S inserted between two carbon atoms, wherein R b is H or a C 1 -C 4 alkyl group. In particular, R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 1 -C 4 alkyl groups. For example, R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently H, phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, S-butyl, t-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s-butoxy or t-butoxy.
在本发明化合物中，R 8通常为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基。优选的是，R 8为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基。特别优选的是，R 8为H或C 1-C 4烷基。例如，R 8可以为H、氯、溴、甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、叔丁氧基、羟甲基、羟乙基、羟正丙基、羟异丙基、羟正丁基、羟仲丁基或羟叔丁基。 In the compound of the present invention, R 8 is usually H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy. Preferably, R 8 is H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkoxy or C 1 -C 4 Haloalkoxy. It is particularly preferred that R 8 is H or C 1 -C 4 alkyl. For example, R 8 can 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.
在本发明化合物中，R 9通常为H或C 1-C 12烷基。优选的是，R 9为H或C 1-C 6烷基。特别优选的是，R 9为H或C 1-C 4烷基。例如，R 9可以为H、甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基，尤其为H或甲基。 In the compounds of the present invention, R 9 is usually H or C 1 -C 12 alkyl. Preferably, R 9 is H or C 1 -C 6 alkyl. It is particularly preferred that R 9 is H or C 1 -C 4 alkyl. For example, R 9 can be H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, especially H or methyl.
在本发明的一些优选实施方案中，In some preferred embodiments of the invention,
n为1-12的整数；n is an integer of 1-12;
m为2、3或4为；m is 2, 3 or 4;
z为0、1、2或3；z is 0, 1, 2 or 3;
p为1、2或3；p is 1, 2 or 3;
R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 1-C 4烷基； R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 1 -C 4 alkyl groups;
R 8为H或C 1-C 4烷基；以及 R 8 is H or C 1 -C 4 alkyl; and
R 9为H或C 1-C 4烷基，尤其是H或甲基。 R 9 is H or C 1 -C 4 alkyl, especially H or methyl.
在本发明的另一实施方案中，式(I)化合物为一种或多种选自下组的化合物：In another embodiment of the present invention, the compound of formula (I) is one or more compounds selected from the following group:
Figure PCTCN2020097175-appb-000008
Figure PCTCN2020097175-appb-000008
根据本发明的第二个方面，提供了一种制备本发明式(I)化合物的方法，包括：According to the second aspect of the present invention, there is provided a method for preparing the compound of formula (I) of the present invention, comprising:
(1)使式(II)化合物(1) Make the compound of formula (II)
Figure PCTCN2020097175-appb-000009
Figure PCTCN2020097175-appb-000009
其中n、m、z、R 2、R 3、R 4、R 5、R 6和R 7如对式(I)化合物所定义， Wherein n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined for the compound of formula (I),
与式(III)化合物反应，React with the compound of formula (III),
Figure PCTCN2020097175-appb-000010
Figure PCTCN2020097175-appb-000010
其中p和R 8如对式(I)化合物所定义，并且X为卤素，例如氟、氯、溴或碘， Wherein p and R 8 are as defined for the compound of formula (I), and X is halogen, such as fluorine, chlorine, bromine or iodine,
得到式(IV)化合物，To obtain the compound of formula (IV),
Figure PCTCN2020097175-appb-000011
Figure PCTCN2020097175-appb-000011
其中n、m、z、p、R 2、R 3、R 4、R 5、R 6、R 7和R 8如对式(I)化合物所定义；以及 Wherein n, m, z, p, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are as defined for the compound of formula (I); and
(2)使式(IV)化合物与式(V)化合物反应，得到式(I)化合物，(2) reacting the compound of formula (IV) with the compound of formula (V) to obtain the compound of formula (I),
Figure PCTCN2020097175-appb-000012
Figure PCTCN2020097175-appb-000012
其中R 9如对式(I)化合物所定义，并且Y为卤素，例如氟、氯、溴或碘。 Where R 9 is as defined for the compound of formula (I), and Y is halogen, such as fluorine, chlorine, bromine or iodine.
在步骤(1)中，式(II)化合物中的端羟基与式(III)化合物中的卤素的反应属于本领域已知的反应类型，反应产生卤化氢。通常而言，该反应在碱性催化剂存在下进行。作为适合该反应的碱性催化剂，可以提及氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物。催化剂的用量也是常规的。通常而言，式(II)化合物与碱性催化剂的摩尔用量比为1:1-1:5。式(II)化合物与式(III)化合物的反应通常在溶剂中进行。作为溶剂的类型，没有特别的限制，只要能将式(II)化合物、式(III)化合物和相应碱性催化剂溶解并且不参与式(II)化合物与式(III)化合 物之间的反应即可，优选该溶剂还有有利于产物，即式(IV)化合物析出。作为该溶剂，通常使用有机溶剂，优选使用甲苯、丙酮、丁酮、甲苯、四氢呋喃、环己烷、1,4-二氧六环、二氯甲烷、乙腈或其任意混合物。溶剂的用量也是常规的，通常而言，溶剂的用量为式(II)化合物和式(III)化合物总重量的1.0-3倍。式(II)化合物和式(III)化合物的用量通常以大致等摩尔量使用。有利的是，式(II)化合物与式(III)化合物的用量摩尔比为1:1-1:1.2。为了实现上述反应，通常将式(II)化合物和碱性催化剂溶解在溶剂中，降温至冰点(约0℃)，然后加入式(III)化合物，加料完毕之后将所得反应混合物先在冰点温度(约0℃)搅拌反应0.5-3小时，优选0.5-1小时，然后升温至25-60℃，优选升温至35-60℃。升温后通常继续反应6-24小时，优选继续反应8-24小时。当然，反应有利地在搅拌下进行。反应完毕之后，通过常规后处理，即获得式(IV)化合物。该后处理通常包括萃取或洗涤(例如用水洗涤，水洗涤之后有利地采用吸水化合物比如硫酸镁或硫酸钠除水)、过滤或离心除去固体杂质，旋蒸除去溶剂，减压蒸馏进一步除去溶剂。如果要获得更高纯度的产物，还可重结晶或柱层析法分离杂质。In step (1), the reaction between the terminal hydroxyl group in the compound of formula (II) and the halogen in the compound of formula (III) belongs to a type of reaction known in the art, and the reaction produces hydrogen halide. Generally speaking, this reaction is carried out in the presence of a basic catalyst. As a basic catalyst suitable for this reaction, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof can be mentioned. The amount of catalyst is also conventional. Generally speaking, the molar ratio of the compound of formula (II) to the basic catalyst is 1:1 to 1:5. The reaction of the compound of formula (II) with the compound of formula (III) is usually carried out in a solvent. The type of solvent is not particularly limited, as long as it can dissolve the compound of formula (II), the compound of formula (III) and the corresponding basic catalyst and does not participate in the reaction between the compound of formula (II) and the compound of formula (III). Preferably, the solvent also facilitates the precipitation of the product, that is, the compound of formula (IV). As the solvent, an organic solvent is generally used, and toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile, or any mixtures thereof are preferably used. The amount of solvent is also conventional. Generally speaking, the amount of solvent is 1.0 to 3 times the total weight of the compound of formula (II) and compound of formula (III). The amount of the compound of formula (II) and the compound of formula (III) is usually used in approximately equimolar amounts. Advantageously, the molar ratio of the compound of formula (II) to the compound of formula (III) is 1:1-1:1.2. In order to achieve the above reaction, usually the compound of formula (II) and a basic catalyst are dissolved in a solvent, the temperature is lowered to the freezing point (about 0°C), and then the compound of formula (III) is added. After the addition is completed, the resulting reaction mixture is first heated to the freezing temperature ( (Approximately 0°C) the reaction is stirred for 0.5-3 hours, preferably 0.5-1 hour, and then the temperature is increased to 25-60°C, preferably to 35-60°C. After the temperature is raised, the reaction is usually continued for 6-24 hours, preferably for 8-24 hours. Of course, the reaction is advantageously carried out under stirring. After the reaction is completed, the compound of formula (IV) can be obtained through conventional post-treatment. This post-treatment usually includes extraction or washing (for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and vacuum distillation to further remove the solvent. If you want to obtain a higher purity product, you can also recrystallization or column chromatography to separate impurities.
在步骤(2)中，式(IV)化合物中的端羟基与式(V)化合物中的酰卤的反应属于本领域已知的反应类型，反应产生卤化氢。通常而言，该反应在催化剂存在下进行。作为适合该反应的催化剂，可以提及三乙胺、碳酸钾或其任意混合物。催化剂的用量也是常规的。通常而言，式(IV)化合物与催化剂的摩尔用量比为1:1-1:3。式(IV)化合物与式(V)化合物的反应通常在溶剂中进行。作为溶剂的类型，没有特别的限制，只要能将式(IV)化合物、式(V)化合物和相应催化剂溶解并且不参与式(IV)化合物与式(V)化合物之间的反应即可，优选该溶剂还有有利于产物，即式(I)化合物析出。作为该溶剂，通常使用有机溶剂，优选使用甲苯、丙酮、丁酮、甲苯、四氢呋喃、环己烷、1,4-二氧六环、二氯甲烷、乙腈或其任意混合物。溶剂的用量也是常规的，通常而言，溶剂的用量为式(IV)化合物和式(V)化合物总重量的1.0-3倍。式(IV)化合物和式(V)化合物的用量通常以大致等摩尔量使用。有利的是，式(IV)化合物与式(IV)化合物的用量摩尔比为1:1-1:1.2。为了实现上述反应，通常将式(IV)化合物和催化剂溶解在溶剂中，降温至冰点(约0℃)，然后加入式(V)化合物在溶剂中的溶液，加料完毕之后将所得反应混合物先在冰点温度(约0℃)搅拌反应0.5-3小时，优选0.5-1小时，然后升温至25-60℃，优选 升温至25-35℃，继续反应6-24小时，优选8-12小时。当然，反应有利地在搅拌下进行。反应完毕之后，通过常规后处理，即获得式(I)化合物。该后处理通常包括萃取或洗涤(例如用水洗涤，水洗涤之后有利地采用吸水化合物比如硫酸镁或硫酸钠除水)、过滤或离心除去固体杂质，旋蒸除去溶剂，减压蒸馏进一步除去溶剂。如果要获得更高纯度的产物，还可重结晶或柱层析法分离杂质。In step (2), the reaction between the terminal hydroxyl group in the compound of formula (IV) and the acid halide in the compound of formula (V) belongs to a type of reaction known in the art, and the reaction produces hydrogen halide. Generally speaking, the reaction is carried out in the presence of a catalyst. As a catalyst suitable for this reaction, triethylamine, potassium carbonate or any mixture thereof can be mentioned. The amount of catalyst is also conventional. Generally speaking, the molar ratio of the compound of formula (IV) to the catalyst is 1:1 to 1:3. The reaction of the compound of formula (IV) with the compound of formula (V) is usually carried out in a solvent. The type of solvent is not particularly limited, as long as it can dissolve the compound of formula (IV), the compound of formula (V) and the corresponding catalyst and does not participate in the reaction between the compound of formula (IV) and the compound of formula (V), preferably The solvent also facilitates the precipitation of the product, that is, the compound of formula (I). As the solvent, an organic solvent is generally used, and toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile, or any mixtures thereof are preferably used. The amount of solvent is also conventional. Generally speaking, the amount of solvent is 1.0 to 3 times the total weight of the compound of formula (IV) and compound of formula (V). The amount of the compound of formula (IV) and the compound of formula (V) is usually used in approximately equimolar amounts. Advantageously, the molar ratio of the compound of formula (IV) to the compound of formula (IV) is 1:1-1:1.2. In order to achieve the above reaction, usually the compound of formula (IV) and the catalyst are dissolved in a solvent, the temperature is lowered to the freezing point (about 0°C), and then a solution of the compound of formula (V) in the solvent is added. After the addition is complete, the resulting reaction mixture The reaction is stirred at freezing temperature (about 0°C) for 0.5-3 hours, preferably 0.5-1 hour, then the temperature is raised to 25-60°C, preferably to 25-35°C, and the reaction is continued for 6-24 hours, preferably 8-12 hours. Of course, the reaction is advantageously carried out under stirring. After the reaction is completed, the compound of formula (I) can be obtained through conventional post-treatment. This post-treatment usually includes extraction or washing (for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and vacuum distillation to further remove the solvent. If you want to obtain a higher purity product, you can also recrystallization or column chromatography to separate impurities.
在本发明的一些优选实施方案中，其中X和Y均为氯。In some preferred embodiments of the present invention, wherein X and Y are both chlorine.
本发明式(I)化合物是一种可混杂光固化的含多硅的氧杂环丁烷类单体，固化速度快，光固化后拉伸性能较好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强，耐热性好。合成方法简单易行，条件温和；原料易得，价格低廉。The compound of formula (I) of the present invention is a polysilicon-containing oxetane monomer that can be mixed with light curing. It has a fast curing speed, good tensile properties after light curing, excellent hydrophobic properties, stain resistance, and Fingerprint, chemical corrosion resistance, strong anti-aging performance, good heat resistance. The synthetic method is simple and feasible, and the conditions are mild; the raw materials are easily available and the price is low.
因此，根据本发明的第三个方面，提供了一种可光固化组合物，该组合物包含本发明的式(I)化合物作为聚合单体。该可光固化组合物除了包含本发明的式(I)化合物以外，通常还包含开环聚合的阳离子光引发剂(可引发阳离子聚合的光引发剂)和自由基光引发剂(可引发自由基聚合的光引发剂)。其中开环聚合的阳离子光引发剂在紫外光辐照下引发式(I)化合物中的氧杂环丁烷结构部分开环聚合，自由基光引发剂在紫外光辐照下引发式(I)化合物中的烯属双键的聚合。当然，该可光固化组合物还可包含其它含有乙烯基醚双键、脂环族环氧基、环氧乙烷基或者氧杂环丁烷基等可阳离子光固化基团的单体、低聚物，例如3,4-环氧环己基甲基3,4-环氧环己基甲酸酯(E4221)。Therefore, according to the third aspect of the present invention, there is provided a photocurable composition comprising the compound of formula (I) of the present invention as a polymerizable monomer. In addition to the compound of formula (I) of the present invention, the photocurable composition usually contains a cationic photoinitiator for ring-opening polymerization (a photoinitiator that can initiate cationic polymerization) and a free radical photoinitiator (which can initiate free radicals). Photoinitiator for polymerization). The cationic photoinitiator for ring-opening polymerization initiates the ring-opening polymerization of the oxetane structure in the compound of formula (I) under ultraviolet light irradiation, and the free radical photoinitiator initiates the formula (I) under ultraviolet light irradiation Polymerization of olefinic double bonds in compounds. Of course, the photocurable composition can also contain other monomers containing vinyl ether double bonds, alicyclic epoxy groups, oxiranyl groups or oxetanyl groups and other cationic photocurable groups, low Polymers, such as 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221).
本发明可光固化组合物可以为光固化涂料组合物、光固化油墨组合物、光致抗蚀组合物等。该组合物在固化后，所得固化产物拉伸性能较好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强。The photocurable composition of the present invention may be a photocurable coating composition, a photocurable ink composition, a photoresist composition, and the like. After the composition is cured, the resulting cured product has good tensile properties, excellent hydrophobic properties, anti-staining, anti-fingerprint, anti-chemical corrosion, and strong anti-aging properties.
作为开环聚合的阳离子光引发剂，常用的有碘鎓盐和硫鎓盐。有利的是，所述碘鎓盐光引发剂和硫鎓盐光引发剂分别具有如下通式(A)和(B)As cationic photoinitiators for ring-opening polymerization, iodonium salts and sulfonium salts are commonly used. Advantageously, the iodonium salt photoinitiator and the sulfonium salt photoinitiator have the following general formulas (A) and (B), respectively
Figure PCTCN2020097175-appb-000013
Figure PCTCN2020097175-appb-000013
其中among them
R a、R b、R c、R d、R e各自独立地是未取代的C 6-C 10芳基，或者被选自卤素、硝基、羰基、C 1-C 12烷基、C 1-C 12烷氧基、苯硫基、苯基和取代苯基的取代基取代的C 6-C 10芳基，优选是苯基或萘基，或者被选自卤素、硝基、C 1-C 6烷基和取代苯基的取代基取代的苯基或萘基，其中所述取代苯基包含的取代基为一个或多个选自卤素、硝基、C 1-C 6烷基和C 1-C 6烷氧基的基团；以及 R a , R b , R c , R d , R e are each independently an unsubstituted C 6 -C 10 aryl group, or are selected from halogen, nitro, carbonyl, C 1 -C 12 alkyl, C 1 C 6 -C 10 aryl substituted with substituents of -C 12 alkoxy, thiophenyl, phenyl and substituted phenyl, preferably phenyl or naphthyl, or selected from halogen, nitro, C 1- C 6 alkyl and substituted phenyl substituted phenyl or naphthyl, wherein the substituted phenyl contains one or more substituents selected from halogen, nitro, C 1 -C 6 alkyl and C 1- C 6 alkoxy group; and
Y、Z是非亲核性阴离子，例如三氟甲磺酸根、BF 4 —、ClO 4 —、PF 6 —、AsF 6 —、SbF 6 —。 Y and Z are non-nucleophilic anions, such as trifluoromethanesulfonate, BF 4 — , ClO 4 — , PF 6 — , AsF 6 — , SbF 6 — .
例如，作为光引发剂，可以使用选自下组中的一种或多种:4-(苯硫基)苯基·二苯基硫鎓六氟磷酸盐、4-(苯硫基)苯基·二苯基硫鎓六氟锑酸盐、双(4-(二苯基锍)苯基)硫醚双六氟磷酸盐、双(4-(二苯基锍)苯基)硫醚双六氟锑酸盐、10-(4-联苯基)-2-异丙基噻吨酮-10-硫鎓六氟磷酸盐、10-(4-联苯基)-2-异丙基噻吨酮-10-硫鎓六氟锑酸盐、六氟磷酸二苯基碘鎓盐(810)、4-辛氧基二苯碘鎓六氟磷酸盐、4-辛氧基二苯碘鎓六氟锑酸盐、4-异丁基苯基·4'-甲基苯基碘鎓六氟磷酸盐、4-异丁基苯基·4'-甲基苯基碘鎓六氟锑酸盐、双(4-十二烷基苯)碘鎓六氟锑酸盐、双(4-十二烷基苯)碘鎓六氟磷酸盐、双(4-叔丁基苯)碘鎓六氟磷酸盐、双(4-叔丁基苯)碘鎓六氟锑酸盐。For example, as the photoinitiator, one or more selected from the following group can be used: 4-(phenylthio)phenyl·diphenylsulfonium hexafluorophosphate, 4-(phenylthio)phenyl ·Diphenylsulfonium hexafluoroantimonate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexa Fluorantimonate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone Ketone-10-sulfonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate (810), 4-octyloxydiphenyliodonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoro Antimonate, 4-isobutylphenyl 4'-methylphenyl iodonium hexafluorophosphate, 4-isobutylphenyl 4'-methylphenyl iodonium hexafluoroantimonate, double (4-Dodecylbenzene) iodonium hexafluoroantimonate, bis(4-dodecylbenzene) iodonium hexafluorophosphate, bis(4-tert-butylbenzene) iodonium hexafluorophosphate, Bis(4-tert-butylbenzene)iodonium hexafluoroantimonate.
作为自由基光引发剂，通常有2-异丙基硫杂蒽酮(ITX)、2-羟基-2-甲基-1-苯基丙酮(1173)、1-羟基环己基苯基甲酮(184)、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮(907)、2,4,6-三甲基苯甲酰基-二苯基氧化膦(TPO)、2,4,6-三甲基苯甲酰基苯基膦酸乙酯(TPO-L)、2-二甲氨基-2-苄基-1-[4-(4-吗啉基)苯基]-1-丁酮(IHT-PI 910)、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮(659)、苯甲酰甲酸甲酯(MBF)等。As free radical photoinitiators, there are usually 2-isopropylthioxanthone (ITX), 2-hydroxy-2-methyl-1-phenylacetone (1173), 1-hydroxycyclohexylphenyl ketone ( 184), 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone (907), 2,4,6-trimethylbenzyl Acyl-diphenylphosphine oxide (TPO), 2,4,6-trimethylbenzoylphenyl phosphonate (TPO-L), 2-dimethylamino-2-benzyl-1-[4 -(4-morpholinyl)phenyl]-1-butanone (IHT-PI 910), 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1 -Acetone (659), methyl benzoylformate (MBF), etc.
对本发明而言，光引发剂的用量是常规的。基于本发明可光固化组合物，开环聚合的阳离子光引发剂的含量通常为0.5-5％，优选为1-3％。基于本发明可光固化组合物，自由基光引发剂的含量通常为0.5-3％，优选为1-2％。For the present invention, the amount of photoinitiator is conventional. Based on the photocurable composition of the present invention, the content of the cationic photoinitiator for ring-opening polymerization is usually 0.5-5%, preferably 1-3%. Based on the photocurable composition of the present invention, the content of the free radical photoinitiator is usually 0.5-3%, preferably 1-2%.
根据本发明的最后一个方面，提供了一种光固化材料，该材料通过将本发明的可光固化组合物光固化而获得。该光固化材料由于包含本发明式(I)化合物作为可光固化单体的缘故，固化速度快、性能易于调节，而且固化后具有拉伸 性能较好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强，耐热性好。According to the last aspect of the present invention, a photocurable material is provided, which is obtained by photocuring the photocurable composition of the present invention. Because the photocurable material contains the compound of formula (I) of the present invention as a photocurable monomer, the curing speed is fast, the performance is easy to adjust, and after curing, it has good tensile properties, excellent hydrophobic properties, stain resistance, and fingerprint resistance. , Anti-chemical corrosion, strong anti-aging performance, good heat resistance.
实施例Example
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。The experimental methods used in the following examples are conventional methods unless otherwise specified.
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。The materials and reagents used in the following examples can be obtained from commercial sources unless otherwise specified.
实施例1Example 1
在装有滴液漏斗、温度探头和回流冷凝管的三口烧瓶中，加入18.60g(20mmol)双羟基硅油(对应于式(II)化合物，其中n＝8，m＝2，z＝1，以及R 2、R 3、R 4、R 5、R 6和R 7全为甲基)和30mL甲苯，冰水浴下搅拌，转速设定300r/min，加入1.67g(60mmol)氢氧化钾，之后缓慢滴加2.83g(22mmol)3-乙基-3-氯甲基氧杂环丁烷，滴加完毕后，保持冰水浴反应30min后撤去冰水浴，50℃油浴再反应24小时，结束反应。反应物用蒸馏水反复洗涤，取上层清液，离心除去固体杂质。用旋转蒸发仪旋蒸(温度45℃，压力0.1MPa)除去大部分溶剂，再将溶液减压蒸馏(温度40-50℃，压力200-300pa)，得到产物。经核磁氢谱表征，确定为如下化合物1a。 In a three-necked flask equipped with a dropping funnel, a temperature probe and a reflux condenser, 18.60g (20mmol) of bishydroxysilicone oil (corresponding to the compound of formula (II), where n=8, m=2, z=1, and R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are all methyl) and 30 mL of toluene. Stir under an ice water bath at a rotation speed of 300 r/min. Add 1.67 g (60 mmol) of potassium hydroxide, then slowly 2.83g (22mmol) of 3-ethyl-3-chloromethyloxetane was added dropwise, and after the addition was completed, the ice-water bath was kept for 30 minutes, and then the ice-water bath was removed, and the reaction was continued in an oil bath at 50°C for 24 hours to complete the reaction. The reactant was washed repeatedly with distilled water, and the supernatant was taken and centrifuged to remove solid impurities. Use a rotary evaporator (temperature 45°C, pressure 0.1MPa) to remove most of the solvent, and then distill the solution under reduced pressure (temperature 40-50°C, pressure 200-300pa) to obtain the product. Characterized by hydrogen NMR spectroscopy, it was identified as the following compound 1a.
Figure PCTCN2020097175-appb-000014
Figure PCTCN2020097175-appb-000014
1H NMR(400MHz,CDCl3)δ: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). 1 H NMR (400MHz, CDCl3) δ: 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).
在装有滴液漏斗、温度探头和回流冷凝管的三口烧瓶中，加入19.72g(20mmol)化合物1a、30mL甲苯和3.03g三乙胺(30mmol)，冰水浴下搅拌，转速设定300r/min，缓慢滴加1.99g(22mmol)丙烯酰氯，然后保持冰水浴反应60min，撤去冰水浴，45℃油浴再反应12小时，结束反应。反应物用蒸馏水反复洗涤，取上层清液，离心除去固体杂质。用旋转蒸发仪旋蒸(温度45℃，压力 0.1MPa)除去大部分溶剂，再将溶液减压蒸馏(温度40-50℃，压力200-300Pa)，得到产物。经核磁氢谱与硅谱表征，确定为化合物1，下文有时称作BODSi-1。In a three-necked flask equipped with a dropping funnel, a temperature probe and a reflux condenser, add 19.72g (20mmol) of compound 1a, 30mL of toluene and 3.03g of triethylamine (30mmol), stir in an ice-water bath, and set the speed to 300r/min , Slowly add 1.99g (22mmol) of acryloyl chloride dropwise, then keep the ice-water bath to react for 60 minutes, remove the ice-water bath, and react for another 12 hours in an oil bath at 45°C to complete the reaction. The reactant was washed repeatedly with distilled water, and the supernatant was taken and centrifuged to remove solid impurities. Use a rotary evaporator (temperature 45°C, pressure 0.1MPa) to remove most of the solvent, and then distill the solution under reduced pressure (temperature 40-50°C, pressure 200-300Pa) to obtain the product. Characterized by hydrogen NMR spectrum and silicon spectrum, it is determined to be compound 1, sometimes referred to as BODSi-1 hereinafter.
Figure PCTCN2020097175-appb-000015
Figure PCTCN2020097175-appb-000015
1H NMR(400MHz,CDCl3)δ: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(t,J＝7.5Hz，4H)3.52(s,4H),3.63(m,2H),3.79(s,2H),4.39-4.14(m,6H),5.83(m,1H),.6.41-6.12(m,2H). 1 H NMR(400MHz,CDCl3)δ: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(t,J=7.5Hz,4H)3.52(s,4H),3.63(m,2H),3.79(s,2H),4.39-4.14(m, 6H), 5.83 (m, 1H), .6.41-6.12 (m, 2H).
实施例2Example 2
重复实施例1，但是将22mmol丙烯酰氯替换为22mmol甲基丙烯酰氯。所得终产物经核磁氢谱与硅谱表征，确定为化合物2，下文有时称作BODSi-2。Example 1 was repeated, but 22 mmol of acryloyl chloride was replaced by 22 mmol of methacryloyl chloride. The resulting final product was characterized by hydrogen nuclear magnetic spectroscopy and silicon spectroscopy and identified as compound 2, sometimes referred to as BODSi-2 hereinafter.
Figure PCTCN2020097175-appb-000016
Figure PCTCN2020097175-appb-000016
1H NMR(400MHz,CDCl3)δ: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),2.01(m,3H)3.35(t,J＝7.5Hz，4H)3.52(s,4H),3.63(m,2H),3.79(s,2H),4.39-4.14(m,6H),6.48-6.40(m,2H). 1 H NMR(400MHz,CDCl3)δ: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),2.01(m,3H)3.35(t,J=7.5Hz,4H)3.52(s,4H),3.63(m,2H),3.79(s,2H), 4.39-4.14 (m, 6H), 6.48-6.40 (m, 2H).
实施例3Example 3
重复实施例1，但是将20mmol双羟基硅油替换为这样的20mmol双羟基硅油，该双羟基硅油对应于式(II)化合物，其中n＝5，m为2，z为1，以及R 2、R 3、R 4、R 5、R 6和R 7全为甲基。所得终产物经核磁氢谱与硅谱表征，确定为化合物3，下文有时称作BODSi-3。 Repeat Example 1, but replace 20 mmol of dihydroxy silicone oil with 20 mmol of dihydroxy silicone oil, which corresponds to the compound of formula (II), where n=5, m is 2, z is 1, and R 2 , R 3. R 4 , R 5 , R 6 and R 7 are all methyl groups. The resulting final product was characterized by hydrogen nuclear magnetic spectroscopy and silicon spectroscopy and identified as compound 3, sometimes referred to as BODSi-3 hereinafter.
Figure PCTCN2020097175-appb-000017
Figure PCTCN2020097175-appb-000017
1H NMR(400MHz,CDCl3)δ:0.07-0.17(m,42H),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(t,J＝7.5Hz，4H)3.52(s,4H),3.63(m,2H),3.79(s,2H),4.39-4.14(m,6H),5.83(m,1H),.6.41-6.12(m,2H). 1 H NMR(400MHz,CDCl3)δ:0.07-0.17(m,42H),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(t,J=7.5Hz,4H)3.52(s,4H),3.63(m,2H),3.79(s,2H),4.39-4.14(m, 6H), 5.83 (m, 1H), .6.41-6.12 (m, 2H).
实施例4Example 4
重复实施例1，但是将20mmol双羟基硅油替换为这样的20mmol双羟基硅油，该双羟基硅油对应于式(II)化合物，其中n＝11，m为2，z为1，以及R 2、R 3、R 4、R 5、R 6和R 7全为甲基。所得终产物经核磁氢谱表征，确定为化合物4，下文有时称作BODSi-4。 Repeat Example 1, but replace 20 mmol of dihydroxy silicone oil with 20 mmol of dihydroxy silicone oil, which corresponds to the compound of formula (II), where n = 11, m is 2, z is 1, and R 2 , R 3. R 4 , R 5 , R 6 and R 7 are all methyl groups. The resulting final product was characterized by hydrogen NMR spectroscopy and identified as compound 4, sometimes referred to as BODSi-4 hereinafter.
Figure PCTCN2020097175-appb-000018
Figure PCTCN2020097175-appb-000018
1H NMR(400MHz,CDCl3)δ:0.07-0.17(m,78H),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(t,J＝7.5Hz，4H)3.52(s,4H),3.63(m,2H),3.79(s,2H),4.39-4.14(m,6H),5.83(m,1H),.6.41-6.12(m,2H). 1 H NMR(400MHz,CDCl3)δ:0.07-0.17(m,78H),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(t,J=7.5Hz,4H)3.52(s,4H),3.63(m,2H),3.79(s,2H),4.39-4.14(m, 6H), 5.83 (m, 1H), .6.41-6.12 (m, 2H).
实施例5Example 5
重复实施例1，但是将20mmol双羟基硅油替换为这样的20mmol双羟基硅油，该双羟基硅油对应于式(II)化合物，其中n＝1，m为2，z为1，以及R 2、R 3、R 4、R 5、R 6和R 7全为甲基。所得终产物经核磁氢谱与硅谱表征，确定为化合物5。 Repeat Example 1, but replace 20 mmol of dihydroxy silicone oil with 20 mmol of dihydroxy silicone oil, which corresponds to the compound of formula (II), where n=1, m is 2, z is 1, and R 2 , R 3. R 4 , R 5 , R 6 and R 7 are all methyl groups. The final product obtained was characterized by hydrogen nuclear magnetic spectroscopy and silicon spectroscopy, and it was determined to be compound 5.
Figure PCTCN2020097175-appb-000019
Figure PCTCN2020097175-appb-000019
1H NMR(400MHz,CDCl3)δ:0.07-0.17(m,16H),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(t,J＝7.5Hz，4H)3.52(s,4H),3.63(m,2H),3.79(s,2H),4.39-4.14(m,6H),5.83(m,1H),.6.41-6.12(m,2H). 1 H NMR(400MHz,CDCl3)δ:0.07-0.17(m,16H),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(t,J=7.5Hz,4H)3.52(s,4H),3.63(m,2H),3.79(s,2H),4.39-4.14(m, 6H), 5.83 (m, 1H), .6.41-6.12 (m, 2H).
实施例6Example 6
重复实施例1，但是将20mmol双羟基硅油替换为这样的20mmol双羟基硅油，该双羟基硅油对应于式(II)化合物，其中n＝1，m为2，z为1，以及R 2、R 3、R 4、R 5、R 6和R 7全为甲基，并且将22mmol 3-乙基-3-氯甲基氧杂环丁烷替换为20mmol 3-羟甲基氧杂环丁烷。所得终产物经核磁氢谱与硅谱表征，确定为化合物6。 Repeat Example 1, but replace 20 mmol of dihydroxy silicone oil with 20 mmol of dihydroxy silicone oil, which corresponds to the compound of formula (II), where n=1, m is 2, z is 1, and R 2 , R 3. R 4 , R 5 , R 6 and R 7 are all methyl groups, and 22 mmol of 3-ethyl-3-chloromethyloxetane is replaced with 20 mmol of 3-hydroxymethyloxetane. The final product obtained was characterized by hydrogen nuclear magnetic spectrum and silicon spectrum, and it was determined to be compound 6.
Figure PCTCN2020097175-appb-000020
Figure PCTCN2020097175-appb-000020
1H NMR(400MHz,CDCl3)δ:0.07-0.17(m,06H),0.61(t,J＝7.0Hz，4H),1.42(m,4H),2.92(s,1H),3.35(m,，6H)3.52(s,4H),3.63(m,2H),4.27(m,2H),4.79-4.54(m,4H),5.83(m,1H),.6.41-6.12(m,2H). 1 H NMR (400MHz, CDCl3) δ: 0.07-0.17 (m, 06H), 0.61 (t, J = 7.0Hz, 4H), 1.42 (m, 4H), 2.92 (s, 1H), 3.35 (m,, 6H) 3.52 (s, 4H), 3.63 (m, 2H), 4.27 (m, 2H), 4.79-4.54 (m, 4H), 5.83 (m, 1H), .6.41-6.12 (m, 2H).
实施例7Example 7
本实施例的目的在于说明本发明化合物的光聚合性能。The purpose of this example is to illustrate the photopolymerization properties of the compounds of the present invention.
以光引发剂六氟磷酸二苯基碘鎓盐(810)与2-异丙基硫杂蒽酮(ITX)以2:1质量比组成的混合物作为光引发体系，采用实时红外(RT-IR)的方法测试了化合物1-6在不同引发剂浓度下的光聚合性能。氧杂环丁烷基的C-O-C键不对称变形振动吸收峰位于980cm -1，C＝C双键上氢的面外弯曲振动吸收峰位于830cm - 1，随着固化反应的进行，C-O-C键会开环断裂，碳碳双键会成为碳碳单键，对应位置吸收峰面积也随之减小。通过RT-IR监测红外吸收峰的面积大小变化， 可以计算出四元氧杂环、碳碳双键的转化率。光源为高压汞灯，发射波长主要为365nm，光强为60mW/cm 2。化合物1的结果如图1和2所示。图1是双键转化率随辐照时间的变化曲线图，图2是氧杂环丁烷环转化率随辐照时间的变化曲线图。结果显示，化合物1具有良好的光聚合性能。另外，化合物2-6中的每一种在0.75％810+0.38％ITX、1.50％810+0.75％ITX、3.00％810+1.50％ITX、4.50％810+2.25％ITX这四个浓度的引发体系下在高压汞灯辐照600秒以后，其单体的四元氧杂环转化率会随引发剂浓度的提高而增大，其四元氧杂环最大转化率都达到了至少60％，碳碳双键最大转化率都达到了至少75％。其中810和ITX各自的浓度均基于化合物1-6各自的重量。因此本发明化合物具有良好的光聚合性能。 A mixture of photoinitiator diphenyliodonium hexafluorophosphate (810) and 2-isopropylthioxanthone (ITX) in a mass ratio of 2:1 was used as the photoinitiator system, and real-time infrared (RT-IR) The method of) tested the photopolymerization performance of compound 1-6 under different initiator concentration. The asymmetric deformation vibration absorption peak of the COC bond of the oxetanyl group is located at 980 cm -1 , and the out-of-plane bending vibration absorption peak of the hydrogen on the C=C double bond is located at 830 cm - 1 . As the curing reaction proceeds, the COC bond will open When the ring is broken, the carbon-carbon double bond will become a carbon-carbon single bond, and the absorption peak area at the corresponding position will decrease accordingly. By monitoring the changes in the area of the infrared absorption peak by RT-IR, the conversion rate of the four-membered oxygen heterocycle and carbon-carbon double bond can be calculated. The light source is a high-pressure mercury lamp, the emission wavelength is mainly 365nm, and the light intensity is 60mW/cm 2 . The results of compound 1 are shown in Figures 1 and 2. Fig. 1 is a graph showing the change of double bond conversion rate with irradiation time, and Fig. 2 is a graph showing the change of oxetane ring conversion rate with irradiation time. The results show that compound 1 has good photopolymerization properties. In addition, each of the compounds 2-6 has an initiation system with four concentrations of 0.75% 810+0.38% ITX, 1.50% 810+0.75% ITX, 3.00% 810+1.50% ITX, and 4.50% 810+2.25% ITX. After being irradiated by a high-pressure mercury lamp for 600 seconds, the conversion rate of the quaternary oxygen heterocyclic ring of the monomer will increase with the increase of the initiator concentration, and the maximum conversion rate of the quaternary oxygen heterocyclic ring of the monomer has reached at least 60%. The maximum conversion rate of carbon double bonds reached at least 75%. The respective concentrations of 810 and ITX are based on the respective weight of compound 1-6. Therefore, the compound of the present invention has good photopolymerization performance.
实施例8Example 8
本实施例的目的在于说明本发明化合物能够改善光固化膜的表面疏水性。The purpose of this example is to show that the compound of the present invention can improve the surface hydrophobicity of the photocurable film.
将化合物1-6各自与3,4-环氧环己基甲基3,4-环氧环己基甲酸酯(E4221)环氧单体以15:85的质量比混合，以基于E4221与化合物1-6各自的总重量分别为3.0wt％810和1.5wt％ITX作引发剂，混合均匀，得到感光液。将所得感光液均匀铺展在70mm×8mm×6mm的硅胶模具中，在60mW/cm 2的高压汞灯下曝光900s，得到固化完全的膜。然后采用OCA20型水接触角测定仪(OCA20型，德国dataphysics公司)对各固化膜的表面疏水性进行测试，测试温度为25℃。同时，利用同样方法制备空白E4221固化膜作为参比。 Compounds 1-6 were each mixed with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221) epoxy monomer in a mass ratio of 15:85, based on E4221 and compound 1 The total weight of each of -6 is 3.0wt% 810 and 1.5wt% ITX as initiators, and they are mixed uniformly to obtain a photosensitive liquid. Spread the obtained photosensitive liquid uniformly in a 70mm×8mm×6mm silicone mold, and expose it to a 60mW/cm 2 high-pressure mercury lamp for 900s to obtain a fully cured film. Then, an OCA20 water contact angle tester (OCA20, German dataphysics company) was used to test the surface hydrophobicity of each cured film, and the test temperature was 25°C. At the same time, use the same method to prepare a blank E4221 cured film as a reference.
结果显示，当E4221聚合体系不添加化合物1时，固化膜的水接触角为62.5°，而额外加入15％化合物1后，固化膜的水接触角明显提高至88.2°。另外，额外加入化合物2-6中之一获得的固化膜的接触角均超过86°。因此，本发明化合物可以显著地提高固化膜的表面疏水性，因而抗沾污，抗指纹。The results showed that when compound 1 was not added to the E4221 polymerization system, the water contact angle of the cured film was 62.5°, and after 15% of compound 1 was added, the water contact angle of the cured film was significantly increased to 88.2°. In addition, the contact angles of the cured films obtained by additionally adding one of the compounds 2-6 all exceeded 86°. Therefore, the compound of the present invention can significantly improve the surface hydrophobicity of the cured film, and thus resist stains and fingerprints.
实施例9Example 9
本实施例的目的在于说明本发明化合物能够改善光固化膜的拉伸性能。The purpose of this example is to show that the compound of the present invention can improve the tensile properties of the photocurable film.
按照实施例8中所述完全相同的方法制得化合物1-6的固化膜。然后采用Instron-1211型电子拉力机(Instron-1211型，美国Instron公司)进行光固化膜的拉 伸性能测试，测试温度为25℃，测试速度为50mm/min。同时，利用同样方法制备空白E4221固化膜作为参比。The cured film of compound 1-6 was prepared in exactly the same way as described in Example 8. Then, an Instron-1211 electronic tensile machine (Instron-1211, Instron, USA) was used to test the tensile properties of the light-cured film at a test temperature of 25°C and a test speed of 50 mm/min. At the same time, use the same method to prepare a blank E4221 cured film as a reference.
结果显示，纯E4221光固化膜的拉伸强度为7.02MPa，断裂伸长率为7.5％；而额外加入15％化合物1后，E4221固化膜的拉伸强度达到11.9MPa和断裂伸长率为15.7％。另外，额外加入化合物2-6中之一获得的固化膜的拉伸强度均超过11.0MPa，断裂伸长率均超过15.2％。因此，本发明化合物可以显著地提高改善固化膜的拉伸性能。The results show that the tensile strength of the pure E4221 light-cured film is 7.02MPa, and the elongation at break is 7.5%; and after adding 15% of compound 1, the tensile strength of the cured film of E4221 reaches 11.9MPa and the elongation at break is 15.7. %. In addition, the tensile strength of the cured film obtained by additionally adding one of the compounds 2-6 all exceeded 11.0 MPa, and the elongation at break all exceeded 15.2%. Therefore, the compound of the present invention can significantly improve the tensile properties of the cured film.

Claims (10)

  1. 下式(I)化合物：Compound of the following formula (I):
    Figure PCTCN2020097175-appb-100001
    Figure PCTCN2020097175-appb-100001
    其中among them
    n为1-50的整数；n is an integer from 1-50;
    m为1-10的整数；m is an integer of 1-10;
    z为0-10的整数；z is an integer of 0-10;
    p为1-6的整数；p is an integer of 1-6;
    R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 6-C 10芳基、C 1-C 12烷基、C 1-C 12烷氧基或者两个碳原子之间插有一个或多个独立地选自N、O、S的杂原子的C 1-C 12烷基； R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy or A C 1 -C 12 alkyl group with one or more heteroatoms independently selected from N, O and S inserted between two carbon atoms;
    R 8为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基；以及 R 8 is H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy; as well as
    R 9为H或C 1-C 12烷基。 R 9 is H or C 1 -C 12 alkyl.
  2. 根据权利要求1的化合物，其中The compound according to claim 1, wherein
    n为1-15的整数，优选为1-12的整数；和/或n is an integer of 1-15, preferably an integer of 1-12; and/or
    m为1-6的整数，优选为2-4的整数；和/或m is an integer of 1-6, preferably an integer of 2-4; and/or
    z为1-6的整数，优选为0-3的整数；和/或z is an integer of 1-6, preferably an integer of 0-3; and/or
    p为1-4的整数，优选为1-3的整数；和/或p is an integer of 1-4, preferably an integer of 1-3; and/or
    R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 6-C 10芳基、C 1-C 6烷基、C 1-C 6烷氧基或者两个碳原子之间插有一个或多个选自NR b、O、S的杂原子的C 1-C 6烷基，其中R b为H或C 1-C 4烷基，优选R 2、R 3、R 4、R 5、R 6、R 7相同或不同并独立地为苯基、C 1-C 4烷基、C 1-C 4烷氧基或者两个碳原子之间插有一个或多个独立地选自NR b、O、S的杂原子的C 1-C 4烷基，其中R b为H或C 1-C 4烷基；和/或 R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or A C 1 -C 6 alkyl group with one or more heteroatoms selected from NR b , O, and S inserted between two carbon atoms, wherein R b is H or C 1 -C 4 alkyl, preferably R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are the same or different and are independently a phenyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or one interposed between two carbon atoms Or more C 1 -C 4 alkyl groups independently selected from heteroatoms of NR b , O, and S, wherein R b is H or C 1 -C 4 alkyl; and/or
    R 8为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基，优选为H或C 1-C 4烷基；和/或 R 8 is H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy, Preferably H or C 1 -C 4 alkyl; and/or
    R 9为H或C 1-C 6烷基，优选为H或C 1-C 4烷基。 R 9 is H or C 1 -C 6 alkyl, preferably H or C 1 -C 4 alkyl.
  3. 根据权利要求1的化合物，其中The compound according to claim 1, wherein
    n为1-12的整数；和/或n is an integer from 1-12; and/or
    m为2、3或4；和/或m is 2, 3 or 4; and/or
    z为0、1、2或3；和/或z is 0, 1, 2 or 3; and/or
    p为1、2或3；和/或p is 1, 2 or 3; and/or
    R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 1-C 4烷基；和/或 R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 1 -C 4 alkyl groups; and/or
    R 8为H或C 1-C 4烷基；和/或 R 8 is H or C 1 -C 4 alkyl; and/or
    R 9为H或C 1-C 4烷基，尤其是H或甲基。 R 9 is H or C 1 -C 4 alkyl, especially H or methyl.
  4. 根据权利要求1的化合物，其为一种或多种选自下组的化合物：The compound according to claim 1, which is one or more compounds selected from the group consisting of:
    Figure PCTCN2020097175-appb-100002
    Figure PCTCN2020097175-appb-100002
    Figure PCTCN2020097175-appb-100003
    Figure PCTCN2020097175-appb-100003
  5. 一种制备根据权利要求1-4中任一项的式(I)化合物的方法，包括：A method for preparing a compound of formula (I) according to any one of claims 1 to 4, comprising:
    (1)使式(II)化合物(1) Make the compound of formula (II)
    Figure PCTCN2020097175-appb-100004
    Figure PCTCN2020097175-appb-100004
    其中n、m、z、R 2、R 3、R 4、R 5、R 6和R 7如权利要求1-4中任一项所定义，与式(III)化合物反应， Wherein n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined in any one of claims 1 to 4 and react with the compound of formula (III),
    Figure PCTCN2020097175-appb-100005
    Figure PCTCN2020097175-appb-100005
    其中p和R 8如权利要求1-4中任一项所定义，并且X为卤素，例如氟、氯、溴或碘， Wherein p and R 8 are as defined in any one of claims 1-4, and X is halogen, such as fluorine, chlorine, bromine or iodine,
    得到式(IV)化合物，To obtain the compound of formula (IV),
    Figure PCTCN2020097175-appb-100006
    Figure PCTCN2020097175-appb-100006
    其中n、m、z、p、R 2、R 3、R 4、R 5、R 6、R 7和R 8权利要求1-4中任一项所定义； Wherein n, m, z, p, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are defined in any one of claims 1-4;
    以及as well as
    (2)使式(IV)化合物与式(V)化合物反应，得到式(I)化合物，(2) reacting the compound of formula (IV) with the compound of formula (V) to obtain the compound of formula (I),
    Figure PCTCN2020097175-appb-100007
    Figure PCTCN2020097175-appb-100007
    其中R 9如权利要求1-4中任一项所定义，并且Y为卤素，例如氟、氯、溴或碘。 Wherein R 9 is as defined in any one of claims 1-4, and Y is halogen, such as fluorine, chlorine, bromine or iodine.
  6. 根据权利要求5的方法，其中在步骤(1)中，The method according to claim 5, wherein in step (1),
    式(II)化合物与式(III)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选是氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物，更优选的是，式(II)化合物与碱性催化剂的摩尔比为1:1-1:5；和/或The reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a basic catalyst. The basic catalyst is preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably , The molar ratio of the compound of formula (II) to the basic catalyst is 1:1-1:5; and/or
    式(II)化合物与式(III)化合物的摩尔比为1:1-1:1.5；和/或The molar ratio of the compound of formula (II) to the compound of formula (III) is 1:1-1:1.5; and/or
    式(II)化合物与式(III)化合物之间的反应先在冰点温度下进行，然后升温至25-60℃，优选升温至35-60℃反应；优选的是，冰点温度下的反应进行0.5-3小时，优选0.5-1小时；和/或，升温后继续反应6-24小时，优选8-24小时。The reaction between the compound of formula (II) and the compound of formula (III) is first carried out at the freezing temperature, and then the temperature is increased to 25-60°C, preferably to 35-60°C; preferably, the reaction at the freezing temperature proceeds to 0.5 -3 hours, preferably 0.5-1 hour; and/or, continue the reaction for 6-24 hours after raising the temperature, preferably 8-24 hours.
  7. 根据权利要求5或6的方法，其中在步骤(2)中，The method according to claim 5 or 6, wherein in step (2),
    式(IV)化合物与式(V)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选为三乙胺、碳酸钾或其任意混合物，更优选的是，式(IV)化合物与催化剂的摩尔比为1:1-1:3(实施例没有使用碱性催化剂)；和/或The reaction between the compound of formula (IV) and the compound of formula (V) is carried out in the presence of a basic catalyst. The basic catalyst is preferably triethylamine, potassium carbonate or any mixture thereof, and more preferably, the compound of formula (IV) and the catalyst The molar ratio of is 1:1-1:3 (the example does not use a basic catalyst); and/or
    式(IV)化合物与式(IV)化合物的摩尔比为1:1-1:1.2；和/或The molar ratio of the compound of formula (IV) to the compound of formula (IV) is 1:1-1:1.2; and/or
    式(IV)化合物与式(IV)化合物的反应先在冰点温度下进行，然后升温至25-60℃，优选升温至25-35℃反应；优选的是，所述冰点温度下的反应进行0.5-3小时，优选0.5-1小时；和/或升温后继续反应6-24小时，优选8-12小时。The reaction between the compound of formula (IV) and the compound of formula (IV) is first carried out at freezing temperature, and then the temperature is raised to 25-60°C, preferably to 25-35°C; preferably, the reaction at the freezing point temperature is carried out 0.5 -3 hours, preferably 0.5-1 hour; and/or continue the reaction for 6-24 hours, preferably 8-12 hours after raising the temperature.
  8. 根据权利要求5-7中任一项，其中X和Y均为氯。According to any one of claims 5-7, wherein X and Y are both chlorine.
  9. 一种可光固化组合物，包含根据权利要求1-4中任一项的式(I)化合物作为聚合单体。A photocurable composition comprising the compound of formula (I) according to any one of claims 1 to 4 as a polymerized monomer.
  10. 一种光固化材料，该材料通过将根据权利要求9的可光固化组合物光固化而获得。A photocurable material obtained by photocuring the photocurable composition according to claim 9.
PCT/CN2020/097175 2019-06-21 2020-06-19 Mixable photocurable polysilicon-containing oxetane monomer and preparation and application thereof WO2020253839A1 (en)

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