WO2024067719A1 - Monomère d'oxacycloalcane de trifluorométhyle et d'organosilicium, sa préparation et son utilisation - Google Patents

Monomère d'oxacycloalcane de trifluorométhyle et d'organosilicium, sa préparation et son utilisation Download PDF

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WO2024067719A1
WO2024067719A1 PCT/CN2023/122139 CN2023122139W WO2024067719A1 WO 2024067719 A1 WO2024067719 A1 WO 2024067719A1 CN 2023122139 W CN2023122139 W CN 2023122139W WO 2024067719 A1 WO2024067719 A1 WO 2024067719A1
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compound
alkyl
formula
alkoxy
reaction
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PCT/CN2023/122139
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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
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of 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; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the technical field to which the present invention belongs is the field of photocurable materials, and specifically relates to a trifluoromethyl organosiloxane 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 organic silicon and organic fluorine, and have outstanding thermal stability, corrosion resistance, 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, so it is urgent to develop new cationic fluorosilicone monomers.
  • the expensive cost and complex synthesis procedures required to prepare fluorosilicone monomers and polymers hinder their widespread application. Based on this, the development of a series of relatively low-cost and hydrophobic cationic fluorosilicone 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 organosiloxane monomers, which have the advantages of good tensile properties, excellent hydrophobic properties, anti-fouling, anti-fingerprint, etc. after photocuring.
  • the inventors have found that by introducing polysiloxane chains and trifluoromethyl groups into epoxy monomers, the trifluoromethyl organosiloxane monomers obtained in this way have 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 organosiloxane monomer, which contains not only a cationic photocurable group but also a polysiloxane chain and a trifluoromethyl group.
  • the fluorosilicone monomer having 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 organosiloxane 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 trifluoromethylorganosiloxane 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;
  • p is an integer from 1 to 6;
  • q is an integer from 0 to 4.
  • R 1 is C 1 -C 12 alkyl or C 1 -C 12 alkoxy
  • R 2 , R 3 and R 4 are the same or different and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, or C 2 -C 12 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, for example C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkylamino-C 1 -C 6 alkyl or C 1 -C 6 alkylthio-C 1 -C 6 alkyl; and
  • R 5 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.
  • n is an integer of 1-20, preferably 2-18;
  • n is an integer of 1-8, preferably 1-5, more preferably 1-3;
  • p is an integer from 1 to 4, for example, 1, 2 or 3;
  • q is an integer from 0 to 3, for example, 0, 1 or 2;
  • 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
  • R 5 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.
  • n is an integer from 3 to 15;
  • n is an integer from 1 to 5;
  • p is 1, 2, or 3;
  • q is 0 or 1
  • 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 ; and
  • R 5 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;
  • n is an integer from 3 to 15;
  • n is an integer from 1 to 5;
  • p 1;
  • q is 0 or 1
  • 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
  • R 5 is H or 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.
  • X is halogen, such as fluorine, chlorine, bromine or iodine,
  • the reaction of the compound of formula (IV) with the compound of formula (V) 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 (IV) to the basic catalyst is 1:1-1:3; and/or
  • the molar ratio of the compound of formula (IV) to the compound of formula (V) is 1:1-1:1.2; and/or
  • reaction between the compound of formula (IV) and the compound of formula (V) is carried out at 80-120° C., preferably 100-120° C.; and/or,
  • reaction between the compound of formula (IV) and the compound of formula (V) is carried out for 6-12 hours, preferably 8-10 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 9 which is a photocurable coating composition, a photocurable ink composition or a photoresist composition.
  • the photocurable composition according to item 9 or 10 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 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221) or 4-vinylepoxycyclohexane (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 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221) or 4-vinylepoxycyclohexane (VOH).
  • FIG1 is a graph showing the change in epoxy group conversion rate with irradiation time in the presence of compound (I-1) prepared in Example 1.
  • FIG. 2 is a graph showing the change in epoxy group conversion rate with irradiation time in the presence of compound (I-2) prepared in Example 2.
  • FIG3 is a graph showing the change in epoxy group conversion rate 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.
  • FIG9 is a graph showing the change in epoxy group conversion rate with irradiation time in the presence of compound (I-6) prepared in Example 10.
  • FIG. 10 is a graph showing the change in epoxy group conversion rate with irradiation time in the presence of compound (I-7) prepared in Example 11.
  • FIG. 11 is a graph showing the change in epoxy group conversion rate with irradiation time in the presence of compound (I-8) prepared in Example 12.
  • FIG. 15 is a thermogravimetric graph of a blank E4221/VOH system cured film and a cured film in the presence of compounds (I-6) to (I-8) prepared in each of Examples 10-12.
  • FIG. 16 is a graph showing mechanical properties of a blank E4221/VOH system cured film and a cured film in the presence of compounds (I-6) to (I-8) prepared in Examples 10-12, respectively.
  • n is an integer from 1 to 50;
  • n is an integer from 0 to 20;
  • p is an integer from 1 to 6;
  • q is an integer from 0 to 4.
  • R 1 is C 1 -C 12 alkyl or C 1 -C 12 alkoxy
  • R 2 , R 3 and R 4 are the same or different and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, or C 2 -C 12 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, for example C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkylamino-C 1 -C 6 alkyl or C 1 -C 6 alkylthio-C 1 -C 6 alkyl; and
  • R 5 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.
  • 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-ethylpropyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, C 1 -C 6 al
  • C 1 -C 4 -alkyl may 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 group refers to a monocyclic, bicyclic or higher number of aromatic hydrocarbon groups containing 6 to m carbon atoms, for example 6 to 10 carbon atoms.
  • C 6 -C m aryl groups there may be mentioned phenyl, tolyl, ethylphenyl, Propylphenyl, butylphenyl, xylyl, methylethylphenyl, diethylphenyl, methylpropylphenyl and naphthyl, etc.; 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.
  • Cn - Cm- haloalkyl refers to a Cn - Cm- alkyl group substituted by one or more identical or different halogen atoms, for example a C1 - C12- haloalkyl group, preferably a C1 - C6- haloalkyl group, and particularly preferably a C1 - C4- haloalkyl group.
  • Cn - Cm- haloalkyl groups mention may be made of monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, dichloromethylethyl, monochlorobutyl, dichloromethylpropyl, trichloromethylpropyl, monochloropentyl, dichloromethylbutyl, monochlorohexyl and isomers thereof, in particular 1-chloromethylethyl, 1,1-dichloromethylethyl, 1-chloromethylpropyl, 2-chloromethylpropyl, 1,1-dichloromethylpropyl, 1,2-dichloromethylpropyl, 2,2-dichloromethylpropyl, 1,1,2-trichloromethylpropyl, 1,2 ...
  • Cn - Cm haloalkoxy refers to a Cn - Cm alkoxy group substituted by one or more identical or different halogen atoms, for example a C1 - C12 haloalkoxy group, more preferably a C1 - C6 haloalkoxy group, and especially preferably a C1 - C4 haloalkoxy group.
  • Cn - Cm haloalkoxy groups there may be mentioned monochloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 4-chlorobutoxy, 5-chloropentyloxy, 6-chlorohexyloxy and isomers thereof, in particular monochloromethoxy, 2-chloroethoxy, 3-chloro-n-propoxy, 2-chloroisopropoxy, 4-chloro-n-butoxy, 3-chloro-sec-butoxy, 2-chloro-tert-butoxy, 5-chloro-n-pentyloxy, 4-chloroisopentyloxy, 6-chloro-n-hexyloxy and the like.
  • Cn - Cm hydroxyalkyl refers to a Cn - Cm alkyl group having a hydroxyl group bonded to any carbon atom of the open-chain Cn-Cm alkane corresponding to the Cn- Cm alkyl group, for example a C1 - C6 hydroxyalkyl group, particularly preferably a C1 - C4 hydroxyalkyl group, such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group and isomers thereof, in particular a hydroxymethyl group, a hydroxyethyl group, a hydroxyn-propyl group, a hydroxyisopropyl group, a hydroxyn-butyl group, a hydroxysec-butyl group, a hydroxytert-butyl group, a hydroxyn-pent
  • 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 1-8, particularly preferably 1-5 or 1-3, for example 1, 2, 3, 4 or 5.
  • p is generally an integer of 1-6, preferably 1-4, for example 1, 2 or 3.
  • q is usually an integer of 0-4, preferably 0-3, for example 0, 1 or 2.
  • 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 alkyl, for example C1 - C3 alkoxy- C1 - C3 alkyl, C1- C3 alkylamino- C1 - C3 alkyl or C1 - C3 alkylthio- C1 - C3 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.
  • R 5 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 5 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.
  • R 5 is H or C 1 -C 4 alkyl.
  • R 5 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, hydroxy-isopropyl, hydroxy-n-butyl, hydroxy-sec-butyl or hydroxy-tert-butyl.
  • n is an integer from 3 to 15;
  • n is an integer from 1 to 5;
  • p is 1, 2, or 3;
  • q is 0 or 1
  • 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 ; and
  • R 5 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.
  • 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 called trifluoromethyl hydrogen-containing 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 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 Karstedt catalyst or Speier catalyst is generally used.
  • the amount of catalyst used is also conventional. Generally speaking, based on the weight of the compound of formula (II), the amount of catalyst used is 2-100ppm.
  • the reaction of the compound of formula (II) with the compound of formula (III) is generally carried out in a solvent.
  • a solvent As the type of solvent, there is no particular restriction, 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 product, that is, the precipitation of 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, 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 usually used in approximately equimolar amounts.
  • the molar ratio of the compound of formula (II) to the compound of formula (III) is 1:1-1:1.5.
  • the compound of formula (II) and the catalyst are usually 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 usually carried out at an elevated temperature, usually aged at 40-70°C. The aging time is usually 30-60 minutes.
  • the reaction temperature between the compound of formula (II) and the compound of formula (III) is usually 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 usually 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.
  • X is halogen, such as fluorine, chlorine, bromine or iodine,
  • the reaction of the hydroxyl group in the compound of formula (IV) with the halogen in the compound of formula (V) belongs to the reaction type known in the art, and the reaction produces hydrogen halide.
  • the reaction is carried out in the presence of a basic catalyst.
  • a basic catalyst suitable for the reaction for example, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof can be mentioned.
  • the amount of catalyst used is also conventional.
  • the molar ratio of the amount of the compound of formula (IV) to the basic catalyst is 1:1-1:3.
  • the reaction of the compound of formula (IV) with the compound of formula (V) is usually carried out in a solvent.
  • the solvent is also conducive to the product, that is, the precipitation of the compound of formula (III).
  • an organic solvent is generally used, preferably toluene, acetone, butanone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile or any mixture thereof.
  • the amount of solvent used is also conventional.
  • the amount of solvent used is 0.5-3 times the total weight of the compound of formula (IV) and the compound of formula (V).
  • the compound of formula (IV) and the compound of formula (V) are usually used in roughly equimolar amounts.
  • the molar ratio of the compound of formula (IV) to the compound of formula (V) is 1:1-1:1.2.
  • the compound of formula (IV), the compound of formula (V) and the catalyst are usually dissolved in a solvent, and then the temperature is raised to the reaction temperature for a period of time to obtain the compound of formula (III).
  • the reaction temperature between the compound of formula (IV) and the compound of formula (V) is usually 80-120°C, preferably 100-120°C.
  • the retention time of the reaction between the compound of formula (IV) and the compound of formula (V) at the reaction temperature is usually 6-12 hours, preferably 8-10 hours.
  • the reaction is advantageously carried out under stirring.
  • the compound of formula (III) is obtained by conventional post-treatment.
  • the post-treatment generally includes washing (e.g., washing with water, advantageously followed by dehydration with a water-absorbing compound such as magnesium sulfate or sodium sulfate), filtering or centrifuging to remove solid impurities, rotary evaporation to remove the solvent, and further distillation under reduced pressure to remove the solvent. If a higher purity product is to be obtained, recrystallization may also be performed.
  • 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.
  • the photocurable composition may also comprise a cationic photoinitiator for ring-opening polymerization (a photoinitiator capable of initiating cationic polymerization) and optionally other monomers or oligomers containing cationic photocurable groups such as vinyl ether double bonds, alicyclic epoxy groups or oxacycloalkyl groups, 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
  • optionally other monomers or oligomers containing cationic photocurable groups such as vinyl ether double bonds, alicyclic epoxy groups or oxacyclo
  • the photocurable composition of the present invention may 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 comprise 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, merocyanine dyes may be mentioned; preferably benzophenone and its derivatives, thioxanthone and its
  • 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 is provided, which is 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 because it contains the compound of formula (I) of the present invention as a photocurable monomer.
  • reaction solution was cooled to room temperature, and part of the toluene was evaporated by rotary evaporation; the solution was then distilled under reduced pressure to obtain the product. Characterization by nuclear magnetic hydrogen spectrum confirmed that it was compound (I-1), hereinafter referred to as GE-FSi 3 .
  • reaction solution was cooled to room temperature, and part of the toluene was evaporated with a rotary evaporator; the solution was then distilled under reduced pressure to obtain the product. Characterization by nuclear magnetic hydrogen spectrum confirmed that it was compound (I-2), hereinafter referred to as GE-FSi 6 .
  • reaction solution was cooled to room temperature, and part of the toluene was evaporated by rotary evaporation; the solution was then distilled under reduced pressure to obtain the product. Characterization by nuclear magnetic hydrogen spectrum confirmed that it was compound (I-3), hereinafter referred to as GE-FSi 9 .
  • reaction solution was cooled to room temperature, and part of the toluene was evaporated by rotary evaporation; the solution was then distilled under reduced pressure to obtain the product. Characterization by nuclear magnetic hydrogen spectrum confirmed that it was compound (I-5), hereinafter referred to as GE-FSi 15 .
  • 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 water contact angle of the cured film is 56.9°, while after the additional addition of compounds (I-1) to (I-3), the water contact angle of the cured film is significantly increased. Therefore, the compound of the present invention can significantly improve the surface hydrophobicity of the cured film, thereby resisting staining and fingerprints.
  • 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 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 41.22%, 44.76% and 46.33%, respectively, which increases to about 2 times. Therefore, the compounds of the present invention can significantly improve the tensile properties of the cured film.
  • the rotary evaporator was used for rotary evaporation at a temperature of 45°C and a pressure of 0.1 MPa, and the resulting solution was then distilled under reduced pressure at 300 Pa and 40°C to obtain compound (III-1) with a yield of 50%.
  • reaction solution was cooled to room temperature, and part of the toluene was evaporated with a rotary evaporator; the solution was then distilled under reduced pressure to obtain the product. Characterized by nuclear magnetic hydrogen spectrum, it was determined to be compound (I-7), hereinafter referred to as XE-FSi 6 .
  • reaction solution was cooled to room temperature, and part of the toluene was evaporated with a rotary evaporator; the solution was then distilled under reduced pressure to obtain the product. Characterized by nuclear magnetic hydrogen spectrum, it was determined to be compound (I-8), hereinafter referred to as XE-FSi 9 .
  • reaction solution was washed three times with distilled water, the supernatant was taken, and the solid impurities were removed by centrifugation, and then the solution was evaporated at a temperature of 45°C and a pressure of 0.1 MPa by rotary evaporation, and then the obtained solution was distilled under reduced pressure at 300 Pa and 40°C to obtain compound (III-2) with a yield of 50%.
  • 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-6) to (I-11) 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-6) to (I-8) are shown in Figures 12-14.
  • the water contact angle of the cured film is 56.9°, while after the additional addition of compounds (I-6) to (I-8), the water contact angle of the cured film is significantly
  • the contact angle of the cured film obtained by adding one of the compounds (I-9) to (I-11) is more than 85°. Therefore, the compound of the present invention can significantly improve the surface hydrophobicity of the cured film, thereby resisting staining and fingerprints.
  • the cured films of each of the compounds (I-6) to (I-8) were prepared in the presence of the same method as described in Example 17.
  • 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 2 and Figure 15.
  • 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 compounds (I-6) to (I-8) were prepared in the presence of the same method as described in Example 17.
  • 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 16.
  • 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 67.87%, 69.92% and 70.64%, respectively, which increases by more than 3 times. Therefore, the compounds of the present invention can significantly improve the tensile properties of the cured film.

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Abstract

La présente invention concerne un composé de formule (I), dans laquelle les variables de n, m, p, q, R1, R2, R3, R4 et R5 sont telles que définies dans la description. Le composé de formule (I) est photopolymérisable ; et après avoir été photodurci, le composé présente les avantages de bonnes propriétés de traction, de bonnes propriétés hydrophobes, de résistance aux taches, de résistance aux empreintes digitales, de résistance à la corrosion chimique, de bonne résistance à la chaleur, etc. La présente invention concerne en outre la préparation du composé de formule (I), une composition photodurcissable comprenant le composé de formule (I), et un matériau photodurci obtenu par photodurcissement de la composition photodurcissable.
PCT/CN2023/122139 2022-09-30 2023-09-27 Monomère d'oxacycloalcane de trifluorométhyle et d'organosilicium, sa préparation et son utilisation WO2024067719A1 (fr)

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