WO2024067720A1 - 三氟甲基有机硅脂环族环氧单体及其制备和应用 - Google Patents

三氟甲基有机硅脂环族环氧单体及其制备和应用 Download PDF

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WO2024067720A1
WO2024067720A1 PCT/CN2023/122140 CN2023122140W WO2024067720A1 WO 2024067720 A1 WO2024067720 A1 WO 2024067720A1 CN 2023122140 W CN2023122140 W CN 2023122140W WO 2024067720 A1 WO2024067720 A1 WO 2024067720A1
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alkyl
compound
formula
alkoxy
integer
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French (fr)
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孙芳
胡韵朗
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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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
    • 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
    • C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
    • C07F7/0878—Si-C bond
    • C07F7/0879—Hydrosilylation reactions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups

Definitions

  • the technical field to which the present invention belongs is the field of photocurable materials, and specifically relates to a trifluoromethyl organosilicone alicyclic epoxy monomer.
  • the present 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.
  • Silicone and fluorocarbon materials have always been regarded as ideal research directions for low surface energy coating materials, but fluorocarbon materials have the disadvantages of poor mechanical properties and high production costs; pure silicon system materials are easily limited in practical applications due to their high flexibility. As people's demand for comprehensive material performance increases, single silicone or organic fluorine materials are difficult to meet production needs. Fluorosilicone polymers combine the advantages of both and have gradually attracted widespread attention in various fields.
  • fluorosilicone polymers Compared with traditional thermal polymerization technology, the method of preparing fluorosilicone polymers by photopolymerizable fluorosilicone monomers or oligomers using green photopolymerization technology has unique advantages such as solvent-free, high efficiency, high energy utilization, room temperature curing, and spatial and temporal control.
  • fluorosilicone polymers have the advantages of both silicone and organic fluorine, and have outstanding thermal stability, corrosion resistance, and hydrophobicity and oleophobicity.
  • most of the current research on photocurable fluorosilicone monomers is focused on the development of fluorosilicone-modified acrylate monomers for free radical photopolymerization, and there are few reports on cationic fluorosilicone monomers.
  • Free radical photopolymerization has the disadvantages of oxygen inhibition and large volume shrinkage, while cationic photopolymerization has the advantages of anti-oxygen inhibition and small volume shrinkage. Therefore, it is urgent to develop new cationic fluorosilicone monomers.
  • alicyclic epoxy monomers not only have the advantages of no oxygen inhibition and low curing shrinkage of traditional epoxy monomers, but also have the characteristics of no obvious induction period, fast polymerization rate, low viscosity, and good weather resistance. They occupy an important position in cationic photocuring systems. Therefore, in some fields that require rapid response, such as power insulation materials, adhesives, electronic packaging, etc., alicyclic epoxy monomers have unique advantages, and their demand is increasing year by year. Based on this, the development of a series of relatively low-cost, hydrophobic trifluoromethyl silicone alicyclic epoxy monomers has important theoretical significance and practical value for promoting the development of cationic photopolymerization technology and fluorosilicone materials.
  • the inventors of the present invention have conducted extensive and in-depth research on cationic photopolymerizable fluorosilicone monomers in order to discover a new type of trifluoromethyl organosilicone alicyclic ring
  • the inventors have found that the trifluoromethyl silicone alicyclic epoxy monomer obtained by introducing polysiloxane chains and trifluoromethyl groups into epoxy monomers has the advantages of good tensile properties, excellent hydrophobic properties, anti-fouling, anti-fingerprint, etc. after photocuring.
  • an object of the present invention is to provide a trifluoromethyl organosilicone alicyclic epoxy monomer, which not only contains a cationic photocurable group, but also contains a polysiloxane chain and a trifluoromethyl group.
  • the fluorosilicone monomer with such a structure has good tensile properties after photocuring, excellent hydrophobicity, anti-fouling, anti-fingerprint, anti-chemical corrosion, and good heat resistance.
  • Another object of the present invention is to provide a method for preparing the trifluoromethyl organosilicone alicyclic epoxy monomer of the present invention.
  • the preparation process is simple and easy, the conditions are mild, and the cost is relatively low.
  • Another object of the present invention is to provide a photocurable composition comprising the trifluoromethyl silicone alicyclic epoxy monomer according to the present invention.
  • Still another object of the present invention is to provide a photocurable material obtained by photocuring the photocurable composition of the present invention.
  • n is an integer from 1 to 50;
  • n is an integer from 0 to 20;
  • R 1 is C 1 -C 12 alkyl or C 1 -C 12 alkoxy
  • R2 , R3 and R4 are the same or different and are independently C6 - C10 aryl, C1 - C12 alkyl, C1 - C12 alkoxy, or C2 - C12 alkyl with one or more heteroatoms independently selected from NRa , O or S inserted between two carbon atoms, wherein Ra is H or C1 - C4 alkyl, for example C1 - C6 alkoxy- C1 - C6 alkyl, C1-C6 alkylamino- C1 - C6 alkyl or C1 - C6 alkylthio -C1 - C6 alkyl.
  • n is an integer of 1-20, preferably 2-18;
  • n is an integer of 0-8, preferably 0-5, more preferably 0-3;
  • R 1 is C 1 -C 6 alkyl or C 1 -C 6 alkoxy; R 1 is preferably C 1 -C 4 alkyl or C 1 -C 4 alkoxy; and/or
  • R2 , R3 and R4 are the same or different and are independently C6 - C10 aryl, C1 - C6 alkyl, C1 -C6 alkoxy or C2- C6 alkyl with one or more heteroatoms selected from NRa , O or S inserted between two carbon atoms, wherein Ra is H or C1 - C4 alkyl, such as C1- C3 alkoxy-C1-C3 alkyl, C1- C3 alkylamino - C1 - C3 alkyl or C1 -C3 alkylthio- C1 - C3 alkyl; preferably, R2 , R3 and R4 are the same or different and are independently phenyl, C1 - C4 alkyl, C1 -C4 alkoxy or C2 - C4 alkyl with one or more heteroatoms selected from NRa , O or S inserted between two carbon atoms, wherein Ra is H or C1- C4 alkyl
  • n is an integer from 3 to 15;
  • n is an integer from 0 to 5;
  • R 1 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy
  • R 2 , R 3 and R 4 are the same or different and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or C 2 -C 4 alkyl with one or more heteroatoms selected from NR a , O or S inserted between two carbon atoms, wherein Ra is H or C 1 -C 4 alkyl, for example C 1 -C 2 alkoxy-C 1 -C 2 alkyl, C 1 -C 2 alkylamino-C 1 -C 2 alkyl or C 1 -C 2 alkylthio-C 1 -C 2 alkyl;
  • n is an integer from 3 to 15;
  • n is an integer from 0 to 5;
  • R1 is C1 - C4 alkyl
  • R 2 , R 3 and R 4 are the same or different and are independently C 1 -C 4 alkyl.
  • n, R 1 , R 2 , R 3 and R 4 are as defined in any one of items 1 to 4,
  • reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a Karstedt catalyst or a Speier catalyst, preferably, the amount of the catalyst is 2-100 ppm based on the weight of the compound of formula (II); 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
  • reaction between the compound of formula (II) and the compound of formula (III) is carried out at 80-110°C, preferably 85-100°C; and/or
  • reaction between the compound of formula (II) and the compound of formula (III) is carried out for 3 to 6 hours, preferably 3.5 to 5.5 hours.
  • a photocurable composition comprising a compound of formula (I) according to any one of items 1 to 4 as a polymerizable monomer.
  • the photocurable composition according to item 7 which is a photocurable coating composition, a photocurable ink composition or a photoresist composition.
  • the photocurable composition according to item 7 or 8 further comprising a cationic photoinitiator for ring-opening polymerization and optionally other monomers or oligomers containing vinyl ether double bonds, alicyclic epoxy groups or oxacycloalkyl groups such as oxirane groups or oxetane groups, for example 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221) or 4-vinylcyclohexene oxide (VOH).
  • a cationic photoinitiator for ring-opening polymerization and optionally other monomers or oligomers containing vinyl ether double bonds, alicyclic epoxy groups or oxacycloalkyl groups such as oxirane groups or oxetane groups, for example 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221) or 4-vinylcycl
  • FIG1 is a graph showing the change in conversion rate of alicyclic epoxy groups with irradiation time in the presence of compound (I-1) prepared in Example 1.
  • FIG. 2 is a graph showing the change in conversion rate of alicyclic epoxy groups with irradiation time in the presence of compound (I-2) prepared in Example 2.
  • FIG3 is a graph showing the change in conversion rate of alicyclic epoxy groups with irradiation time in the presence of compound (I-3) prepared in Example 3.
  • 4-6 are contact angle graphs of blank E4221/VOH system cured films and cured films in the presence of compounds (I-1) to (I-3) prepared in Examples 1-3, respectively.
  • FIG. 7 is a thermogravimetric graph of a blank E4221/VOH system cured film and a cured film in the presence of compounds (I-1) to (I-3) prepared in each of Examples 1 to 3.
  • FIG. 7 is a thermogravimetric graph of a blank E4221/VOH system cured film and a cured film in the presence of compounds (I-1) to (I-3) prepared in each of Examples 1 to 3.
  • FIG. 7 is a thermogravimetric graph of a blank E4221/VOH system cured film and a cured film in the presence of compounds (I-1) to (I-3) prepared in each of Examples 1 to 3.
  • FIG. 7 is a thermogravimetric graph of a blank E4221/VOH system cured film and a cured film in the presence of compounds (I-1) to (I-3) prepared in each of Examples 1 to 3.
  • FIG. 7 is a thermogravimetric graph of a blank E4221/VOH system cured film and a cured film in the presence
  • FIG8 is a graph showing the mechanical properties of a blank E4221/VOH system cured film and a cured film in the presence of compounds (I-1) to (I-3) prepared in each of Examples 1 to 3.
  • n is an integer from 1 to 50;
  • n is an integer from 0 to 20;
  • R 1 is C 1 -C 12 alkyl or C 1 -C 12 alkoxy
  • R2 , R3 and R4 are the same or different and are independently C6 - C10 aryl, C1 - C12 alkyl, C1 - C12 alkoxy, or C2 - C12 alkyl with one or more heteroatoms independently selected from NRa , O or S inserted between two carbon atoms, wherein Ra is H or C1 - C4 alkyl, for example C1 - C6 alkoxy- C1 - C6 alkyl, C1-C6 alkylamino- C1 - C6 alkyl or C1 - C6 alkylthio -C1 - C6 alkyl.
  • the compound of formula (I) contains both a trifluoromethyl structure and a polysiloxane structure.
  • the compound having such a structure can be photocured by cationic light, and after photocuring, has good tensile properties, excellent hydrophobic properties, anti-fouling, anti-fingerprint, anti-chemical corrosion, and good heat resistance.
  • C n -C m denotes in each case that the number of carbon atoms contained in the group is nm.
  • Halogen refers to fluorine, chlorine, bromine and iodine. In the present invention, preferably, the halogen includes fluorine, chlorine or a combination thereof.
  • Cn - Cm- alkyl refers to branched or unbranched saturated hydrocarbon radicals having n-m, for example 1 to 12, preferably 1 to 6 and particularly preferably 1 to 4 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, in particular methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethyl propyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, n-hexyl,
  • C 1 -C 6 alkyl can be methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers thereof, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc.
  • C 1 -C 4 alkyl can be methyl, ethyl, propyl, butyl and isomers thereof, in particular methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.
  • C 6 -C m aryl refers to a monocyclic, bicyclic or higher ring aromatic hydrocarbon group containing 6 to m carbon atoms, for example 6 to 10 carbon atoms.
  • C 6 -C m aryl groups phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methyl ethylphenyl, diethylphenyl, methyl propylphenyl and naphthyl can be mentioned; preferably phenyl or naphthyl, especially phenyl.
  • C n -C m alkoxy refers to a C n -C m alkyl group having an oxygen atom as a linking group bonded to any carbon atom of an open-chain C n -C m alkane corresponding to the C n -C m alkyl group, for example, a C 1 -C 12 alkoxy group, more preferably a C 1 -C 6 alkoxy group, and particularly preferably a C 1 -C 4 alkoxy group.
  • the C 1 -C 6 alkoxy group may be a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, and isomers thereof, in particular, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a 2-butoxy group, a tert-butoxy group, a n-pentoxy group, an isopentoxy group, a n-hexoxy group, and the like.
  • the C 1 -C 4 alkoxy group may be a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and isomers thereof, in particular, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, an isobutoxy group, or a tert-butoxy group.
  • n is generally an integer of 1-50, preferably 1-20, particularly preferably an integer of 2-18, in particular an integer of 3-15, for example 3, 4, 5, 6, 7, 8 or 9.
  • m is generally an integer of 0-20, preferably 0-8, particularly preferably an integer of 0-5 or 0-3, for example 0, 1, 2, 3, 4 or 5.
  • R1 is usually C1 - C12 alkyl or C1 - C12 alkoxy.
  • R1 is C1 - C6 alkyl or C1 - C6 alkoxy.
  • R1 is C1 - C4 alkyl or C1 - C4 alkoxy.
  • R1 is C1 - C4 alkyl.
  • R1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • R2 , R3 and R4 are the same or different and are usually independently C6 - C10 aryl, C1 - C12 alkyl, C1-C12 alkoxy or C2 - C12 alkyl with one or more heteroatoms independently selected from NRa , O or S inserted between two carbon atoms, wherein Ra is H or C1 - C4 alkyl, for example C1 - C6 alkoxy- C1 -C6 alkyl, C1-C6 alkylamino-C1-C6 alkyl or C1 - C6 alkylthio -C1 - C6 alkyl.
  • R2 , R3 and R4 are the same or different and are independently C6 - C10 aryl, C1 - C6 alkyl, C1 - C6 alkoxy or C2 - C6 alkyl with one or more heteroatoms selected from NRa , O or S inserted between two carbon atoms, wherein Ra is H or C1 - C4 C 1 -C 3 alkoxy-C 1 -C 3 alkyl, C 1 -C 3 alkylamino-C 1 -C 3 alkyl or C 1 -C 3 alkylthio-C 1 -C 3 alkyl.
  • R 2 , R 3 and R 4 are the same or different and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or C 2 -C 4 alkyl with one or more heteroatoms independently selected from NR a , O or S inserted between two carbon atoms, wherein Ra is H or C 1 -C 4 alkyl, such as C 1 -C 2 alkoxy-C 1 -C 2 alkyl, C 1 -C 2 alkylamino-C 1 -C 2 alkyl or C 1 -C 2 alkylthio-C 1 -C 2 alkyl.
  • R 2 , R 3 and R 4 are the same or different and are independently C 1 -C 4 alkyl.
  • R2 , R3 and R4 are the same or different and are independently phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy or tert-butoxy.
  • n is an integer from 3 to 15;
  • n is an integer from 0 to 5;
  • R 1 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy
  • R2 , R3 and R4 are the same or different and are independently phenyl, C1 - C4 alkyl, C1 - C4 alkoxy or C2- C4 alkyl with one or more heteroatoms selected from NRa , O or S inserted between two carbon atoms, wherein Ra is H or C1 - C4 alkyl, for example C1 - C2 alkoxy- C1 - C2 alkyl, C1 - C2 alkylamino- C1 - C2 alkyl or C1 - C2 alkylthio- C1 - C2 alkyl.
  • the compound of formula (I) is a compound selected from the group consisting of:
  • the silicon atom of the compound of formula (II) contains a hydrogen atom, and therefore, the compound of formula (II) can be referred to as trifluoromethyl hydrogenated silicone oil.
  • the compound of formula (II) can be synthesized according to conventional methods or can be obtained from commercial sources.
  • the addition reaction of the hydrogen atom bonded to the silicon atom in the compound of formula (II) and the unsaturated carbon-carbon double bond in the compound of formula (III) belongs to the reaction type known in the art. Generally speaking, the reaction is carried out in the presence of a catalyst.
  • a catalyst suitable for the reaction a Karstedt catalyst or a Speier catalyst is generally used.
  • the amount of the catalyst is also conventional.
  • the amount of the catalyst is 2-100 ppm.
  • the reaction of the compound of formula (II) with the compound of formula (III) is generally carried out in a solvent.
  • a solvent there is no particular limitation, as long as the compound of formula (II), the compound of formula (III) and the catalyst can be dissolved and do not participate in the reaction between the compound of formula (II) and the compound of formula (III), preferably the solvent is also conducive to the precipitation of the product, i.e., the compound of formula (I).
  • an organic solvent is generally used, preferably petroleum ether, dichloromethane, toluene or any mixture thereof.
  • the amount of solvent used is also conventional, and generally speaking, the amount of solvent used is 1.5-3 times the total weight of the compound of formula (II) and the compound of formula (III).
  • the compound of formula (II) and the compound of formula (III) are generally used in approximately equimolar amounts.
  • the molar ratio of the compound of formula (II) to the compound of formula (III) is 1:1-1:1.5.
  • the compound of formula (II) and the catalyst are generally dissolved in a solvent and aged for a period of time, then contacted with the compound of formula (III), and then heated to the reaction temperature for a period of time to obtain the compound of formula (I). Aging is generally carried out at an elevated temperature, generally aged at 40-70°C.
  • the aging time is generally 30-60 minutes.
  • the reaction temperature between the compound of formula (II) and the compound of formula (III) is generally 80-110°C, preferably 85-100°C.
  • the retention time of the reaction between the compound of formula (II) and the compound of formula (III) at the reaction temperature is generally 3-6 hours, preferably 3.5-5.5 hours.
  • the reaction can be advantageously carried out under stirring.
  • the compound of formula (I) is obtained by conventional post-treatment.
  • the post-treatment generally includes filtering or centrifuging to remove solid impurities, rotary evaporation to remove the solvent, and reduced pressure distillation to further remove the solvent. If a higher purity product is to be obtained, recrystallization can also be performed.
  • the compound of formula (III) can be synthesized according to conventional methods or can be obtained from commercial sources.
  • the compound of formula (I) of the present invention is a cationic photocurable monomer, which has good tensile properties after photocuring polymerization, excellent hydrophobicity, anti-fouling, anti-fingerprint, anti-chemical corrosion and good heat resistance.
  • a photocurable composition which comprises the compound of formula (I) of the present invention as a polymerizable monomer.
  • it may also contain a cationic photoinitiator for ring-opening polymerization (a photoinitiator capable of initiating cationic polymerization) and optionally other monomers or oligomers containing vinyl ether double bonds, alicyclic epoxy groups or oxacycloalkyl groups such as oxirane or oxetane groups, which can be photocured by cationic light, such as 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221) or 4-vinyl epoxycyclohexane (VOH).
  • a cationic photoinitiator for ring-opening polymerization a photoinitiator capable of initiating cationic polymerization
  • other monomers or oligomers containing vinyl ether double bonds such as oxirane or oxet
  • the photocurable composition of the present invention can be a photocurable coating composition, a photocurable ink composition or a photoresist composition. After the composition is cured, the obtained cured product has good tensile properties, excellent hydrophobic properties, anti-fouling, anti-fingerprint, anti-chemical corrosion, and good heat resistance.
  • iodonium salts and sulfonium salts are commonly used.
  • the iodonium salt photoinitiator and sulfonium salt photoinitiator have the following general formulas (A) and (B), respectively:
  • Ra , Rb , Rc , Rd and Re are each independently unsubstituted C6 - C10 aryl, or C6 - C10 aryl substituted with a substituent selected from halogen, nitro, carbonyl, C1 - C12 alkyl, C1 - C12 alkoxy, phenylthio, phenyl and substituted phenyl, preferably phenyl or naphthyl, or phenyl or naphthyl substituted with a substituent selected from halogen, nitro, C1 - C6 alkyl and substituted phenyl, wherein the substituent contained in the substituted phenyl is one or more groups selected from halogen, nitro, C1 - C6 alkyl and C1 - C6 alkoxy; and
  • Y and Z are non-nucleophilic anions, for example triflate, toluenesulfonate, C 1 -C 6 carboxylate, BF 4 ⁇ , ClO 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ or SbF 6 ⁇ .
  • the photoinitiator one or more selected from the group consisting of 4-(phenylthio)phenyl ⁇ diphenylsulfonium hexafluorophosphate, 4-(phenylthio)phenyl ⁇ diphenylsulfonium hexafluoroantimonate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexafluoroantimonate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulf
  • the photocurable composition of the present invention may further contain a sensitizer.
  • a sensitizer for example, benzophenone and its derivatives such as 4-(4-methylphenylthio)benzophenone or 4,4'-di(diethylamino)benzophenone, thioxanthone and its derivatives such as 2-isopropylthioxanthone, anthraquinone and its derivatives such as 2-ethylanthraquinone, coumarin derivatives such as 5,7-dimethoxy-3-(4-dodecylbenzoyl)coumarin, camphorquinone, phenothiazine and its derivatives, 3-(aroylmethylene)thiazoline, rhodanine and its derivatives, eosin, rhodamine, acridine, Anthocyanin and merocyanine dyes; preferably benzophenone and its derivatives, thioxanthone and its derivatives,
  • the amount of photoinitiator used is conventional. Based on the total amount of the photocurable composition of the present invention, the content of photoinitiator is usually 0.5-5 mol %, preferably 0.5-1 mol %.
  • a photocurable material obtained by photocuring the photocurable composition of the present invention.
  • the photocuring conditions are not particularly limited as long as the photocurable composition of the present invention can be photocured.
  • the photocurable material has the advantages of good tensile properties, excellent hydrophobic properties, anti-fouling, anti-fingerprint, anti-chemical corrosion, and good heat resistance due to the inclusion of the compound of formula (I) of the present invention as a photocurable monomer.
  • the purpose of this example is to illustrate the photopolymerization properties of the compounds of the present invention.
  • a mixture of diphenyliodonium hexafluorophosphate (810) and 2-isopropylthioxanthone (ITX, sensitizer) in a mass ratio of 2:1 was used as a photoinitiator system.
  • the photopolymerization kinetics in the presence of compounds (I-1) to (I-5) were tested by real-time infrared (RT-IR) method, and the effects of each on the photopolymerization performance of E4221 at different contents were investigated.
  • the vibration absorption peak of the COC of the monomer E4221/VOH ternary oxygen heterocycle used is located at 750 cm -1 .
  • the photocurable liquid composed of the monomer and the photoinitiator is evenly applied on a potassium bromide salt sheet, and the liquid sample is irradiated for 900s with a high-pressure mercury lamp, in which the main emission wavelength of the mercury lamp is 365nm and an optical fiber with a diameter of 5mm is used. One end of the optical fiber is 10cm away from the test sample, and the irradiation intensity is 20mW cm -2 .
  • the real-time conversion rate and polymerization rate of different epoxy groups are characterized by measuring the change in the COC bond peak area at 750cm -1 .
  • the purpose of this example is to illustrate that the compound of the present invention can improve the surface hydrophobicity of the photocured film.
  • the surface hydrophobicity of the photocured film was characterized by using a DSA25 water contact angle tester at a test temperature of 25°C.
  • a blank E4221/VOH cured film was prepared using the same method as a reference. The results of the reference and in the presence of compounds (I-1) to (I-3) are shown in Figures 4-6.
  • the cured films of each of the compounds (I-1) to (I-3) were prepared in the presence of the compounds according to the same method as described in Example 7.
  • the heat resistance of each photocured film was then determined using a thermogravimetric analyzer.
  • the test conditions were: under nitrogen protection, temperature range 30-700°C, and heating rate 10°C/min.
  • a blank E4221/VOH cured film was prepared using the same method as a reference. The results are shown in Table 1 and Figure 7.
  • the purpose of this example is to illustrate that the compounds of the present invention can improve the tensile properties of photocured films.
  • the cured films of the compounds (I-1) to (I-3) were prepared in the presence of the compounds (I-1) to (I-3) in exactly the same manner as described in Example 7.
  • the tensile properties of the photocured films were then tested using an electronic universal testing machine.
  • the test temperature was 25°C and the test speed was 1 mm/min.
  • a blank E4221/VOH cured film was prepared using the same method as a reference. The results are shown in Figure 8.
  • the tensile strength of the pure E4221/VOH photocured film is 0.26 MPa, and the elongation at break is 22.96%.
  • the tensile strength of the photocured film changes slightly, and the elongation at break increases to 54.17%, 60.22% and 68.51%, respectively, which increases to about 3 times. Therefore, the compounds of the present invention can significantly improve the tensile properties of the cured film.

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Abstract

本发明涉及式(I)化合物，其中各变量n、m、R1、R2、R3和R4如说明书中所定义。式(I)化合物可光聚合，光固化后具有拉伸性能好，疏水性能优异，抗沾污，抗指纹，抗化学品腐蚀，耐热性好等优点。本发明还涉及式(I)化合物的制备，包含式(I)化合物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。

Description

三氟甲基有机硅脂环族环氧单体及其制备和应用 技术领域
本发明所属技术领域为光固化材料领域，具体来说涉及一种三氟甲基有机硅脂环族环氧单体。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。
背景技术
有机硅类和氟碳类材料一直被视为低表面能涂层材料方面的理想研究方向，但是氟碳类材料有着机械性能差、生产成本高的缺点；纯硅体系的材料容易因为柔性过高而在实际应用中有所局限。随着人们对材料综合性能的需求越来越高，单一的有机硅或有机氟材料难以满足生产需要，氟硅氧烷聚合物结合了两者的优点，逐渐在各领域受到了广泛关注。
与传统的热聚合技术相比，利用绿色光聚合技术通过可光聚合的氟硅单体或低聚物制备氟硅聚合物的方法具有无溶剂、高效、能源利用率高、可室温固化以及空间和时间控制等独特优势。如前所述，氟硅氧烷聚合物兼具有机硅和有机氟的优点，具有突出的热稳定性、耐腐蚀性、疏水疏油性。但是目前对可光固化氟硅单体的研究，大部分集中在用于自由基光聚合的氟硅改性丙烯酸酯类单体的开发，对阳离子型氟硅单体的报道较少。自由基光聚合存在氧阻聚、体积收缩大的缺点，阳离子光聚合具有抗氧阻聚、体积收缩小的优点，因此亟待开发新型的阳离子型氟硅单体。而脂环族环氧类单体作为反应性最强的单体种类之一，除了具有传统环氧单体的无氧阻聚和低固化收缩率等优势，还兼具无明显诱导期、聚合速率快、低粘度、耐候性好等特点，在阳离子光固化体系中，占据了重要的一席之地。因此，在一些需要快速响应的领域，如电力绝缘材料、胶粘剂、电子封装等，脂环族环氧类单体有着得天独厚的优势，其需求量也在逐年增大。基于此，开发一系列成本相对低廉、疏水性良好的三氟甲基有机硅脂环族环氧单体，对促进阳离子光聚合技术及氟硅材料发展具有重要的理论意义和实际价值。
发明内容
鉴于现有技术的上述状况，本发明的发明人在阳离子光聚合型氟硅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三氟甲基有机硅脂环族环 氧单体，该单体光固化后具有拉伸性能好，疏水性能优异，抗沾污，抗指纹等优点。本发明人发现，将聚硅氧烷链及三氟甲基引入到环氧类单体中，如此获得的三氟甲基有机硅脂环族环氧单体光固化后具有拉伸性能好，疏水性能优异，抗沾污，抗指纹等优点。
因此，本发明的一个目的是提供一种三氟甲基有机硅脂环族环氧单体，该单体不仅含有可阳离子光固化的基团，而且还含有聚硅氧烷链和三氟甲基。具有如此结构的氟硅单体光固化后拉伸性能好，疏水性能优异，抗沾污，抗指纹，抗化学品腐蚀，耐热性好。
本发明的另一目的是提供一种制备本发明三氟甲基有机硅脂环族环氧单体的方法。该制备过程简单易行，条件温和，成本也相对低廉。
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三氟甲基有机硅脂环族环氧单体。
本发明的又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。
实现本发明上述目的的技术方案可以概括如下：
1.下式(Ⅰ)化合物：
n为1-50的整数；
m为0-20的整数；
R1为C1-C12烷基或者C1-C12烷氧基；
R2、R3和R4相同或不同，并独立地为C6-C10芳基、C1-C12烷基、C1-C12烷氧基或者两个碳原子之间插有一个或多个独立地选自NRa、O或S的杂原子的C2-C12烷基，其中Ra为H或C1-C4烷基，例如C1-C6烷氧基-C1-C6烷基、C1-C6烷基氨基-C1-C6烷基或C1-C6烷硫基-C1-C6烷基。
2.根据第1项的化合物，其中
n为1-20，优选2-18的整数；和/或
m为0-8，优选0-5，更优选0-3的整数；和/或
R1为C1-C6烷基或者C1-C6烷氧基；R1优选为C1-C4烷基或者C1-C4烷氧基；和/或
R2、R3和R4相同或不同，并独立地为C6-C10芳基、C1-C6烷基、C1-C6烷氧基或者两个碳原子之间插有一个或多个选自NRa、O或S的杂原子的C2-C6烷基，其中Ra为H或C1-C4烷基，例如C1-C3烷氧基-C1-C3烷基、C1-C3烷基氨基-C1-C3烷基或C1-C3烷硫基-C1-C3烷基；优选的是，R2、R3和R4相同或不同，并独立地为苯基、C1-C4烷基、C1-C4烷氧基或者两个碳原子之间插有一个或多个独立地选自NRa、O或S的杂原子的C2-C4烷基，其中Ra为H或C1-C4烷基，例如C1-C2烷氧基-C1-C2烷基、C1-C2烷基氨基-C1-C2烷基或C1-C2烷硫基-C1-C2烷基。
3.根据第1项的化合物，其中
n为3-15的整数；
m为0-5的整数；
R1为C1-C4烷基或者C1-C4烷氧基；
R2、R3和R4相同或不同，并独立地为苯基、C1-C4烷基、C1-C4烷氧基或者两个碳原子之间插有一个或多个选自NRa、O或S的杂原子的C2-C4烷基，其中Ra为H或C1-C4烷基，例如C1-C2烷氧基-C1-C2烷基、C1-C2烷基氨基-C1-C2烷基或C1-C2烷硫基-C1-C2烷基；
优选的是，
n为3-15的整数；
m为0-5的整数；
R1为C1-C4烷基；
R2、R3和R4相同或不同，并独立地为C1-C4烷基。
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：

5.一种制备根据第1-4项中任一项的式(I)化合物的方法，包括使式(II)化合物：
其中n、R1、R2、R3和R4如第1-4项中任一项所定义，
与式(III)化合物反应：
其中m如第1-4项中任一项所定义，
得到式(I)化合物。
6.根据第5项的方法，其中
式(II)化合物与式(III)化合物的反应在Karstedt催化剂或Speier催化剂存在下进行，优选的是，该催化剂的用量基于式(II)化合物的重量为2-100ppm；和/或
式(II)化合物与式(III)化合物的用量摩尔比为1:1-1:1.5；和/或
式(II)化合物与式(III)化合物之间的反应在80-110℃，优选85-100℃下进行；和/或
式(II)化合物与式(III)化合物之间的反应进行3-6小时，优选3.5-5.5小时。
7.一种可光固化组合物，包含根据第1-4项中任一项的式(Ⅰ)化合物作为可聚合单体。
8.根据第7项的可光固化组合物，其为光固化涂料组合物、光固化油墨组合物或光致抗蚀组合物。
9.根据第7或8项的可光固化组合物，还包含用于开环聚合的阳离子光引发剂以及任选地其它含有乙烯基醚双键、脂环族环氧基或氧杂环烷基如环氧乙烷基或者氧杂环丁烷基的单体或低聚物，例如3,4-环氧环己基甲基3,4-环氧环己基甲酸酯(E4221)或4-乙烯基环氧环己烷(VOH)。
10.一种光固化材料，该材料通过将根据第7-9项中任一项的可光固化组合物光固化而获得。
附图说明
图1是在实施例1所制备的化合物(I-1)存在下脂环族环氧基团转化率随辐照时间的变化曲线图。
图2是在实施例2所制备的化合物(I-2)存在下脂环族环氧基团转化率随辐照时间的变化曲线图。
图3是在实施例3所制备的化合物(I-3)存在下脂环族环氧基团转化率随辐照时间的变化曲线图。
图4-6是空白E4221/VOH体系固化膜和在实施例1-3各自制备的化合物(I-1)至(I-3)存在下的固化膜的接触角图。
图7是空白E4221/VOH体系固化膜和在实施例1-3各自制备的化合物(I-1)至(I-3)存在下的固化膜的热重曲线图。
图8是空白E4221/VOH体系固化膜和在实施例1-3各自制备的化合物(I-1)至(I-3)存在下的固化膜的力学性能曲线图。
具体实施方式
根据本发明的一个方面，提供了一种下式(Ⅰ)化合物：
其中
n为1-50的整数；
m为0-20的整数；
R1为C1-C12烷基或者C1-C12烷氧基；
R2、R3和R4相同或不同，并独立地为C6-C10芳基、C1-C12烷基、C1-C12烷氧基或者两个碳原子之间插有一个或多个独立地选自NRa、O或S的杂原子的C2-C12烷基，其中Ra为H或C1-C4烷基，例如C1-C6烷氧基-C1-C6烷基、C1-C6烷基氨基-C1-C6烷基或C1-C6烷硫基-C1-C6烷基。
在本发明中，式(I)化合物既包含三氟甲基结构，又包含聚硅氧烷结构部分。具有如此结构的化合物可以阳离子光固化，并且光固化后拉伸性能好，疏水性能优异，抗沾污，抗指纹，抗化学品腐蚀，耐热性好。
在本发明中，前缀“Cn-Cm”在每种情况下表示该基团中包含的碳原子数为n-m个。
“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。
本文所用的术语“Cn-Cm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个碳原子的支化或未支化饱和烃基，例如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基及其异构体，特别是甲基、乙基、正丙基、1-甲基乙基、正丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、正戊基、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、1,1-二甲基丙基、1,2-二甲基丙基、正己基、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、正庚基、正辛基、2-乙基己基、正壬基、正癸基、正十一烷基、正十二烷基等。C1-C6烷基可以是甲基、乙基、丙基、丁基、戊基、己基及其异构体，特别是甲基、乙基、正丙基、异丙基、正丁基、2-丁基、叔丁基、正戊基、异戊基、正己基等。C1-C4烷基可以是甲基、乙基、丙基、丁基及其异构体，特别是甲基、乙基、正丙基、1-甲基乙基、正丁基、1-甲基丙基、2-甲基丙基或1,1-二甲基乙基。
本文所用术语“C6-Cm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C6-Cm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。
本文所用的术语“Cn-Cm烷氧基”是指在Cn-Cm烷基对应的开链Cn-Cm烷烃的任何碳原子上键合有一个氧原子作为连接基团的Cn-Cm烷基，例如C1-C12烷氧基，更优选C1-C6烷氧基，尤其优选C1-C4烷氧基。C1-C6烷氧基可以是甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基及其异构体，特别是甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、2-丁氧基、叔丁氧基、正戊氧基、异戊氧基、正己氧基等。C1-C4烷氧基可以是甲氧基、乙氧基、丙氧基、丁氧基及其异构体，特别是甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基或叔丁氧基。
在本发明化合物中，n通常为1-50，优选1-20的整数，特别优选为2-18的整数，尤其为3-15的整数，例如为3、4、5、6、7、8或9。
在本发明化合物中，m通常为0-20，优选0-8的整数，特别优选为0-5或0-3的整数，例如为0、1、2、3、4或5。
在本发明化合物中，R1通常为C1-C12烷基或者C1-C12烷氧基。优选的是，R1为C1-C6烷基或者C1-C6烷氧基。特别优选的是，R1为C1-C4烷基或者C1-C4烷氧基。尤其是R1为C1-C4烷基。例如，R1为甲基、乙基、正丙基、异丙基、正丁基、仲丁基或叔丁基。
在本发明化合物中，R2、R3和R4相同或不同，并通常独立地为C6-C10芳基、C1-C12烷基、C1-C12烷氧基或者两个碳原子之间插有一个或多个独立地选自NRa、O或S的杂原子的C2-C12烷基，其中Ra为H或C1-C4烷基，例如C1-C6烷氧基-C1-C6烷基、C1-C6烷基氨基-C1-C6烷基或C1-C6烷硫基-C1-C6烷基。优选的是，R2、R3和R4相同或不同，并独立地为C6-C10芳基、C1-C6烷基、C1-C6烷氧基或者两个碳原子之间插有一个或多个选自NRa、O或S的杂原子的C2-C6烷基，其中Ra为H或C1-C4 烷基，例如C1-C3烷氧基-C1-C3烷基、C1-C3烷基氨基-C1-C3烷基或C1-C3烷硫基-C1-C3烷基。特别优选的是，R2、R3和R4相同或不同，并独立地为苯基、C1-C4烷基、C1-C4烷氧基或者两个碳原子之间插有一个或多个独立地选自NRa、O或S的杂原子的C2-C4烷基，其中Ra为H或C1-C4烷基，例如C1-C2烷氧基-C1-C2烷基、C1-C2烷基氨基-C1-C2烷基或C1-C2烷硫基-C1-C2烷基。尤其是R2、R3和R4相同或不同，并独立地为C1-C4烷基。例如，R2、R3和R4相同或不同，并独立地为苯基、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。
在本发明的一些优选实施方案中，
n为3-15的整数；
m为0-5的整数；
R1为C1-C4烷基或者C1-C4烷氧基；
R2、R3和R4相同或不同，并独立地为苯基、C1-C4烷基、C1-C4烷氧基或者两个碳原子之间插有一个或多个选自NRa、O或S的杂原子的C2-C4烷基，其中Ra为H或C1-C4烷基，例如C1-C2烷氧基-C1-C2烷基、C1-C2烷基氨基-C1-C2烷基或C1-C2烷硫基-C1-C2烷基。
在本发明的另一实施方案中，式(I)化合物为选自下组的化合物：

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，包括使式(Ⅱ)化合物：
其中n、R1、R2、R3和R4如对式(I)化合物所定义，
与式(Ⅲ)化合物反应：
其中m如对式(I)化合物所定义，
得到式(I)化合物。
式(II)化合物的硅原子上含有氢原子，因此，式(II)化合物可称作三氟甲基含氢硅油。式(II)化合物可根据常规方法合成或者可从商业途径得到。式(II)化合物中硅原子键合的氢原子与式(III)化合物中的不饱和碳碳双键的加成反应属于本领域已知的反应类型。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，通常采用Karstedt催化剂或Speier催化剂。催化剂的用量也是常规的。通常而言，基于式(II)化合物的重量，催化剂的用量为2-100ppm。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，优选使用石油醚、二氯甲烷、甲苯或其任意混合物。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1.5-3倍。式(II)化合物和式(III)化合物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1:1-1:1.5。为了实现上述反应，通常先将式(II)化合物与催化剂溶解在溶剂中陈化一段时间后，再与式(III)化合物接触，然后升温至反应温度保持一段时间，得到式(I)化合物。陈化通常在升高的温度下进行，通常在40-70℃下陈化。陈化时间通常为30-60分钟。式(II)化合物与式(III)化合物之间的反应温度通常为80-110℃，优选85-100℃。式(II)化合物与式(III)化合物之间的反应在反应温度下的保持时间通常为3-6小时，优选3.5-5.5小时。当然，反应可以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。
式(III)化合物可根据常规方法合成或者可从商业途径得到。
本发明式(Ⅰ)化合物是一种阳离子光固化单体，光固化聚合之后拉伸性能较好，疏水性能优异，抗沾污，抗指纹，抗化学品腐蚀，耐热性好。
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)化合物作为可聚合单体。该可光固化组合物除了包含本发明的 式(Ⅰ)化合物以外，还可包含用于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)以及任选地其它含有乙烯基醚双键、脂环族环氧基或氧杂环烷基如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或低聚物，例如3,4-环氧环己基甲基3,4-环氧环己基甲酸酯(E4221)或4-乙烯基环氧环己烷(VOH)。本发明可光固化组合物可以为光固化涂料组合物、光固化油墨组合物或光致抗蚀组合物等。该组合物在固化后，所得固化产物拉伸性能较好，疏水性能优异，抗沾污，抗指纹，抗化学品腐蚀，耐热性好。
作为开环聚合的光引发剂，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)：
其中
Ra、Rb、Rc、Rd和Re各自独立地是未取代的C6-C10芳基，或者被选自卤素、硝基、羰基、C1-C12烷基、C1-C12烷氧基、苯硫基、苯基和取代苯基的取代基取代的C6-C10芳基，优选是苯基或萘基，或者被选自卤素、硝基、C1-C6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、C1-C6烷基和C1-C6烷氧基的基团；以及
Y和Z是非亲核性阴离子，例如三氟甲磺酸根、甲苯磺酸根、C1-C6羧酸根、BF4 -、ClO4 -、PF6 -、AsF6 -或SbF6 -。
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)碘鎓六氟磷酸盐或双(4-叔丁基苯)碘鎓六氟锑酸盐。
本发明可光固化组合物还可以包含增感剂。作为增感剂，例如可以提及二苯甲酮及其衍生物如4-(4-甲基苯硫基)二苯甲酮或4,4’-二(二乙氨基)二苯甲酮、硫杂蒽酮及其衍生物如2-异丙基硫杂蒽酮、蒽醌及其衍生物如2-乙基蒽醌、香豆素衍生物如5,7-二甲氧基-3-(4-十二烷基苯甲酰基)香豆素、樟脑醌、吩噻嗪及其衍生物、3-(芳酰基亚甲基)噻唑啉、绕丹宁及其衍生物、曙红、罗丹明、吖啶、 花青素、部花青染料；优选二苯甲酮及其衍生物、硫杂蒽酮及其衍生物、蒽醌及其衍生物、香豆素及其衍生物，尤其优选2-异丙基硫杂蒽酮。
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的总量，光引发剂的含量通常为0.5-5mol％，优选为0.5-1mol％。
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。光固化条件不受特别限制，只要能使本发明的可光固化组合物进行光固化。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，具有拉伸性能较好，疏水性能优异，抗沾污，抗指纹，抗化学品腐蚀，耐热性好的优点。
实施例
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。
下述实施例中所用的材料和试剂如表A所列，其他材料和试剂均可从商业途径得到。
表A-实验材料和试剂
下述实施例中所用的仪器如表B所列。
表B-实验仪器

实施例1
保持阴离子开环聚合所需的无水无氧环境。先用真空泵将装有回流冷凝管、滴液漏斗的150mL三口烧瓶抽至真空，然后全程保持通入氮气，用注射器将6.25mL正丁基锂(1.6M，正己烷溶液)注入三口瓶内，冰水浴保持0℃，将5.14g(0.011mol)三氟丙基甲基环三硅氧烷和15ml四氢呋喃注入滴液漏斗。最后加入1.04g(0.011mol)二甲基氯硅烷以终止反应，并将溶液在室温下再搅拌过夜。将反应液离心10分钟，取清液旋蒸除去四氢呋喃。将有机相真空蒸馏以除去残留的三氟丙基甲基环三硅氧烷获得硅链长度为3的三氟甲基含氢硅油FSi3H(对应于式(II)化合物，其中n＝3，R1为正丁基，以及R2、R3和R4为甲基)。
[FSi3H]:1H NMR(400MHz,氯仿-d)δ4.74(ddp,1H),2.17-1.97(m,6H),1.45-1.26(m,4H),0.92(t,J＝6.9Hz,3H),0.87-0.69(m,6H),0.67-0.56(m,2H),0.29-0.07(m,15H)。
实验过程中保持无水无氧环境。先用真空泵将装有回流冷凝管、滴液漏斗的150mL三口烧瓶抽至真空，然后全程保持通入氮气。使用注射器进行加料操作。在15ppm Karstedt催化剂(浓度为100ppm，在甲苯中)的催化下，将10mmol FSi3H、30mL无水甲苯加入三口烧瓶内，升温至40℃，搅拌2小时；将11mmol4-乙烯基环氧环己烷加入滴液漏斗中，以约1滴/秒的速度滴加，滴加完毕后，保持40℃反应1小时；然后，升温至85～90℃，反应5.5小时，结束加热。反应液冷却至室温，用旋转蒸发器旋蒸旋出部分甲苯；再将溶液减压蒸馏即可得到产物。经核磁氢谱表征，确定为化合物(I-1)，下文称作CE-FSi3。
[CE-FSi3]:1H NMR(400MHz,氯仿-d)δ3.26-3.08(m,2H),2.27-1.93(m,9H),1.90-1.04(m,10H),0.92(t,J＝7.1Hz,3H),0.83-0.70(m,7H),0.67-0.57(m,2H),0.57-0.45(m,2H),0.21-0.06(m,15H)。
实施例2
FSi6H(对应于式(II)化合物，其中n＝6，R1为正丁基，以及R2、R3和R4为甲基)的合成类似于实施例1中FSi3H的合成，不同之处在于使用25ml四氢呋喃和10.28g(0.022mol)三氟丙基甲基环三硅氧烷。
[FSi6H]:1H NMR(400MHz,氯仿-d)δ4.77(hept,1H),2.27-1.92(m,15H),1.52-1.18(m,4H),0.93(t,J＝6.9Hz,3H),0.88-0.76(m,14H),0.70-0.58(m,2H),0.33-0.09(m,28H)。
实验过程中保持无水无氧环境。先用真空泵将装有回流冷凝管、滴液漏斗的150mL三口烧瓶抽至真空，然后全程保持通入氮气。使用注射器进行加料操作。在15ppm Karstedt催化剂(浓度为100ppm，在甲苯中)的催化下，将10mmol FSi6H、30mL无水甲苯加入三口烧瓶内，升温至40℃，搅拌2小时；将11mmol4-乙烯基环氧环己烷加入滴液漏斗中，以约1滴/秒的速度滴加，滴加完毕后，保持40℃反应1小时；然后，升温至85～90℃，反应5.5小时，结束加热。反应液冷却至室温，用旋转蒸发器旋蒸旋出部分甲苯；再将溶液减压蒸馏即可得到产物。经核磁氢谱表征，确定为化合物(I-2)，下文称作CE-FSi6。
[CE-FSi6]:1H NMR(400MHz,氯仿-d)δ3.22-3.09(m,2H),2.22-1.97(m,16H),1.85-1.04(m,9H),0.91(t,J＝6.9Hz,4H),0.77(dqd,J＝17.7,9.9,8.6,4.8Hz,13H),0.67-0.58(m,2H),0.58-0.47(m,2H),0.21-0.05(m,27H)。
实施例3
FSi9H(对应于式(II)化合物，其中n＝9，R1为正丁基，以及R2、R3和R4为甲基)的合成类似于实施例1中FSi3H的合成，不同之处在于使用35ml四氢呋喃和15.42g(0.033mol)三氟丙基甲基环三硅氧烷。
[FSi9H]:1H NMR(400MHz,氯仿-d)δ4.82-4.69(m,1H),2.18-1.99(m,17H),1.45-1.27(m,3H),0.92(t,J＝6.9Hz,3H),0.79(qq,J＝8.4,4.9,4.0Hz,17H),0.69-0.57(m,2H),0.30-0.10(m,32H)。
实验过程中保持无水无氧环境。先用真空泵将装有回流冷凝管、滴液漏斗的150mL三口烧瓶抽至真空，然后全程保持通入氮气。使用注射器进行加料操作。在15ppm Karstedt催化剂(浓度为100ppm，在甲苯中)的催化下，将10mmol FSi9H、30mL无水甲苯加入三口烧瓶内，升温至40℃，搅拌2小时；将11mmol4-乙烯基环氧环己烷加入滴液漏斗中，以约1滴/秒的速度滴加，滴加完毕后，保持40℃反应1小时；然后，升温至85～90℃，反应5.5小时，结束加热。反应液冷却至室温，用旋转蒸发器旋蒸旋出部分甲苯；再将溶液减压蒸馏即可得到产物。经核磁氢谱表征，确定为化合物(I-3)，下文称作CE-FSi9。
[CE-FSi9]:1H NMR(400MHz,氯仿-d)δ3.21-3.10(m,2H),2.24-1.96(m,21H),1.70-1.11(m,11H),0.92(t,J＝7.0Hz,3H),0.77(ddt,J＝17.6,13.2,8.0Hz,18H),0.67-0.59(m,2H),0.53(ddt,J＝12.3,6.3,3.3Hz,2H),0.28-0.06(m,33H)。
实施例4
FSi12H(对应于式(II)化合物，其中n＝12，R1为正丁基，以及R2、R3和R4为甲基)的合成类似于实施例1中FSi3H的合成，不同之处在于使用45ml四氢呋喃和20.56g(0.044mol)三氟丙基甲基环三硅氧烷。
[FSi12H]:1H NMR(400MHz,氯仿-d)δ4.82-4.69(m,1H),1.90-1.04(m,27H),1.45-1.27(m,3H),0.92(t,J＝7.1Hz,3H),0.83-0.70(m,25H),0.69-0.57(m,2H),0.30-0.10(m,42H)。
实验过程中保持无水无氧环境。先用真空泵将装有回流冷凝管、滴液漏斗的150mL三口烧瓶抽至真空，然后全程保持通入氮气。使用注射器进行加料操作。在15ppm Karstedt催化剂(浓度为100ppm，在甲苯中)的催化下，将10mmol FSi12H、30mL无水甲苯加入三口烧瓶内，升温至40℃，搅拌2小时；将11mmol4-乙烯基环氧环己烷加入滴液漏斗中，以约1滴/秒的速度滴加，滴加完毕后， 保持40℃反应1小时；然后，升温至85～90℃，反应5.5小时，结束加热。反应液冷却至室温，用旋转蒸发器旋蒸旋出部分甲苯；再将溶液减压蒸馏即可得到产物。经核磁氢谱表征，确定为化合物(I-4)，下文称作CE-FSi12。
[CE-FSi12]:1H NMR(400MHz,氯仿-d)δ3.26-3.08(m,2H),2.27-1.93(m,9H),1.90-1.04(m,27H),0.92(t,J＝7.1Hz,3H),0.83-0.70(m,25H),0.67-0.57(m,2H),0.57-0.45(m,2H),0.21-0.06(m,42H)。
实施例5
FSi15H(对应于式(II)化合物，其中n＝15，R1为正丁基，以及R2、R3和R4为甲基)的合成类似于实施例1中FSi3H的合成，不同之处在于使用55ml四氢呋喃和25.7g(0.055mol)三氟丙基甲基环三硅氧烷。
[FSi15H]:1H NMR(400MHz,氯仿-d)δ4.82(m,1H),2.27-1.93(m,33H),1.52-1.18(m,4H),0.92(t,J＝7.1Hz,3H),0.83-0.70(m,31H),0.70-0.58(m,2H),0.21-0.06(m,51H)。
实验过程中保持无水无氧环境。先用真空泵将装有回流冷凝管、滴液漏斗的150mL三口烧瓶抽至真空，然后全程保持通入氮气。使用注射器进行加料操作。在15ppm Karstedt催化剂(浓度为100ppm，在甲苯中)的催化下，将10mmol FSi15H、30mL无水甲苯加入三口烧瓶内，升温至40℃，搅拌2小时；将11mmol4-乙烯基环氧环己烷加入滴液漏斗中，以约1滴/秒的速度滴加，滴加完毕后，保持40℃反应1小时；然后，升温至85～90℃，反应5.5小时，结束加热。反应液冷却至室温，用旋转蒸发器旋蒸旋出部分甲苯；再将溶液减压蒸馏即可得到产物。经核磁氢谱表征，确定为化合物(I-5)，下文称作CE-FSi15。
[CE-FSi15]:1H NMR(400MHz,氯仿-d)δ3.26-3.08(m,2H),2.27-1.93(m,33H),1.90-1.04(m,10H),0.92(t,J＝7.1Hz,3H),0.83-0.70(m,31H),0.67-0.57(m,2H),0.57-0.45(m,2H),0.21-0.06(m,51H)。
实施例6
本实施例的目的在于说明本发明化合物的光聚合性能。
将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，增感剂)以2:1质量比组成的混合物用作光引发体系，采用实时红外(RT-IR)的方法测试了在化合物(I-1)至(I-5)存在下的光聚合动力学性能，并考察各自在不同含量下对E4221光聚合性能的影响。所使用单体E4221/VOH三元氧杂环的C-O-C的振动吸收峰位于750cm-1位置，将单体和光引发剂组成的可光固化液体均匀涂抹在溴化钾盐片上，用高压汞灯照射液体样品900s，其中汞灯主要发射波长为365nm，并且带有直径为5mm的光导纤维。光纤一端距离测试样品距离为10cm，辐照强度为20mW cm-2。通过测量在750cm-1处C-O-C键峰面积的变化，表征了不同环氧基团的实时转化率和聚合速率。
其中在化合物(I-1)至(I-3)存在下各自的结果分别如图1-3所示。结果显示，化合物(I-1)至(I-3)的加入可以明显改善E4221/VOH单体的转化率和转化速率。另外，化合物(I-1)至(I-3)在0-3mol％添加范围内，可以明显提高单体E4221/VOH的转化率，其最大转化率达到了75％。其中810和ITX各自的浓度均基于化合物(I-1)至(I-3)各自的摩尔含量。因此本发明化合物可以提高E4221/VOH单体的光聚合性能。
实施例7
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。
称取X1mol的上述有机硅单体(化合物(I-1)至(I-3))，X2mol的E4221，X3mol的VOH，X4mol的光引发剂六氟磷酸二苯基碘鎓盐(810)和X5mol的增感剂2-异丙基硫杂蒽酮(ITX)加入到棕色瓶中并搅拌均匀，避光保存，配方各组分摩尔比例为：单体(X1):E4221(X2):VOH(X3):810(X4):ITX(X5)＝X1:50:50:0.5:0.25(均为摩尔比)。在2mm×4mm×17mm的聚四氟乙烯模具中加入搅拌均匀的感光液，然后将模具放置于汞灯下照射(光强为20mW cm-2)，照射时间900s后取出固化膜，进行水接触角测试。
采用DSA25型水接触角测定仪对光固化膜的表面疏水性进行表征，测试温度为25℃。同时，利用同样方法制备空白E4221/VOH固化膜作为参比。参比和在化合物(I-1)至(I-3)存在下的结果见图4-6。
由图4-6可见，当E4221/VOH聚合体系不添加本发明化合物时，固化膜的水接触角为56.9°，而额外加入化合物(I-1)至(I-3)后，固化膜的水接触角明显提高。
实施例8
按照实施例7中所述完全相同的方法分别制得在化合物(I-1)至(I-3)存在下各自的固化膜。然后采用热失重分析仪测定各光固化膜的耐热性。测试条件为：氮气保护下，温度范围30-700℃，升温速度为10℃/min。同时，利用同样方法制备空白E4221/VOH固化膜作为参比。其结果见表1和图7。
由表1和图7可见，加入化合物(I-1)至(I-3)中任何一种后，固化膜的初始分解温度(T5％)及最大热失重温度Tmax1明显提高，同时最大热失重温度Tmax2也有所提高或保持相当，因而耐热性明显被改善。
表1
实施例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。
按照实施例7中所述完全相同的方法分别制得在化合物(I-1)至(I-3)存在下各自的固化膜。然后采用电子万能试验机测试进行光固化膜的拉伸性能测试。测试温度为25℃，测试速度为1mm/min。同时，利用同样方法制备空白E4221/VOH固化膜作为参比。其结果见图8。
由图8可见，纯E4221/VOH光固化膜的拉伸强度为0.26MPa，断裂伸长率为22.96％。额外加入化合物(I-1)至(I-3)作为单体后，光固化膜的拉伸强度变化较小，断裂伸长率分别增至54.17％、60.22％和68.51％，增加至3倍左右。因此，本发明化合物能够明显改善固化膜的拉伸性能。

Claims (10)

  1. 下式(Ⅰ)化合物：
    n为1-50的整数；
    m为0-20的整数；
    R1为C1-C12烷基或者C1-C12烷氧基；
    R2、R3和R4相同或不同，并独立地为C6-C10芳基、C1-C12烷基、C1-C12烷氧基或者两个碳原子之间插有一个或多个独立地选自NRa、O或S的杂原子的C2-C12烷基，其中Ra为H或C1-C4烷基，例如C1-C6烷氧基-C1-C6烷基、C1-C6烷基氨基-C1-C6烷基或C1-C6烷硫基-C1-C6烷基。
  2. 根据权利要求1的化合物，其中
    n为1-20，优选2-18的整数；和/或
    m为0-8，优选0-5，更优选0-3的整数；和/或
    R1为C1-C6烷基或者C1-C6烷氧基；R1优选为C1-C4烷基或者C1-C4烷氧基；和/或
    R2、R3和R4相同或不同，并独立地为C6-C10芳基、C1-C6烷基、C1-C6烷氧基或者两个碳原子之间插有一个或多个选自NRa、O或S的杂原子的C2-C6烷基，其中Ra为H或C1-C4烷基，例如C1-C3烷氧基-C1-C3烷基、C1-C3烷基氨基-C1-C3烷基或C1-C3烷硫基-C1-C3烷基；优选的是，R2、R3和R4相同或不同，并独立地为苯基、C1-C4烷基、C1-C4烷氧基或者两个碳原子之间插有一个或多个独立地选自NRa、O或S的杂原子的C2-C4烷基，其中Ra为H或C1-C4烷基，例如C1-C2烷氧基-C1-C2烷基、C1-C2烷基氨基-C1-C2烷基或C1-C2烷硫基-C1-C2烷基。
  3. 根据权利要求1的化合物，其中
    n为3-15的整数；
    m为0-5的整数；
    R1为C1-C4烷基或者C1-C4烷氧基；
    R2、R3和R4相同或不同，并独立地为苯基、C1-C4烷基、C1-C4烷氧基或者两 个碳原子之间插有一个或多个选自NRa、O或S的杂原子的C2-C4烷基，其中Ra为H或C1-C4烷基，例如C1-C2烷氧基-C1-C2烷基、C1-C2烷基氨基-C1-C2烷基或C1-C2烷硫基-C1-C2烷基；
    优选的是，
    n为3-15的整数；
    m为0-5的整数；
    R1为C1-C4烷基；
    R2、R3和R4相同或不同，并独立地为C1-C4烷基。
  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：

  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，包括使式(II)化合物：
    其中n、R1、R2、R3和R4如权利要求1-4中任一项所定义，
    与式(III)化合物反应：
    其中m如权利要求1-4中任一项所定义，
    得到式(I)化合物。
  6. 根据权利要求5的方法，其中
    式(II)化合物与式(III)化合物的反应在Karstedt催化剂或Speier催化剂存在下进行，优选的是，所述催化剂的用量基于式(II)化合物的重量为2-100ppm；和/或
    式(II)化合物与式(III)化合物的用量摩尔比为1:1-1:1.5；和/或
    式(II)化合物与式(III)化合物之间的反应在80-110℃，优选85-100℃下进行；和/或
    式(II)化合物与式(III)化合物之间的反应进行3-6小时，优选3.5-5.5小时。
  7. 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)化合物作为可聚合单体。
  8. 根据权利要求7的可光固化组合物，其为光固化涂料组合物、光固化油墨组合物或光致抗蚀组合物。
  9. 根据权利要求7或8的可光固化组合物，还包含用于开环聚合的阳离子光引发剂以及任选地其它含有乙烯基醚双键、脂环族环氧基或氧杂环烷基如环氧乙烷基或者氧杂环丁烷基的单体或低聚物，例如3,4-环氧环己基甲基3,4-环氧环己基甲酸酯(E4221)或4-乙烯基环氧环己烷(VOH)。
  10. 一种光固化材料，所述材料通过将根据权利要求7-9中任一项的可光固化组合物光固化而获得。
PCT/CN2023/122140 2022-09-30 2023-09-27 三氟甲基有机硅脂环族环氧单体及其制备和应用 WO2024067720A1 (zh)

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