WO2022267989A1 - Eugenol bio-based silicon-containing oxetane monomer and preparation method therefor - Google Patents

Eugenol bio-based silicon-containing oxetane monomer and preparation method therefor Download PDF

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WO2022267989A1
WO2022267989A1 PCT/CN2022/099400 CN2022099400W WO2022267989A1 WO 2022267989 A1 WO2022267989 A1 WO 2022267989A1 CN 2022099400 W CN2022099400 W CN 2022099400W WO 2022267989 A1 WO2022267989 A1 WO 2022267989A1
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compound
formula
alkyl
alkylene
alkoxy
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PCT/CN2022/099400
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French (fr)
Chinese (zh)
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孙芳
杨宗鑫
邹应全
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湖北固润科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • 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 System
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
    • 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 System
    • 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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the invention relates to the field of photocurable materials, in particular to a eugenol bio-based silicon-containing oxetane monomer.
  • the present invention also relates to a preparation method of the monomer, a photocurable composition comprising the monomer and a photocurable material obtained from the photocurable composition.
  • Photopolymerization technology is the process of using light to initiate the conversion of liquid oligomers or monomers with active substances into solid products. Compared with traditional thermal polymerization technology, photopolymerization can achieve efficient and pollution-free production without using volatile organic solvents, saving a lot of energy. Therefore, photopolymerization technology is regarded as a green process because of its unique low energy consumption requirements, fast curing, solvent-free formula, no pollution, room temperature treatment and environmental protection, so it is widely used in photocuring coatings, adhesives and printing inks. and other fields are widely used.
  • oxetane monomer is a cationic photocuring system.
  • Oxycyclane monomer is the main raw material of high-end cationic photocurable products. This system not only has low viscosity and low toxicity.
  • people have put forward higher requirements for the heat resistance, water repellency, surface anti-staining, corrosion resistance and anti-fingerprint of photo-curing materials. Require. Consumers are increasingly demanding the appearance of products. In addition to beautiful colors and comfortable handles, they also require the surface to have anti-fingerprint and anti-stain properties. was wiped clean.
  • the base material is prepared from the base material, with fast polymerization rate. After photocuring, it has the advantages of good tensile properties, good heat resistance, excellent hydrophobic properties, anti-staining, and anti-fingerprints.
  • the present inventors unexpectedly found that the cationic photopolymerizable eugenol bio-based silicon-containing oxetane monomer of formula (I) of the present invention has good polymerization rate and conversion rate and promotes the synthesis of other cationic monomers. Polymerization, and the photocurable material obtained therefrom has good mechanical properties, especially tensile properties and thermal stability, excellent hydrophobic properties and anti-staining and anti-fingerprints.
  • the monomer has a good polymerization rate and conversion rate and promotes the polymerization of other cationic monomers, and the photocurable material obtained therefrom has good mechanical properties, especially tensile properties and heat resistance, excellent hydrophobic properties, and Stain, anti-fingerprint, anti-chemical corrosion, strong anti-aging performance.
  • Another object of the present invention is to provide a method for preparing the eugenol bio-based silicon-containing oxetane monomer of the present invention.
  • the preparation method is simple and easy, the conditions are mild, the raw materials are readily available and the price is low.
  • Yet another object of the present invention is to provide a photocurable composition comprising the eugenol bio-based silicone-containing oxetane monomer according to the present invention.
  • Another object of the present invention is to provide a photocurable material obtained from the photocurable composition of the present invention.
  • Another object of the present invention is to provide the use of the compound of formula (I) of the present invention in photocurable coatings, adhesives and inks.
  • n 1-50;
  • L is a direct bond or a divalent linking group with 1-30 carbon atoms
  • R 1 , R 2 , R 3 , R 4 , R 5 are the same or different, and are independently organic groups with 1-12 carbon atoms;
  • R 6 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 1-30;
  • R 1 is C 1 -C 12 alkyl or C 1 -C 12 alkoxy
  • R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and are independently represented by one or more C 2 -C 12 alkyl separated by non-adjacent heteroatoms selected from NR a , O, S, or C separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S 2 -C 12 alkoxy, and
  • L is a direct bond, C 1 -C 30 alkylene, C 1 -C 30 alkyleneoxy, C 2 - separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S C 30 alkylene, or C 2 -C 30 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S,
  • R a is H or C 1 -C 4 alkyl.
  • - m is 1-20, preferably 2-15;
  • 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;
  • R a is H or C 1 -C 4 alkyl; preferably, R 2 , R 3 , R 4 , R 5 , the same or different, and independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or one or more independently selected from NR a , O, S C 2 -C 4 alkyl interspersed by non-adjacent heteroatoms, wherein R a is H or C 1 -C 4 alkyl;
  • -R 6 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 ;
  • -L is C 2 -C 30 alkylene, C 2 -C 30 alkyleneoxy, C 2 -C 30 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S Alkylene, or C 2 -C 30 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkane base.
  • n 1-9;
  • R 1 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy
  • R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or one or more independently selected from NR a , C 1 -C 4 alkyl separated by non-adjacent heteroatoms of O, S, wherein R a is H or C 1 -C 4 alkyl;
  • R 6 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; as well as
  • L is L 1 -OL 2 , wherein L 1 and L 2 are independently a divalent linking group with 1-20, preferably 1-15 carbon atoms, more preferably C 1 -C 15 alkylene;
  • n 3-9;
  • R 1 is C 1 -C 4 alkyl
  • R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently C 1 -C 4 alkyl;
  • R 6 is H or C 1 -C 4 alkyl
  • L is L 1 -OL 2 , wherein L 1 and L 2 are independently C 1 -C 6 alkylene.
  • L is L 1 -OL 2 , wherein L 1 and L 2 are independently of each other a divalent linking group having 1-20, preferably 1-15 carbon atoms, more preferably C 1 -C 15 alkylene, especially C 1 -C 6 alkylene.
  • L is a divalent linking group having 1-20 , preferably 1-15 carbon atoms, more preferably C 1 -C 15 alkylene, especially C 1 -C 6 alkylene, and X is halogen , such as fluorine, chlorine, bromine or iodine,
  • L 2 is a divalent linking group having 1-20, preferably 1-15 carbon atoms, more preferably a C 1 -C 15 alkylene group, especially a C 1 -C 6 alkylene group, R 6 is as in paragraph as defined in any one of items 1-5, and X is halogen, such as chlorine, bromine or iodine.
  • reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a basic catalyst, preferably sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, More preferably, the molar ratio of the compound of formula (II) to the basic catalyst is 1:1-1:5;
  • reaction between the compound of formula (II) and the compound of formula (III) is carried out at 30-120°C, preferably 40-70°C;
  • reaction between the compound of formula (II) and the compound of formula (III) is carried out for 3-16 hours, preferably 4-10 hours.
  • reaction of the compound of formula (IV) with the compound of formula (VI) is carried out in the presence of a basic catalyst, preferably sodium hydride, 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 1:1-1:5;
  • reaction between the compound of formula (IV) and the compound of formula (VI) is carried out at 40-100°C, preferably at 60-90°C; preferably, the reaction is carried out for 3-24 hours, preferably 4-10 hours.
  • reaction of the compound of formula (VI) with the compound of formula (VII) is carried out in the presence of Karstedt catalyst or SpeIer catalyst, preferably, the amount of catalyst is 2-500ppm based on the weight of formula (VII);
  • reaction between the compound of formula (VI) and the compound of formula (VII) is carried out at 80-110°C, preferably 85-100°C;
  • reaction between the compound of formula (VI) and the compound of formula (VII) is carried out for 3-6 hours, preferably 3.5-5.5 hours.
  • a photocurable composition comprising a compound of formula (I) according to any one of items 1-5 as a polymerizable monomer.
  • Fig. 1 is a graph showing the change of E4221 conversion rate with irradiation time in the system containing compound 1 prepared in Example 1.
  • Fig. 2 is a graph showing the change of E4221 conversion rate with irradiation time in the system containing compound 2 prepared in Example 2.
  • Fig. 3 is a graph showing the change of E4221 conversion rate with irradiation time in the system containing compound 3 prepared in Example 3.
  • FIG. 4 is a graph showing the conversion rate of Compound 1 in the system containing Compound 1 prepared in Example 1 as a function of irradiation time.
  • Fig. 5 is a graph of the conversion of compound 2 in the system containing compound 2 prepared in Example 2 as a function of irradiation time.
  • Fig. 6 is a graph showing the conversion of compound 3 in the system containing compound 3 prepared in Example 3 as a function of irradiation time.
  • Fig. 7 is a contact angle graph of a blank E4221 cured film and a cured film of a system comprising compounds 1-3 prepared in each of Examples 1-3.
  • Fig. 8 is a thermogravimetric graph of cured films of blank E4221 and cured films of systems comprising compounds 1-3 prepared in each of Examples 1-3.
  • Fig. 9 is a graph showing the mechanical properties of a blank E4221 cured film and a cured film of a system containing compounds 1-3 prepared in each of Examples 1-3.
  • a numerical range is used to indicate a range in which the numerical values described before and after are taken as the minimum value and the maximum value, respectively.
  • n 1-50;
  • L is a direct bond or a divalent linking group with 1-30 carbon atoms
  • R 1 , R 2 , R 3 , R 4 , R 5 are the same or different, and are independently organic groups with 1-12 carbon atoms;
  • R 6 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 prefix "C n -C m " indicates 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, it is preferred that the halogen includes fluorine, chlorine or a combination thereof.
  • C n -C m alkyl refers to a branched or unbranched saturated hydrocarbon group having nm, such as 1-12, preferably 1-6, particularly preferably 1-4 carbon atoms, such as Methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methyl Butyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2- Dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethyl Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,
  • the C 1 -C 6 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl and isomers thereof.
  • C 1 -C 4 Alkyl can be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl groups and their isomers.
  • C 6 -C m aryl refers to a monocyclic, bicyclic or multicyclic aromatic hydrocarbon group containing 6-m carbon atoms, for example 6-10 carbon atoms.
  • C 6 -C m aryl groups mention may be made of phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methylethylphenyl, diethylphenyl, Methyl-propylphenyl and naphthyl, etc.; preferably phenyl or naphthyl, especially phenyl.
  • C n -C m alkoxy refers to a C n -C m alkyl corresponding to any carbon atom of an open chain C n -C m alkane bonded with an oxygen atom as a linking group C n -C m alkyl, such as C 1 -C 12 alkoxy, more preferably C 1 -C 6 alkoxy, especially preferably C 1 -C 4 alkoxy.
  • C 1 -C 6 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentyloxy, isopentyloxy group, hexyloxy group and its isomers.
  • C 1 -C 4 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and its isomers body.
  • C n -C m haloalkyl refers to C n -C m alkyl substituted by one or more same or different halogen atoms, such as C 1 -C 12 haloalkyl, preferably C 1 -C 6 Haloalkyl, particularly preferably C 1 -C 4 haloalkyl.
  • Cn- Cm haloalkyl groups mention may be made of monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, 1-chloromethylethyl, monochlorobutyl Base, 1-chloromethylpropyl, 2-chloromethylpropyl, 1,1-dichloromethylethyl, 1-chloropentyl, 1-chloromethylbutyl, 2-chloromethylbutyl, 3-chloromethylbutyl, 2,2-dichloromethylpropyl, 1-chloroethylpropyl, monochlorohexyl, 1,1-dichloromethylpropyl, 1,2-dichloromethyl Propyl, 1-chloromethylpentyl, 2-chloromethylpentyl, 3-chloromethylpentyl, 4-chloromethylpentyl, 1,1-dichloromethylbutyl, 1,
  • C n -C m haloalkoxy refers to C n -C m alkoxy substituted by one or more same or different halogen atoms, such as C 1 -C 12 haloalkoxy, more preferably C 1 -C 6 haloalkoxy, especially preferably C 1 -C 4 haloalkoxy.
  • C n -C m haloalkoxy mention may be made of monochloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 2-chloroisopropoxy, 4-chloro-n-butoxy , 3-chloro-sec-butoxy, 2-chloro-tert-butoxy, 5-chloropentyloxy, 4-chloroisoamyloxy, 6-chlorohexyloxy and its isomers.
  • C n -C m hydroxyalkyl refers to a C n -C m that has a hydroxyl group bonded to any carbon atom of an open chain C n -C m alkane corresponding to a C n -C m alkyl group.
  • Alkyl such as C 1 -C 6 hydroxyalkyl, especially preferably C 1 -C 4 hydroxyalkyl, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, hydroxybutyl, hydroxypentyl, Hydroxyhexyl and its isomers.
  • C 1 -C 30 alkylene as used herein includes C 1 -C 26 alkylene, C 1 -C 18 alkylene, C 1 -C 12 alkylene, C 1 -C 6 alkylene, C 2 -C 26 alkylene, C 2 -C 18 alkylene, C 2 -C 12 alkylene, C 2 -C 6 alkylene, C 3 -C 26 alkylene, C 3 -C 18 alkylene Alkyl, C 3 -C 12 alkylene or C 3 -C 6 alkylene.
  • C 1 -C 30 alkyleneoxy as used herein includes C 1 -C 26 alkyleneoxy, C 1 -C 18 alkyleneoxy, C 1 -C 12 alkyleneoxy, C 1 -C 6 alkylene Alkoxy, C 2 -C 26 Alkyleneoxy, C 2 -C 18 Alkyleneoxy, C 2 -C 12 Alkyleneoxy, C 2 -C 6 Alkyleneoxy, C 3 -C 26 Alkylene Alkoxy, C 3 -C 18 alkyleneoxy, C 3 -C 12 alkyleneoxy or C 3 -C 6 alkyleneoxy.
  • the propylene group between the silicon and the benzene ring in the compound of formula (I) may be -CH 2 -CH 2 -CH 2 - or -CH(CH 3 )-CH 2 -, and is preferably -CH( CH3 ) -CH2- .
  • m is generally 1-50, such as 1-40, 1-30, 1-20, 1-18, 1-15, 1-12, 1-9, 2-40, 2-30, 2- 20, 2-18, 2-15, 2-12, 2-9, 3-40, 3-30, 3-20, 3-18, 3-15, 3-12 or 3-9, such as 3, 4, 5, 6, 7, 8 or 9.
  • R 1 , R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently an organic group with 1-12 carbon atoms, such as an organic group with 1-6 or 1-4 carbon atoms .
  • R 1 is usually C 1 -C 12 alkyl or C 1 -C 12 alkoxy.
  • R 1 is C 1 -C 6 alkyl or C 1 -C 6 alkoxy.
  • R 1 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy.
  • R 1 is C 1 -C 4 alkyl.
  • R 1 is methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl or tert-butyl.
  • R 2 , R 3 , R 4 , and R 5 are the same or different, and are usually independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 Alkoxy or C 1 -C 12 alkyl interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
  • R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or replaced by one or multiple non-adjacent heteroatom-interrupted C 1 -C 6 alkyl groups independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
  • R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or replaced by one or more independently A C 1 -C 4 alkyl group selected from NR a , O, S with non-adjacent heteroatom intervals, wherein R a is H or C 1 -C 4 alkyl.
  • R 2 , R 3 , R 4 , R 5 are the same or different, and are independently C 1 -C 4 alkyl.
  • R 2 , R 3 , R 4 , and R 5 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.
  • non-adjacent heteroatom means that there is a non-adjacent heteroatom between two carbon atoms, for example, two carbon atoms of the divalent linking group.
  • an ethylene group interrupted by O can be represented as: -CH2 - O-CH2-.
  • R 6 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 6 is H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkoxy or C 1 -C 4 Haloalkoxy. It is particularly preferred that R 6 is H or C 1 -C 4 alkyl.
  • R can be H, chloro, bromo, methyl, ethyl, n - propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy , isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxy-sec-butyl or hydroxy tert-butyl.
  • L is a direct bond or a divalent linking group with 1-30 carbon atoms, for example with 1-28, 1-18, 1-12, 2-30, 2-28, 2-18 or 2 - a divalent linking group of 12 carbon atoms, for example a divalent linking group having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms.
  • the divalent linking group has one or more non-adjacent heteroatoms independently selected from NR a , O, S, preferably O, wherein R a is H or C 1 -C 4 alkyl.
  • L is a direct bond, C 1 -C 30 alkylene, C 1 -C 30 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 30 alkylene group separated by heteroatoms, or a C 2 -C 30 alkylene group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
  • L is a direct bond, C 1 -C 18 alkylene, C 1 -C 18 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 18 alkylene group interrupted by heteroatoms, or a C 2 -C 18 alkyleneoxy group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, and S, wherein R a is H or C 1 -C 4 alkyl.
  • L is a direct bond, C 1 -C 12 alkylene, C 1 -C 12 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 12 alkylene group interrupted by heteroatoms, or a C 2 -C 12 alkyleneoxy group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
  • L is a direct bond, C 2 -C 12 alkylene, C 2 -C 12 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S
  • L is L 1 -OL 2
  • L 1 and L 2 are independently 1-20, preferably 1-15, 1-12, 1-6, 2-20, 2-15, A divalent linking group of 2-12 or 2-6 carbon atoms.
  • L 1 and L 2 independently of each other are C 1 -C 15 alkylene, preferably C 1 -C 10 alkylene, preferably C 1 -C 6 alkylene, such as methylene, ethylene, propylene group, butylene, pentylene or hexylene.
  • L 1 is C 1 -C 6 alkylene, preferably C 2 -C 6 alkylene and L 2 is C 1 -C 6 alkylene, preferably C 1 -C 4 alkylene.
  • the propylene group between the silicon and the benzene ring in the compound of formula (I) is -CH 2 -CH 2 -CH 2 - or -CH(CH 3 )-CH 2 -, preferably is -CH(CH 3 )-CH 2 -.
  • each variable in the compound of formula (I) is defined as follows:
  • n 1-30;
  • L is a direct bond or a divalent linking group with 1-12 carbon atoms
  • R 1 , R 2 , R 3 , R 4 , R 5 are the same or different, and are independently organic groups with 1-6 carbon atoms;
  • R 6 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.
  • each variable in the compound of formula (I) is defined as follows:
  • n 1-15;
  • L is a direct bond or a divalent linking group with 1-12 carbon atoms
  • R 1 , R 2 , R 3 , R 4 , R 5 are the same or different, and are independently organic groups with 1-6 carbon atoms;
  • R 6 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.
  • each variable in the compound of formula (I) is defined as follows:
  • n 1-30;
  • R 1 is C 1 -C 12 alkyl or C 1 -C 12 alkoxy
  • R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and are independently represented by one or more C 2 -C 12 alkyl separated by non-adjacent heteroatoms selected from NR a , O, S, or C separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S 2 -C 12 alkoxy, and
  • L is a direct bond, C 1 -C 30 alkylene, C 1 -C 30 alkyleneoxy, C 2 - separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S C 30 alkylene, or C 2 -C 30 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S,
  • R a is H or C 1 -C 4 alkyl.
  • the compound of formula (I) of the present invention satisfies at least one of the following definitions, preferably all:
  • - m is 1-20, preferably 2-15;
  • 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;
  • R a is H or C 1 -C 4 alkyl; preferably, R 2 , R 3 , R 4 , R 5 , the same or different, and independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or one or more independently selected from NR a , O, S C 2 -C 4 alkyl interspersed by non-adjacent heteroatoms, wherein R a is H or C 1 -C 4 alkyl;
  • -R 6 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 ;
  • -L is C 2 -C 30 alkylene, C 2 -C 30 alkyleneoxy, C 2 -C 30 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S Alkylene, or C 2 -C 30 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkane base.
  • n 1-20;
  • R 1 is C 1 -C 12 alkyl or C 1 -C 12 alkoxy
  • R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and are independently represented by one or more C 2 -C 12 alkyl separated by non-adjacent heteroatoms selected from NR a , O, S, or C separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S 2 -C 12 alkoxy, wherein R a is H or C 1 -C 4 alkyl, and
  • L is a direct bond, C 1 -C 30 alkylene, C 1 -C 30 alkyleneoxy, C 2 - separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S C 30 alkylene, or C 2 -C 30 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
  • each variable in the compound of formula (I) has the following definitions:
  • n 1-9;
  • R 1 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy
  • R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or one or more independently selected from NR a , C 1 -C 4 alkyl separated by non-adjacent heteroatoms of O, S, wherein R a is H or C 1 -C 4 alkyl;
  • R 6 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; as well as
  • L is L 1 -OL 2 , wherein L 1 and L 2 are independently a divalent linking group having 1-20, preferably 1-15 carbon atoms, more preferably C 1 -C 15 alkylene.
  • n 1-12;
  • R 1 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy
  • R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or one or more independently selected from NR a , C 1 -C 4 alkyl separated by non-adjacent heteroatoms of O, S, wherein R a is H or C 1 -C 4 alkyl;
  • R 6 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; as well as
  • L is L 1 -OL 2 , wherein L 1 and L 2 are independently C 1 -C 15 alkylene.
  • n 3-9;
  • R 1 is C 1 -C 4 alkyl
  • R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently C 1 -C 4 alkyl;
  • R 6 is H or C 1 -C 4 alkyl, especially H or ethyl, and
  • L is L 1 -OL 2 , wherein L 1 and L 2 are independently C 1 -C 6 alkylene.
  • the compound of formula (I) is one or more compounds selected from the group consisting of:
  • L in the compound of formula (I) is L 1 -OL 2 , wherein L 1 and L 2 are as defined above, preferably C 1 -C 15 alkylene, more preferably C 1 -C 6 alkylene.
  • the compound of formula (VI) can be prepared by the following steps:
  • L is a divalent linking group having 1-20 , preferably 1-15 carbon atoms, more preferably C 1 -C 15 alkylene, especially C 1 -C 6 alkylene, and X is halogen, such as fluorine, chlorine, bromine or iodine,
  • L 2 is a divalent linking group having 1-20, preferably 1-15 carbon atoms, more preferably a C 1 -C 15 alkylene group, especially a C 1 -C 6 alkylene group and R 6 is as above for the formula (I)
  • X is halogen such as chlorine, bromine or iodine.
  • step (1) the reaction of the phenolic hydroxyl group in the compound of formula (II) with the halogen in the compound of formula (III) belongs to the type of reaction known in the art, and the reaction produces hydrogen halide.
  • the reaction is carried out in the presence of a basic catalyst.
  • basic catalysts suitable for this reaction mention may be made of sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof.
  • the amount of catalyst used is also conventional.
  • the molar ratio of the compound of formula (II) to the basic catalyst is 1:1-1:5, preferably 1:1-1:3.
  • the reaction of the compound of formula (II) with the compound of formula (III) is usually carried out in a solvent.
  • the solvent is also conducive to the precipitation of the product, that is, the compound of formula (IV).
  • an organic solvent is usually used, preferably toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile or any mixture thereof.
  • the amount of solvent used is also conventional, generally speaking, the amount of solvent used is 1.0-3 times the total weight of the compound of formula (II) and 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 that of formula (III) is 1:0.75-1:1.5, or 1:1-1:1.3.
  • the compound of formula (II) is usually dissolved in a solvent, a basic catalyst is added, and then the compound of formula (III) is added. After the addition is complete, the resulting reaction mixture is stirred evenly, and then the temperature is raised to 30-120° C., preferably to 40-70°C.
  • the reaction is usually continued for 3-16 hours, preferably for 4-10 hours. Of course, the reaction is advantageously carried out with stirring.
  • the compound of formula (IV) can be obtained through conventional post-treatment.
  • the post-treatment usually includes extraction or washing (such as washing with water, after which water-absorbing compounds such as magnesium sulfate or sodium sulfate are advantageously used to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove solvents, and vacuum distillation to further remove solvents. If a higher purity product is to be obtained, the product can also be obtained by recrystallization or column chromatography.
  • step (2) the reaction of the terminal hydroxyl group in the compound of formula (IV) with the halogen in the compound of formula (V) is known to produce hydrogen halide.
  • the reaction is carried out in the presence of a catalyst.
  • a catalyst As suitable catalysts for this reaction, mention may be made of sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof.
  • the amount of catalyst used is also conventional.
  • the molar ratio of the compound of formula (IV) to the catalyst is 1:1-1:5, preferably 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 type of solvent there is no special limitation, as long as the compound of formula (IV), compound of formula (V) and corresponding catalyst can be dissolved and do not participate in the reaction between the compound of formula (IV) and compound of formula (V), preferably
  • the solvent also facilitates the precipitation of the product, namely the compound of formula (VI).
  • an organic solvent is usually used, preferably toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile or any mixture thereof.
  • the amount of solvent used is also conventional, generally speaking, the amount of solvent used is 1.0-3 times the total weight of the compound of formula (IV) and compound of formula (V).
  • the compound of formula (IV) and the compound of formula (V) are usually used in approximately equimolar amounts.
  • the molar ratio of the compound of formula (IV) to the compound of formula (IV) is 1:0.75-1:1.5, or 1:1-1:1.2.
  • the compound of formula (IV) and the catalyst are usually dissolved in a solvent, and then the solution of the compound of formula (V) in the solvent is added. After the addition, the temperature is raised to 40-100° C., preferably to 60-90° C.
  • the reaction is usually continued for 3-24 hours, preferably for 4-10 hours. Of course, the reaction is advantageously carried out with stirring.
  • the compound of formula (VI) can be obtained through conventional post-treatment.
  • the post-treatment usually includes extraction or washing (such as washing with water, after which water-absorbing compounds such as magnesium sulfate or sodium sulfate are advantageously used to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove solvents, and vacuum distillation to further remove solvents. If a higher purity product is to be obtained, impurities can also be separated by recrystallization or column chromatography.
  • the silicon atom of the compound of formula (VII) contains hydrogen atoms, therefore, the compound of formula (VII) can be called hydrogen-containing silicone oil.
  • Addition reactions of silicon-bonded hydrogen atoms in compounds of formula (VII) to unsaturated carbon-carbon double bonds in compounds of formula (VI) are of the type known in the art.
  • the reaction is carried out in the presence of a catalyst.
  • a catalyst suitable for this reaction a Karstedt catalyst or a Speier catalyst is generally used.
  • the amount of catalyst used is also conventional.
  • the catalyst is used in an amount of 2-500 ppm, preferably 10-300 ppm.
  • the reaction of the compound of formula (VI) with the compound of formula (VII) is usually carried out in a solvent.
  • a solvent As the type of solvent, there is no particular limitation, as long as the compound of formula (VI), the compound of formula (VII) and the catalyst can be dissolved and it does not participate in the reaction between the compound of formula (VI) and the compound of formula (VII).
  • the solvent also facilitates the precipitation of the product, the compound of formula (I).
  • an organic solvent is usually used, preferably petroleum ether, dichloromethane, toluene, xylene 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 (VI) and compound of formula (VII).
  • the compound of formula (VI) and the compound of formula (VII) are usually used in approximately equimolar amounts.
  • the molar ratio of the compound of formula (VI) to the compound of formula (VII) is 1:0.75-1:1.5.
  • the compound of formula (VI) and the catalyst are usually dissolved in a solvent and aged for a period of time, then contacted with the compound of formula (VII), 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 elevated temperature, usually at 40-70°C. The aging time is usually 30-60 minutes.
  • the reaction temperature between the compound of formula (VI) and the compound of formula (VII) is usually 80-110°C, preferably 85-100°C.
  • the holding time of the reaction between the compound of formula (VI) and the compound of formula (VII) at the reaction temperature is usually 3-6 hours, preferably 3.5-5.5 hours.
  • the reaction is advantageously carried out with stirring.
  • the product of the compound of formula (I) can be obtained through conventional post-treatment.
  • the post-treatment usually includes filtration or centrifugation to remove solid impurities, rotary evaporation to remove solvent, and vacuum distillation to further remove solvent. If a higher purity product is to be obtained, it can also be recrystallized.
  • the compound of formula (I) of the present invention is a cationic photocurable monomer, which has fast polymerization rate, high conversion rate and can promote the polymerization of other cationic monomers.
  • the photocurable material obtained after photocuring polymerization has mechanical properties, especially tensile properties. Good, excellent hydrophobic performance, anti-stain, anti-fingerprint, anti-chemical corrosion, strong anti-aging performance, good heat resistance.
  • a photocurable composition comprising the compound of formula (I) of the present invention as a polymerizable monomer.
  • the photocurable composition may also contain a cationic photoinitiator for ring-opening polymerization (a photoinitiator capable of initiating cationic polymerization) and optionally other photoinitiators containing cationic photocurable groups Groups such as vinyl ether double bonds, alicyclic epoxy, oxiranyl or oxetanyl monomers, oligomers, such as 3,4-epoxycyclohexylmethyl3,4- Epoxycyclohexyl carboxylate (E4221).
  • a cationic photoinitiator for ring-opening polymerization a photoinitiator capable of initiating cationic polymerization
  • other photoinitiators containing cationic photocurable groups Groups such as vinyl ether double bonds, alicyclic epoxy, oxiranyl or oxetanyl monomers, oli
  • the amount of the compound of formula (I) of the present invention may be at least 0.5 mol%, at least 1 mol%, at least 2 mol%, for example 0.5-12 mol%, based on the total amount of polymerized monomers, Or 0.5-10mol%, or 1-10mol%.
  • the photocurable composition of the present invention may be a photocurable coating composition, a photocurable ink composition, a photoresist composition, and the like. After the composition is cured, the obtained cured product has good tensile properties, excellent hydrophobic properties, stain resistance, fingerprint resistance, chemical corrosion resistance and strong aging resistance.
  • iodonium salts and sulfonium salts are commonly used.
  • the iodonium salt photoinitiator and the sulfonium salt photoinitiator have the following general formulas (A) and (B) respectively
  • R a , R b , R c , R d , R e are each independently unsubstituted C 6 -C 10 aryl, or are selected from halogen, nitro, carbonyl, C 1 -C 12 alkyl, C 1 C 6 -C 10 aryl substituted by substituents of -C 12 alkoxy, phenylthio, phenyl and substituted phenyl, preferably phenyl or naphthyl, or selected from halogen, nitro, C 1 - C 6 alkyl and substituted phenyl or naphthyl substituted by substituents of phenyl, wherein the substituted phenyl contains one or more substituents selected from halogen, nitro, C 1 -C 6 alkyl and C 1 -C 6 alkoxy radicals; and
  • Y and Z are non-nucleophilic anions, such as trifluoromethanesulfonate, BF 4 - , ClO 4 - , PF 6 - , AsF 6 - , SbF 6 - .
  • a 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 bishexafluorophosphate Fluoroantimonate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone Keto-10-sulfonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate
  • the photocurable composition of the present invention may also contain a sensitizer.
  • a sensitizer mention may be made, for example, of 2-isopropylthioxanthone.
  • the amount of photoinitiator used is conventional. Based on the total molar amount of polymerized monomers in the photocurable composition of the present invention, the content of the photoinitiator is generally 0.5-5 mol%, preferably 1-3 mol%.
  • a photocurable material obtained from the photocurable composition of the present invention is obtained by photocuring the photocurable composition of the invention.
  • the light-curing material has good mechanical properties, especially tensile properties, excellent hydrophobic properties, and has the advantages of anti-staining, anti-fingerprint, anti-chemical corrosion, strong anti-aging performance and good heat resistance.
  • the compounds of formula (I) according to the invention can also be used in photocurable coatings, adhesives, inks and photoresists. Accordingly, the present invention also relates to the use of compounds of formula (I) in photocurable coatings, adhesives, inks and photoresists.
  • the purpose of this example is to illustrate the photopolymerizable properties of the compounds of the present invention.
  • the preparation process of photocurable composition is as follows:
  • the preparation method of the photocurable composition containing compound 2-3 is consistent with that of compound 1.
  • X 1 of the compounds 1, 2 and 3 of the present invention ie Eugenol-Si 3 , Eugenol-Si 6 and Eugenol-Si 9
  • Table 1-3 The mole percentage X 1 of the compounds 1, 2 and 3 of the present invention (ie Eugenol-Si 3 , Eugenol-Si 6 and Eugenol-Si 9 ) in each photocomposition is shown in Table 1-3 below, and X 1 +X 2 as mentioned above Fixed at 100, X 3 and X 4 remain the same.
  • a mixture of photoinitiator diphenyliodonium hexafluorophosphate (810) and 2-isopropylthioxanthone (ITX, sensitizer) in a molar ratio of 2:1 was used as the photoinitiation system, and real-time infrared
  • the (RT-IR) method was used to test the photopolymerization kinetics of compounds 1-3, and to investigate the effects of each of them on the photopolymerization performance of E4221 at different contents.
  • the vibration absorption peak of the COC of the three-membered oxygen heterocycle of the monomer E4221 used is located at 750 cm -1
  • the vibration absorption peak of the COC of the four-membered oxygen heterocycle of compound 1-3 as a polymerized monomer is 980 cm -1 .
  • the photocurable liquid composed of the precursor and the photoinitiator is evenly spread on the potassium bromide salt sheet (take a little photocurable liquid with a thin tube, click it on the potassium bromide salt sheet, and then spread it evenly), and irradiate it with a high-pressure mercury lamp Liquid sample 900s, in which the main emission wavelength of the mercury lamp is 365nm, and it has an optical fiber with a diameter of 5mm.
  • the distance between one end of the optical fiber and the test sample is 10cm, and the radiation intensity is 20mW cm - 2 .
  • the purpose of this example is to illustrate that the compound of the present invention can improve the surface hydrophobicity of the photocured film.
  • a water contact angle test was performed.
  • the surface hydrophobicity of the photocured film was characterized by a DSA25 water contact angle measuring instrument, and the test temperature was 25°C. At the same time, use the same method to prepare a blank E4221 cured film as a reference. The results for reference and compounds 1-3 are shown in Figure 7.
  • the respective cured films of compounds 1-3 were prepared in exactly the same manner as described in Example 6. Then, the heat resistance of each photocured film was measured using a thermogravimetric analyzer (DTG-60AH Shimadzu Enterprise Management (China) Co., Ltd.). The test conditions are: under nitrogen protection, the temperature range is 25-700°C, and the heating rate is 10°C/min. At the same time, use the same method to prepare a blank E4221 cured film as a reference. The results are shown in Figure 8 and Table 4.
  • the initial decomposition temperature (T 5% ) and the maximum thermal weight loss temperature of the cured film are the decomposition temperature (T max1 ) and the first stage of the fastest weight loss.
  • the decomposition temperature (T max2 ) is obviously increased when the weight loss is the fastest in the second stage, so the heat resistance is obviously improved.
  • the purpose of this example is to illustrate that the compounds of the present invention can improve the tensile properties of photocured films.
  • the respective cured films of compounds 1-3 were prepared in exactly the same manner as described in Example 6. Then, the electronic universal testing machine (E44.304, Meters Industrial Systems (China) Co., Ltd.) was used to test the tensile properties of the light-cured film according to the international standard ISO 1184-1983 "Determination of Tensile Properties of Plastic Films". The test temperature is 25°C, the humidity is 60%, and the test speed is 1mm/min. At the same time, use the same method to prepare a blank E4221 cured film as a reference. The results are shown in Figure 9 and Table 5.
  • E44.304 Meters Industrial Systems (China) Co., Ltd.
  • the tensile strength of the pure E4221 light-cured film is 6.10 MPa, and the elongation at break is 1.7%.
  • the tensile strength and elongation at break of the light-cured film gradually increased after the addition of compound 1-3 monomers.
  • the compounds of the present invention are able to significantly improve the tensile properties of cured films.

Abstract

The present invention relates to a eugenol bio-based silicon-containing oxetane monomer, a method for preparing the monomer, a photocurable composition containing the monomer, and a photocurable material prepared from the photocurable composition. The eugenol bio-based silicon-containing oxetane monomer of the present invention is good in polymerization rate and conversion rate and promotes polymerization of other cationic monomers; moreover, the photocurable material prepared therefrom has good mechanical properties and thermal stability, excellent hydrophobic properties, and is stain-resistant and fingerprint-resistant.

Description

丁香酚生物基含硅氧杂环丁烷单体及其制备方法Eugenol bio-based silicon-containing oxetane monomer and preparation method thereof 技术领域technical field
本发明涉及光固化材料领域，具体来说涉及一种丁香酚生物基含硅氧杂环丁烷单体。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得到的光固化材料。The invention relates to the field of photocurable materials, in particular to a eugenol bio-based silicon-containing oxetane monomer. The present invention also relates to a preparation method of the monomer, a photocurable composition comprising the monomer and a photocurable material obtained from the photocurable composition.
背景技术Background technique
光聚合技术是利用光来引发带有活性物质的液态低聚物或单体转变为固态产物的过程。相比于传统的热聚合技术，光聚合无需使用挥发性有机溶剂即可实现高效的无污染生产，节省了大量能源。因此，光聚合技术以其特有的低能耗要求、快速固化、无溶剂配方、无污染、室温处理和环保等特点而被视为一种绿色工艺，因而在光固化涂料、粘合剂和油墨印刷等领域应用广泛。Photopolymerization technology is the process of using light to initiate the conversion of liquid oligomers or monomers with active substances into solid products. Compared with traditional thermal polymerization technology, photopolymerization can achieve efficient and pollution-free production without using volatile organic solvents, saving a lot of energy. Therefore, photopolymerization technology is regarded as a green process because of its unique low energy consumption requirements, fast curing, solvent-free formula, no pollution, room temperature treatment and environmental protection, so it is widely used in photocuring coatings, adhesives and printing inks. and other fields are widely used.
相比于自由基光聚合体系，阳离子光聚合以其不受氧抑制、收缩率低、可后固化、光固化材料机械性能好以及对各种基材有良好的附着力等优点而备受关注。氧杂环烷烃单体属阳离子光固化体系。氧杂环烷烃单体是高端阳离子光固化产品的主要原料，这种体系不仅粘度低且毒性低。然而，在紫外光固化以节能、环保、高效等优点迅速发展的同时，对于光固化材料的耐热性、拒水性、表面的抗沾污、耐腐蚀及抗指纹等方面人们提出了更高的要求。消费者对产品外观的要求日益提高，除了色彩美观以及手感舒适外，还要求表面具有抗指纹、耐沾污的性能，即使用时产品表面不易留下指纹等痕迹，或者即使留下痕迹也很容易被擦净。Compared with radical photopolymerization systems, cationic photopolymerization has attracted much attention due to its advantages such as no oxygen inhibition, low shrinkage, post-curing, good mechanical properties of photocurable materials, and good adhesion to various substrates. . The oxetane monomer is a cationic photocuring system. Oxycyclane monomer is the main raw material of high-end cationic photocurable products. This system not only has low viscosity and low toxicity. However, with the rapid development of UV curing with the advantages of energy saving, environmental protection, and high efficiency, people have put forward higher requirements for the heat resistance, water repellency, surface anti-staining, corrosion resistance and anti-fingerprint of photo-curing materials. Require. Consumers are increasingly demanding the appearance of products. In addition to beautiful colors and comfortable handles, they also require the surface to have anti-fingerprint and anti-stain properties. was wiped clean.
另外，目前用于光聚合的大多数预聚物和单体仍是化石基的。由于化石资源的不可再生特性和对环境有一定污染，迫切需要用可再生的生物基预聚物或单体代替化石基预聚物或单体，使光聚合技术更加环保。目前，能够满足前述要求的光固化阳离子单体的种类较少，需要开发更多类型的可阳离子光固化单体。Additionally, most prepolymers and monomers currently used for photopolymerization are still fossil-based. Due to the non-renewable characteristics of fossil resources and certain pollution to the environment, it is urgent to replace fossil-based prepolymers or monomers with renewable bio-based prepolymers or monomers to make photopolymerization technology more environmentally friendly. At present, there are few types of photocurable cationic monomers that can meet the aforementioned requirements, and more types of cationic photocurable monomers need to be developed.
发明内容Contents of the invention
鉴于现有技术的上述状况，本发明的发明人在丁香酚生物基材料方面进行了 广泛而又深入的研究，以期发现一类新型的可阳离子光固化单体，该单体由生物In view of the above-mentioned situation of the prior art, the inventors of the present invention have carried out extensive and in-depth research on eugenol bio-based materials, in order to find a class of novel cationic photocurable monomers, which are produced by biological
基材料制备而成，聚合速率快，光固化后具有拉伸性能好，耐热性好，疏水性能优良，抗沾污，抗指纹等优点。本发明人出乎意料的发现，本发明的式(I)的可阳离子光聚合的丁香酚生物基含硅氧杂环丁烷单体具有良好的聚合速率和转化率且促进其他阳离子单体的聚合，且由其得到的光固化材料具有良好的机械性能，特别是拉伸性能和热稳定性，疏水性能优良且抗沾污，抗指纹。It is prepared from the base material, with fast polymerization rate. After photocuring, it has the advantages of good tensile properties, good heat resistance, excellent hydrophobic properties, anti-staining, and anti-fingerprints. The present inventors unexpectedly found that the cationic photopolymerizable eugenol bio-based silicon-containing oxetane monomer of formula (I) of the present invention has good polymerization rate and conversion rate and promotes the synthesis of other cationic monomers. Polymerization, and the photocurable material obtained therefrom has good mechanical properties, especially tensile properties and thermal stability, excellent hydrophobic properties and anti-staining and anti-fingerprints.
因此，本发明的一个目的是提供一种丁香酚生物基含硅氧杂环丁烷单体，该单体由生物基材料制备而成。所述单体具有良好的聚合速率和转化率且促进其他阳离子单体的聚合，并且由其得到的光固化材料具有良好的机械性能，特别是拉伸性能和耐热性，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强。It is therefore an object of the present invention to provide a eugenol bio-based silicon-containing oxetane monomer prepared from bio-based materials. The monomer has a good polymerization rate and conversion rate and promotes the polymerization of other cationic monomers, and the photocurable material obtained therefrom has good mechanical properties, especially tensile properties and heat resistance, excellent hydrophobic properties, and Stain, anti-fingerprint, anti-chemical corrosion, strong anti-aging performance.
本发明的另一目的是提供一种制备本发明丁香酚生物基含硅氧杂环丁烷单体的方法。该制备方法简单易行，条件温和，原料易得，价格低廉。Another object of the present invention is to provide a method for preparing the eugenol bio-based silicon-containing oxetane monomer of the present invention. The preparation method is simple and easy, the conditions are mild, the raw materials are readily available and the price is low.
本发明的再一个目的是提供一种可光固化组合物，该组合物包含根据本发明的丁香酚生物基含硅氧杂环丁烷单体。Yet another object of the present invention is to provide a photocurable composition comprising the eugenol bio-based silicone-containing oxetane monomer according to the present invention.
本发明的再一个目的是提供一种由本发明的可光固化组合物得到的光固化材料。Another object of the present invention is to provide a photocurable material obtained from the photocurable composition of the present invention.
本发明的再一个目的是提供本发明的式(I)化合物在光固化涂料、粘合剂和油墨中的用途。Another object of the present invention is to provide the use of the compound of formula (I) of the present invention in photocurable coatings, adhesives and inks.
实现本发明上述目的的技术方案可以概括如下：The technical scheme that realizes the above-mentioned purpose of the present invention can be summarized as follows:
1.下式(I)化合物：1. Compounds of the following formula (I):
Figure PCTCN2022099400-appb-000001
Figure PCTCN2022099400-appb-000001
其中in
m为1-50；m is 1-50;
L为直接键或具有1-30个碳原子的二价连接基团；L is a direct bond or a divalent linking group with 1-30 carbon atoms;
R 1、R 2、R 3、R 4、R 5相同或不同，并独立地为具有1-12碳原子的有机基团；以及 R 1 , R 2 , R 3 , R 4 , R 5 are the same or different, and are independently organic groups with 1-12 carbon atoms; and
R 6为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基。 R 6 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.
2.根据第1项的化合物，其中2. A compound according to item 1, wherein
m为1-30；m is 1-30;
R 1为C 1-C 12烷基或者C 1-C 12烷氧基； R 1 is C 1 -C 12 alkyl or C 1 -C 12 alkoxy;
R 2、R 3、R 4、R 5相同或不同，并独立地为C 6-C 10芳基、C 1-C 12烷基、C 1-C 12烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 12烷基，或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 12烷氧基，以及 R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and are independently represented by one or more C 2 -C 12 alkyl separated by non-adjacent heteroatoms selected from NR a , O, S, or C separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S 2 -C 12 alkoxy, and
L为直接键、C 1-C 30亚烷基、C 1-C 30亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷氧基， L is a direct bond, C 1 -C 30 alkylene, C 1 -C 30 alkyleneoxy, C 2 - separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S C 30 alkylene, or C 2 -C 30 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S,
其中R a为H或C 1-C 4烷基。 Wherein R a is H or C 1 -C 4 alkyl.
3.根据第1或2项的化合物，其满足下述定义中的至少一个，优选全部：3. The compound according to item 1 or 2, which satisfies at least one, preferably all, of the following definitions:
-m为1-20，优选为2-15；- m is 1-20, preferably 2-15;
-R 1为C 1-C 6烷基或者C 1-C 6烷氧基；R 1优选为C 1-C 4烷基或者C 1-C 4烷氧基； -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;
-R 2、R 3、R 4、R 5、相同或不同，并独立地为C 6-C 10芳基、C 1-C 6烷基、C 1-C 6烷氧基或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 6烷基，其中R a为H或C 1-C 4烷基；优选的是，R 2、R 3、R 4、R 5、相同或不同，并独立地为苯基、C 1-C 4烷基、C 1-C 4烷氧基或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 4烷基，其中R a为H或C 1-C 4烷基； -R 2 , R 3 , R 4 , R 5 , the same or different, and independently C 6 -C 10 aryl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or replaced by one or more C 2 -C 6 alkyl groups independently selected from NR a , O, and S with non-adjacent heteroatom intervals, wherein R a is H or C 1 -C 4 alkyl; preferably, R 2 , R 3 , R 4 , R 5 , the same or different, and independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or one or more independently selected from NR a , O, S C 2 -C 4 alkyl interspersed by non-adjacent heteroatoms, wherein R a is H or C 1 -C 4 alkyl;
-R 6为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基； -R 6 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 ;
-L为C 2-C 30亚烷基、C 2-C 30亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷基、或者被一个或多个独立地选自NR a、O、 S的非相邻杂原子间隔的C 2-C 30亚烷氧基，其中R a为H或C 1-C 4烷基。 -L is C 2 -C 30 alkylene, C 2 -C 30 alkyleneoxy, C 2 -C 30 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S Alkylene, or C 2 -C 30 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkane base.
4.根据第1项的化合物，其中4. A compound according to item 1, wherein
m为1-9；m is 1-9;
R 1为C 1-C 4烷基或者C 1-C 4烷氧基； R 1 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy;
R 2、R 3、R 4、R 5相同或不同，并独立地为苯基、C 1-C 4烷基、C 1-C 4烷氧基或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 1-C 4烷基，其中R a为H或C 1-C 4烷基； R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or one or more independently selected from NR a , C 1 -C 4 alkyl separated by non-adjacent heteroatoms of O, S, wherein R a is H or C 1 -C 4 alkyl;
R 6为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基；以及 R 6 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; as well as
L为L 1-O-L 2，其中L 1和L 2相互独立地为具有1-20，优选1-15个碳原子的二价连接基团，更优选C 1-C 15亚烷基； L is L 1 -OL 2 , wherein L 1 and L 2 are independently a divalent linking group with 1-20, preferably 1-15 carbon atoms, more preferably C 1 -C 15 alkylene;
优选的是，Preferably,
m为3-9；m is 3-9;
R 1为C 1-C 4烷基； R 1 is C 1 -C 4 alkyl;
R 2、R 3、R 4、R 5相同或不同，并独立地为C 1-C 4烷基； R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently C 1 -C 4 alkyl;
R 6为H或C 1-C 4烷基，以及 R 6 is H or C 1 -C 4 alkyl, and
L为L 1-O-L 2，其中L 1和L 2相互独立地为C 1-C 6亚烷基。 L is L 1 -OL 2 , wherein L 1 and L 2 are independently C 1 -C 6 alkylene.
5.根据第1-4项中任一项的化合物，其中式(I)化合物选自下组：5. The compound according to any one of items 1-4, wherein the compound of formula (I) is selected from the group consisting of:
Figure PCTCN2022099400-appb-000002
Figure PCTCN2022099400-appb-000002
Figure PCTCN2022099400-appb-000003
Figure PCTCN2022099400-appb-000003
6.一种制备根据第1-5项中任一项的式(I)化合物的方法，包括：6. A method for preparing a compound of formula (I) according to any one of items 1-5, comprising:
使得式(VI)化合物与式(Ⅶ)化合物反应得到式(I)化合物Make the compound of formula (VI) react with the compound of formula (VII) to obtain the compound of formula (I)
Figure PCTCN2022099400-appb-000004
Figure PCTCN2022099400-appb-000004
其中L和R 6如第1-5项中任一项所定义， wherein L and R are as defined in any one of items 1-5,
Figure PCTCN2022099400-appb-000005
Figure PCTCN2022099400-appb-000005
其中m、R 1、R 2、R 3、R 4和R 5如第1-5项中任一项所定义。 wherein m, R 1 , R 2 , R 3 , R 4 and R 5 are as defined in any one of items 1-5.
7.根据第6项的方法，其中L为L 1-O-L 2，其中L 1和L 2相互独立地为具有 1-20，优选1-15个碳原子的二价连接基团，更优选为C 1-C 15亚烷基，尤其是C 1-C 6亚烷基。 7. The method according to item 6, wherein L is L 1 -OL 2 , wherein L 1 and L 2 are independently of each other a divalent linking group having 1-20, preferably 1-15 carbon atoms, more preferably C 1 -C 15 alkylene, especially C 1 -C 6 alkylene.
8.根据第6或7项的方法，其中式(VI)的化合物通过如下步骤制备：8. The method according to item 6 or 7, wherein the compound of formula (VI) is prepared by the following steps:
(1)使式(Ⅱ)化合物：(1) make formula (II) compound:
Figure PCTCN2022099400-appb-000006
Figure PCTCN2022099400-appb-000006
与式(Ⅲ)化合物反应，React with the compound of formula (III),
Figure PCTCN2022099400-appb-000007
Figure PCTCN2022099400-appb-000007
其中L 1为具有1-20，优选1-15个碳原子的二价连接基团，更优选为C 1-C 15亚烷基，尤其是C 1-C 6亚烷基，并且X为卤素，例如氟、氯、溴或碘， wherein L is a divalent linking group having 1-20 , preferably 1-15 carbon atoms, more preferably C 1 -C 15 alkylene, especially C 1 -C 6 alkylene, and X is halogen , such as fluorine, chlorine, bromine or iodine,
得到式(Ⅳ)化合物Obtain the compound of formula (Ⅳ)
Figure PCTCN2022099400-appb-000008
Figure PCTCN2022099400-appb-000008
其中L 1如对式(III)化合物所定义； Wherein L is as defined for the compound of formula (III);
以及as well as
(2)使式(Ⅳ)化合物与式(Ⅴ)化合物反应得到式(Ⅵ)化合物(2) react the compound of formula (Ⅳ) with the compound of formula (Ⅴ) to obtain the compound of formula (Ⅵ)
Figure PCTCN2022099400-appb-000009
Figure PCTCN2022099400-appb-000009
其中L 2为具有1-20，优选1-15个碳原子的二价连接基团，更优选为C 1-C 15亚烷基，尤其是C 1-C 6亚烷基，R 6如第1-5项中任一项所定义，并且X为卤素，例如氯、溴或碘。 Wherein L 2 is a divalent linking group having 1-20, preferably 1-15 carbon atoms, more preferably a C 1 -C 15 alkylene group, especially a C 1 -C 6 alkylene group, R 6 is as in paragraph as defined in any one of items 1-5, and X is halogen, such as chlorine, bromine or iodine.
9.根据第8项的方法，其中在步骤(1)中的反应满足下述条件中的至少一个：9. The method according to item 8, wherein the reaction in step (1) meets at least one of the following conditions:
-式(Ⅱ)化合物与式(Ⅲ)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选是氢化钠、氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物， 更优选的是，式(Ⅱ)化合物与碱性催化剂的摩尔比为1:1-1:5；- the reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a basic catalyst, preferably sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, More preferably, the molar ratio of the compound of formula (II) to the basic catalyst is 1:1-1:5;
-式(Ⅱ)化合物与式(Ⅲ)化合物的摩尔比为1:0.75-1:1.5；- the molar ratio of the compound of formula (II) to the compound of formula (III) is 1:0.75-1:1.5;
-式(Ⅱ)化合物与式(Ⅲ)化合物之间的反应在30-120℃，优选40-70℃下进行；- the reaction between the compound of formula (II) and the compound of formula (III) is carried out at 30-120°C, preferably 40-70°C;
-式(Ⅱ)化合物与式(Ⅲ)化合物之间的反应进行3-16小时，优选4-10小时。- The reaction between the compound of formula (II) and the compound of formula (III) is carried out for 3-16 hours, preferably 4-10 hours.
10.根据第8或9项的方法，其中在步骤(2)中的反应满足下述条件中的至少一个：10. The method according to item 8 or 9, wherein the reaction in step (2) meets at least one of the following conditions:
-式(Ⅳ)化合物与式(Ⅵ)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选是氢化钠、氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物，更优选的是，式(Ⅳ)化合物与碱性催化剂的摩尔比为1:1-1:5；-the reaction of the compound of formula (IV) with the compound of formula (VI) is carried out in the presence of a basic catalyst, preferably sodium hydride, 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 1:1-1:5;
-式(Ⅳ)化合物与式(Ⅵ)化合物的摩尔比为1:0.75-1:1.5；- the molar ratio of the compound of formula (IV) to the compound of formula (VI) is 1:0.75-1:1.5;
-式(Ⅳ)化合物与式(Ⅵ)化合物之间的反应在40-100℃，优选在60-90℃下进行；优选的是，反应进行3-24小时，优选4-10小时。- The reaction between the compound of formula (IV) and the compound of formula (VI) is carried out at 40-100°C, preferably at 60-90°C; preferably, the reaction is carried out for 3-24 hours, preferably 4-10 hours.
11.根据第6-10项中任一项的方法，其中式(Ⅵ)化合物与式(Ⅶ)化合物的反应满足下述条件中的至少一个：11. The method according to any one of items 6-10, wherein the reaction of the compound of formula (VI) with the compound of formula (VII) satisfies at least one of the following conditions:
-式(Ⅵ)化合物与式(Ⅶ)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，催化剂的量基于式(VII)的重量为2-500ppm；- the reaction of the compound of formula (VI) with the compound of formula (VII) is carried out in the presence of Karstedt catalyst or SpeIer catalyst, preferably, the amount of catalyst is 2-500ppm based on the weight of formula (VII);
-式(Ⅵ)化合物与式(Ⅶ)化合物的摩尔比为1:0.75-1:1.5；- the molar ratio of the compound of formula (VI) to the compound of formula (VII) is 1:0.75-1:1.5;
-式(Ⅵ)化合物与式(Ⅶ)化合物之间的反应在80-110℃，优选85-100℃下进行；- the reaction between the compound of formula (VI) and the compound of formula (VII) is carried out at 80-110°C, preferably 85-100°C;
-式(Ⅵ)化合物与式(Ⅶ)化合物之间的反应进行3-6小时，优选3.5-5.5小时。- The reaction between the compound of formula (VI) and the compound of formula (VII) is carried out for 3-6 hours, preferably 3.5-5.5 hours.
12.一种可光固化组合物，包含根据第1-5项中任一项的式(Ⅰ)化合物作为聚合单体。12. A photocurable composition comprising a compound of formula (I) according to any one of items 1-5 as a polymerizable monomer.
13.一种由第12项的可光固化组合物得到的光固化材料。13. A photocurable material obtained from the photocurable composition of item 12.
14.根据第1-5项中任一项的式(I)化合物在光固化涂料、粘合剂、油墨和光致抗蚀剂中的用途。14. Use of compounds of formula (I) according to any one of items 1-5 in photocurable coatings, adhesives, inks and photoresists.
15.一种式(VI)化合物：15. A compound of formula (VI):
Figure PCTCN2022099400-appb-000010
Figure PCTCN2022099400-appb-000010
其中L和R 6如第1-5项中任一项所定义。 wherein L and R are as defined in any one of items 1-5.
附图说明Description of drawings
图1是包含实施例1所制备的化合物1的体系中的E4221转化率随辐照时间的变化曲线图。Fig. 1 is a graph showing the change of E4221 conversion rate with irradiation time in the system containing compound 1 prepared in Example 1.
图2是包含实施例2所制备的化合物2的体系中的E4221转化率随辐照时间的变化曲线图。Fig. 2 is a graph showing the change of E4221 conversion rate with irradiation time in the system containing compound 2 prepared in Example 2.
图3是包含实施例3所制备的化合物3的体系中的E4221转化率随辐照时间的变化曲线图。Fig. 3 is a graph showing the change of E4221 conversion rate with irradiation time in the system containing compound 3 prepared in Example 3.
图4是包含实施例1所制备的化合物1的体系中的化合物1的转化率随辐照时间的变化曲线图。FIG. 4 is a graph showing the conversion rate of Compound 1 in the system containing Compound 1 prepared in Example 1 as a function of irradiation time.
图5是包含实施例2所制备的化合物2的体系中的化合物2的转化率随辐照时间的变化曲线图。Fig. 5 is a graph of the conversion of compound 2 in the system containing compound 2 prepared in Example 2 as a function of irradiation time.
图6是包含实施例3所制备的化合物3的体系中的化合物3的转化率随辐照时间的变化曲线图。Fig. 6 is a graph showing the conversion of compound 3 in the system containing compound 3 prepared in Example 3 as a function of irradiation time.
图7是空白E4221固化膜和包含实施例1-3各自制备的化合物1-3的体系的固化膜的接触角图。Fig. 7 is a contact angle graph of a blank E4221 cured film and a cured film of a system comprising compounds 1-3 prepared in each of Examples 1-3.
图8是空白E4221固化膜和包含实施例1-3各自制备的化合物1-3的体系的固化膜的热重曲线图。Fig. 8 is a thermogravimetric graph of cured films of blank E4221 and cured films of systems comprising compounds 1-3 prepared in each of Examples 1-3.
图9是空白E4221固化膜和包含实施例1-3各自制备的化合物1-3的体系的固化膜的力学性能曲线图。Fig. 9 is a graph showing the mechanical properties of a blank E4221 cured film and a cured film of a system containing compounds 1-3 prepared in each of Examples 1-3.
具体实施方式detailed description
以下对本发明的实施方式进行说明。但是，本发明不限于以下的实施方式。Embodiments of the present invention will be described below. However, the present invention is not limited to the following embodiments.
本文中，使用数值范围表示前后所记载的数值分别作为最小值和最大值的范 围。Herein, a numerical range is used to indicate a range in which the numerical values described before and after are taken as the minimum value and the maximum value, respectively.
本文对相关特征公开具体值(包括范围的端点)可以相互结合成一个新的范围。Specific values disclosed herein for related features (including range endpoints) may be combined with each other to form a new range.
根据本发明的一个方面，提供了一种下式(Ⅰ)化合物：According to one aspect of the present invention, a kind of following formula (I) compound is provided:
Figure PCTCN2022099400-appb-000011
Figure PCTCN2022099400-appb-000011
其中in
m为1-50；m is 1-50;
L为直接键或具有1-30个碳原子的二价连接基团；L is a direct bond or a divalent linking group with 1-30 carbon atoms;
R 1、R 2、R 3、R 4、R 5相同或不同，并独立地为具有1-12碳原子的有机基团；以及 R 1 , R 2 , R 3 , R 4 , R 5 are the same or different, and are independently organic groups with 1-12 carbon atoms; and
R 6为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基。 R 6 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.
在本发明中，前缀“C n-C m”在每种情况下表示该基团中包含的碳原子数为n-m个。 In the present invention, the prefix "C n -C m " indicates in each case that the number of carbon atoms contained in the group is nm.
“卤素”是指氟、氯、溴和碘。在本发明中，优选的是，卤素包括氟、氯或其组合。"Halogen" refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferred that the halogen includes fluorine, chlorine or a combination thereof.
本文所用的术语“C n-C m烷基”是指具有n-m个，例如1-12个，优选1-6个，特别优选1-4个碳原子的支化或未支化饱和烃基，例如甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、己基、1,1-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基、庚基、辛基、2-乙基己基、壬基、癸基、十一烷基、十二烷基及其异构体。C 1-C 6烷基可以是甲基、乙基、丙基、异丙基、正丁基、2-丁基、叔丁基、戊基、异戊基、己基及其异构体。C 1-C 4烷基可以是 甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基及其异构体。 The term "C n -C m alkyl" as used herein refers to a branched or unbranched saturated hydrocarbon group having nm, such as 1-12, preferably 1-6, particularly preferably 1-4 carbon atoms, such as Methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methyl Butyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2- Dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethyl Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl , 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2 - methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and isomers thereof. The C 1 -C 6 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl and isomers thereof. C 1 -C 4 Alkyl can be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl groups and their isomers.
本文所用术语“C 6-C m芳基”是指含有6-m个碳原子，例如6-10个碳原子的单环、双环或更多环芳族烃基。作为C 6-C m芳基的实例，可提及苯基、甲苯基、乙苯基、丙苯基、丁苯基、二甲苯基、甲基·乙基苯基、二乙基苯基、甲基·丙基苯基和萘基等；优选苯基或萘基，尤其是苯基。 The term "C 6 -C m aryl" as used herein refers to a monocyclic, bicyclic or multicyclic aromatic hydrocarbon group containing 6-m carbon atoms, for example 6-10 carbon atoms. As examples of C 6 -C m aryl groups, mention may be made of phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methylethylphenyl, diethylphenyl, Methyl-propylphenyl and naphthyl, etc.; preferably phenyl or naphthyl, especially phenyl.
本文所用的术语“C n-C m烷氧基”是指在C n-C m烷基对应的开链C n-C m烷烃的任何碳原子上键合有一个氧原子作为连接基团的C n-C m烷基，例如C 1-C 12烷氧基，更优选C 1-C 6烷氧基，尤其优选C 1-C 4烷氧基。C 1-C 6烷氧基可以是甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、2-丁氧基、叔丁氧基、戊氧基、异戊氧基、己氧基及其异构体。C 1-C 4烷氧基可以是甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基、叔丁氧基及其异构体。 The term "C n -C m alkoxy" as used herein refers to a C n -C m alkyl corresponding to any carbon atom of an open chain C n -C m alkane bonded with an oxygen atom as a linking group C n -C m alkyl, such as C 1 -C 12 alkoxy, more preferably C 1 -C 6 alkoxy, especially preferably C 1 -C 4 alkoxy. C 1 -C 6 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentyloxy, isopentyloxy group, hexyloxy group and its isomers. C 1 -C 4 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and its isomers body.
本文所用的术语“C n-C m卤代烷基”是指被一个或多个相同或不同卤素原子取代的C n-C m烷基，例如C 1-C 12卤代烷基，优选C 1-C 6卤代烷基，特别优选C 1-C 4卤代烷基。作为C n-C m卤代烷基的实例，可以提及一氯甲基、一氯乙基、二氯乙基、三氯乙基、一氯丙基、1-氯甲基乙基、一氯丁基、1-氯甲基丙基、2-氯甲基丙基、1,1-二氯甲基乙基、一氯戊基、1-氯甲基丁基、2-氯甲基丁基、3-氯甲基丁基、2,2-二氯甲基丙基、1-氯乙基丙基、一氯己基、1,1-二氯甲基丙基、1,2-二氯甲基丙基、1-氯甲基戊基、2-氯甲基戊基、3-氯甲基戊基、4-氯甲基戊基、1,1-二氯甲基丁基、1,2-二氯甲基丁基、1,3-二氯甲基丁基、2,2-二氯甲基丁基、2,3-二氯甲基丁基、3,3-二氯甲基丁基、1-氯乙基丁基、2-氯乙基丁基、1,1,2-三氯甲基丙基、1,2,2-三氯甲基丙基、1-氯乙基-1-甲基丙基、1-乙基-2-氯甲基丙基及其异构体。 The term "C n -C m haloalkyl" as used herein refers to C n -C m alkyl substituted by one or more same or different halogen atoms, such as C 1 -C 12 haloalkyl, preferably C 1 -C 6 Haloalkyl, particularly preferably C 1 -C 4 haloalkyl. As examples of Cn- Cm haloalkyl groups, mention may be made of monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, 1-chloromethylethyl, monochlorobutyl Base, 1-chloromethylpropyl, 2-chloromethylpropyl, 1,1-dichloromethylethyl, 1-chloropentyl, 1-chloromethylbutyl, 2-chloromethylbutyl, 3-chloromethylbutyl, 2,2-dichloromethylpropyl, 1-chloroethylpropyl, monochlorohexyl, 1,1-dichloromethylpropyl, 1,2-dichloromethyl Propyl, 1-chloromethylpentyl, 2-chloromethylpentyl, 3-chloromethylpentyl, 4-chloromethylpentyl, 1,1-dichloromethylbutyl, 1,2- Dichloromethylbutyl, 1,3-dichloromethylbutyl, 2,2-dichloromethylbutyl, 2,3-dichloromethylbutyl, 3,3-dichloromethylbutyl , 1-chloroethylbutyl, 2-chloroethylbutyl, 1,1,2-trichloromethylpropyl, 1,2,2-trichloromethylpropyl, 1-chloroethyl-1 - methylpropyl, 1-ethyl-2-chloromethylpropyl and isomers thereof.
本文所用的术语“C n-C m卤代烷氧基”是指被一个或多个相同或不同卤素原子取代的C n-C m烷氧基，例如C 1-C 12卤代烷氧基，更优选C 1-C 6卤代烷氧基，尤其优选C 1-C 4卤代烷氧基。作为C n-C m卤代烷氧基的实例，可以提及一氯甲氧基、2-氯乙氧基、3-氯丙氧基、2-氯异丙氧基、4-氯正丁氧基、3-氯仲丁氧基、2-氯叔丁氧基、5-氯戊氧基、4-氯异戊氧基、6-氯己氧基及其异构体。 The term "C n -C m haloalkoxy" as used herein refers to C n -C m alkoxy substituted by one or more same or different halogen atoms, such as C 1 -C 12 haloalkoxy, more preferably C 1 -C 6 haloalkoxy, especially preferably C 1 -C 4 haloalkoxy. As examples of C n -C m haloalkoxy, mention may be made of monochloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 2-chloroisopropoxy, 4-chloro-n-butoxy , 3-chloro-sec-butoxy, 2-chloro-tert-butoxy, 5-chloropentyloxy, 4-chloroisoamyloxy, 6-chlorohexyloxy and its isomers.
本文所用的术语“C n-C m羟烷基”是指在C n-C m烷基对应的开链C n-C m烷烃的 任何碳原子上键合有一个羟基的C n-C m烷基，例如C 1-C 6羟烷基，尤其优选C 1-C 4羟烷基，例如羟甲基、羟乙基、羟丙基、羟异丙基、羟丁基、羟戊基、羟己基及其异构体。 As used herein, the term "C n -C m hydroxyalkyl" refers to a C n -C m that has a hydroxyl group bonded to any carbon atom of an open chain C n -C m alkane corresponding to a C n -C m alkyl group. Alkyl, such as C 1 -C 6 hydroxyalkyl, especially preferably C 1 -C 4 hydroxyalkyl, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, hydroxybutyl, hydroxypentyl, Hydroxyhexyl and its isomers.
本文所用的术语C 1-C 30亚烷基包括C 1-C 26亚烷基、C 1-C 18亚烷基、C 1-C 12亚烷基、C 1-C 6亚烷基、C 2-C 26亚烷基、C 2-C 18亚烷基、C 2-C 12亚烷基、C 2-C 6亚烷基、C 3-C 26亚烷基、C 3-C 18亚烷基、C 3-C 12亚烷基或C 3-C 6亚烷基。 The term C 1 -C 30 alkylene as used herein includes C 1 -C 26 alkylene, C 1 -C 18 alkylene, C 1 -C 12 alkylene, C 1 -C 6 alkylene, C 2 -C 26 alkylene, C 2 -C 18 alkylene, C 2 -C 12 alkylene, C 2 -C 6 alkylene, C 3 -C 26 alkylene, C 3 -C 18 alkylene Alkyl, C 3 -C 12 alkylene or C 3 -C 6 alkylene.
本文所用的术语C 1-C 30亚烷氧基包括C 1-C 26亚烷氧基、C 1-C 18亚烷氧基、C 1-C 12亚烷氧基、C 1-C 6亚烷氧基、C 2-C 26亚烷氧基、C 2-C 18亚烷氧基、C 2-C 12亚烷氧基、C 2-C 6亚烷氧基、C 3-C 26亚烷氧基、C 3-C 18亚烷氧基、C 3-C 12亚烷氧基或C 3-C 6亚烷氧基。 The term C 1 -C 30 alkyleneoxy as used herein includes C 1 -C 26 alkyleneoxy, C 1 -C 18 alkyleneoxy, C 1 -C 12 alkyleneoxy, C 1 -C 6 alkylene Alkoxy, C 2 -C 26 Alkyleneoxy, C 2 -C 18 Alkyleneoxy, C 2 -C 12 Alkyleneoxy, C 2 -C 6 Alkyleneoxy, C 3 -C 26 Alkylene Alkoxy, C 3 -C 18 alkyleneoxy, C 3 -C 12 alkyleneoxy or C 3 -C 6 alkyleneoxy.
在本文中，式(I)化合物中硅和苯环之间的亚丙基可以为-CH 2-CH 2-CH 2-或-CH(CH 3)-CH 2-，且优选为-CH(CH 3)-CH 2-。 Herein, the propylene group between the silicon and the benzene ring in the compound of formula (I) may be -CH 2 -CH 2 -CH 2 - or -CH(CH 3 )-CH 2 -, and is preferably -CH( CH3 ) -CH2- .
在本文中，丙烯基可以为-CH＝CH-CH 3或-CH 2-CH＝CH 2，且优选为-CH＝CH-CH 3。 Herein, the propenyl group may be -CH=CH-CH 3 or -CH 2 -CH=CH 2 , and is preferably -CH=CH-CH 3 .
根据本发明，m通常为1-50，例如1-40、1-30、1-20、1-18、1-15、1-12、1-9、2-40、2-30、2-20、2-18、2-15、2-12、2-9、3-40、3-30、3-20、3-18、3-15、3-12或3-9，例如为3、4、5、6、7、8或9。According to the present invention, m is generally 1-50, such as 1-40, 1-30, 1-20, 1-18, 1-15, 1-12, 1-9, 2-40, 2-30, 2- 20, 2-18, 2-15, 2-12, 2-9, 3-40, 3-30, 3-20, 3-18, 3-15, 3-12 or 3-9, such as 3, 4, 5, 6, 7, 8 or 9.
R 1、R 2、R 3、R 4、R 5相同或不同，并独立地为具有1-12个碳原子的有机基团，例如具有1-6或1-4个碳原子的有机基团。 R 1 , R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently an organic group with 1-12 carbon atoms, such as an organic group with 1-6 or 1-4 carbon atoms .
根据本发明的一个优选实施方案，R 1通常为C 1-C 12烷基或者C 1-C 12烷氧基。优选的是，R 1为C 1-C 6烷基或者C 1-C 6烷氧基。特别优选的是，R 1为C 1-C 4烷基或者C 1-C 4烷氧基。尤其是R 1为C 1-C 4烷基。例如，R 1为甲基、乙基、正丙基、异丙基、正丁基、仲丁基或叔丁基。 According to a preferred embodiment of the present invention, R 1 is usually C 1 -C 12 alkyl or C 1 -C 12 alkoxy. Preferably, R 1 is C 1 -C 6 alkyl or C 1 -C 6 alkoxy. Particularly preferably, R 1 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy. Especially R 1 is C 1 -C 4 alkyl. For example, R 1 is methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl or tert-butyl.
根据本发明的一个优选实施方案，R 2、R 3、R 4、R 5相同或不同，并通常独立地为C 6-C 10芳基、C 1-C 12烷基、C 1-C 12烷氧基或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 1-C 12烷基，其中R a为H或C 1-C 4烷基。优选的是，R 2、R 3、R 4、R 5相同或不同，并独立地为C 6-C 10芳基、C 1-C 6烷基、C 1-C 6烷氧基或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 1-C 6烷基，其中R a为H或C 1-C 4烷基。特别优选的是，R 2、R 3、R 4、R 5相同或不同，并独立地为苯基、C 1- C 4烷基、C 1-C 4烷氧基或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 1-C 4烷基，其中R a为H或C 1-C 4烷基。尤其是R 2、R 3、R 4、R 5相同或不同，并独立地为C 1-C 4烷基。例如，R 2、R 3、R 4、R 5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。 According to a preferred embodiment of the present invention, R 2 , R 3 , R 4 , and R 5 are the same or different, and are usually independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 Alkoxy or C 1 -C 12 alkyl interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl. Preferably, R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or replaced by one or multiple non-adjacent heteroatom-interrupted C 1 -C 6 alkyl groups independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl. It is particularly preferred that R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or replaced by one or more independently A C 1 -C 4 alkyl group selected from NR a , O, S with non-adjacent heteroatom intervals, wherein R a is H or C 1 -C 4 alkyl. Especially R 2 , R 3 , R 4 , R 5 are the same or different, and are independently C 1 -C 4 alkyl. For example, R 2 , R 3 , R 4 , and R 5 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.
本领域技术人员可以理解，被所述非相邻杂原子间隔是指，在两个碳原子，例如所述二价连接基团的两个碳原子中间存在非相邻杂原子。例如，被O间隔的亚乙基可以表示为：-CH 2-O-CH 2-。 Those skilled in the art can understand that being spaced by the non-adjacent heteroatom means that there is a non-adjacent heteroatom between two carbon atoms, for example, two carbon atoms of the divalent linking group. For example, an ethylene group interrupted by O can be represented as: -CH2 - O-CH2-.
根据本发明，R 6通常为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基。优选的是，R 6为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基。特别优选的是，R 6为H或C 1-C 4烷基。例如，R 6可以为H、氯、溴、甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、叔丁氧基、羟甲基、羟乙基、羟正丙基、羟异丙基、羟正丁基、羟仲丁基或羟叔丁基。 According to the present invention, R 6 is usually H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy. Preferably, R 6 is H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkoxy or C 1 -C 4 Haloalkoxy. It is particularly preferred that R 6 is H or C 1 -C 4 alkyl. For example, R can be H, chloro, bromo, methyl, ethyl, n - propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy , isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxy-sec-butyl or hydroxy tert-butyl.
根据本发明，L为直接键或具有1-30个碳原子的二价连接基团，例如具有1-28，1-18，1-12，2-30，2-28，2-18或2-12个碳原子的二价连接基团，例如具有2、3、4、5、6、7、8、9、10、11或12个碳原子的二价连接基团。根据一个实施方案，二价连接基团具有一个或多个独立地选自NR a、O、S，优选O的非相邻杂原子，其中R a为H或C 1-C 4烷基。 According to the invention, L is a direct bond or a divalent linking group with 1-30 carbon atoms, for example with 1-28, 1-18, 1-12, 2-30, 2-28, 2-18 or 2 - a divalent linking group of 12 carbon atoms, for example a divalent linking group having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. According to one embodiment, the divalent linking group has one or more non-adjacent heteroatoms independently selected from NR a , O, S, preferably O, wherein R a is H or C 1 -C 4 alkyl.
在一个优选实施方案中，L为直接键、C 1-C 30亚烷基、C 1-C 30亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷氧基，其中R a为H或C 1-C 4烷基。 In a preferred embodiment, L is a direct bond, C 1 -C 30 alkylene, C 1 -C 30 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 30 alkylene group separated by heteroatoms, or a C 2 -C 30 alkylene group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
在一个优选实施方案中，L为直接键、C 1-C 18亚烷基、C 1-C 18亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 18亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 18亚烷氧基，其中R a为H或C 1-C 4烷基。 In a preferred embodiment, L is a direct bond, C 1 -C 18 alkylene, C 1 -C 18 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 18 alkylene group interrupted by heteroatoms, or a C 2 -C 18 alkyleneoxy group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, and S, wherein R a is H or C 1 -C 4 alkyl.
在一个优选实施方案中，L为直接键、C 1-C 12亚烷基、C 1-C 12亚烷氧基、被一 个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 12亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 12亚烷氧基，其中R a为H或C 1-C 4烷基。 In a preferred embodiment, L is a direct bond, C 1 -C 12 alkylene, C 1 -C 12 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 12 alkylene group interrupted by heteroatoms, or a C 2 -C 12 alkyleneoxy group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
在一个优选实施方案中，L为直接键、C 2-C 12亚烷基、C 2-C 12亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 12亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 12亚烷氧基，其中R a为H或C 1-C 4烷基。 In a preferred embodiment, L is a direct bond, C 2 -C 12 alkylene, C 2 -C 12 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 12 alkylene group interrupted by heteroatoms, or a C 2 -C 12 alkyleneoxy group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
在一个优选实施方案中，L为L 1-O-L 2，L 1和L 2相互独立地为具有1-20，优选1-15，1-12，1-6，2-20，2-15，2-12或2-6个碳原子的二价连接基团。优选L 1和L 2相互独立地为C 1-C 15亚烷基，优选C 1-C 10亚烷基，优选C 1-C 6亚烷基，例如亚甲基、亚乙基、亚丙基、亚丁基、亚戊基或亚己基。例如，L 1为C 1-C 6亚烷基，优选C 2-C 6亚烷基且L 2为C 1-C 6亚烷基，优选C 1-C 4亚烷基。 In a preferred embodiment, L is L 1 -OL 2 , L 1 and L 2 are independently 1-20, preferably 1-15, 1-12, 1-6, 2-20, 2-15, A divalent linking group of 2-12 or 2-6 carbon atoms. Preferably L 1 and L 2 independently of each other are C 1 -C 15 alkylene, preferably C 1 -C 10 alkylene, preferably C 1 -C 6 alkylene, such as methylene, ethylene, propylene group, butylene, pentylene or hexylene. For example, L 1 is C 1 -C 6 alkylene, preferably C 2 -C 6 alkylene and L 2 is C 1 -C 6 alkylene, preferably C 1 -C 4 alkylene.
在本发明的一个实施方案中，式(I)化合物中的硅和苯环之间的亚丙基为-CH 2-CH 2-CH 2-或-CH(CH 3)-CH 2-，优选为-CH(CH 3)-CH 2-。 In one embodiment of the present invention, the propylene group between the silicon and the benzene ring in the compound of formula (I) is -CH 2 -CH 2 -CH 2 - or -CH(CH 3 )-CH 2 -, preferably is -CH(CH 3 )-CH 2 -.
在本发明的一个实施方案中，式(I)化合物中的各变量如下所定义：In one embodiment of the invention, each variable in the compound of formula (I) is defined as follows:
m为1-30；m is 1-30;
L为直接键或具有1-12个碳原子的二价连接基团；L is a direct bond or a divalent linking group with 1-12 carbon atoms;
R 1、R 2、R 3、R 4、R 5相同或不同，并独立地为具有1-6碳原子的有机基团；以及 R 1 , R 2 , R 3 , R 4 , R 5 are the same or different, and are independently organic groups with 1-6 carbon atoms; and
R 6为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基。 R 6 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.
在本发明的一个实施方案中，式(I)化合物中的各变量如下所定义：In one embodiment of the invention, each variable in the compound of formula (I) is defined as follows:
m为1-15；m is 1-15;
L为直接键或具有1-12个碳原子的二价连接基团；L is a direct bond or a divalent linking group with 1-12 carbon atoms;
R 1、R 2、R 3、R 4、R 5相同或不同，并独立地为具有1-6碳原子的有机基团；以及 R 1 , R 2 , R 3 , R 4 , R 5 are the same or different, and are independently organic groups with 1-6 carbon atoms; and
R 6为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基。 R 6 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.
在本发明的一个实施方案中，式(I)化合物中的各变量如下所定义：In one embodiment of the invention, each variable in the compound of formula (I) is defined as follows:
m为1-30；m is 1-30;
R 1为C 1-C 12烷基或者C 1-C 12烷氧基；和 R 1 is C 1 -C 12 alkyl or C 1 -C 12 alkoxy; and
R 2、R 3、R 4、R 5相同或不同，并独立地为C 6-C 10芳基、C 1-C 12烷基、C 1-C 12烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 12烷基，或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 12烷氧基，以及 R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and are independently represented by one or more C 2 -C 12 alkyl separated by non-adjacent heteroatoms selected from NR a , O, S, or C separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S 2 -C 12 alkoxy, and
L为直接键、C 1-C 30亚烷基、C 1-C 30亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷氧基， L is a direct bond, C 1 -C 30 alkylene, C 1 -C 30 alkyleneoxy, C 2 - separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S C 30 alkylene, or C 2 -C 30 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S,
其中R a为H或C 1-C 4烷基。 Wherein R a is H or C 1 -C 4 alkyl.
在本发明的一个优选实施方案中，本发明的式(I)化合物满足下述定义中的至少一个，优选全部：In a preferred embodiment of the present invention, the compound of formula (I) of the present invention satisfies at least one of the following definitions, preferably all:
-m为1-20，优选为2-15；- m is 1-20, preferably 2-15;
-R 1为C 1-C 6烷基或者C 1-C 6烷氧基；R 1优选为C 1-C 4烷基或者C 1-C 4烷氧基； -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;
-R 2、R 3、R 4、R 5、相同或不同，并独立地为C 6-C 10芳基、C 1-C 6烷基、C 1-C 6烷氧基或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 6烷基，其中R a为H或C 1-C 4烷基；优选的是，R 2、R 3、R 4、R 5、相同或不同，并独立地为苯基、C 1-C 4烷基、C 1-C 4烷氧基或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 4烷基，其中R a为H或C 1-C 4烷基； -R 2 , R 3 , R 4 , R 5 , the same or different, and independently C 6 -C 10 aryl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or replaced by one or more C 2 -C 6 alkyl groups independently selected from NR a , O, and S with non-adjacent heteroatom intervals, wherein R a is H or C 1 -C 4 alkyl; preferably, R 2 , R 3 , R 4 , R 5 , the same or different, and independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or one or more independently selected from NR a , O, S C 2 -C 4 alkyl interspersed by non-adjacent heteroatoms, wherein R a is H or C 1 -C 4 alkyl;
-R 6为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基； -R 6 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 ;
-L为C 2-C 30亚烷基、C 2-C 30亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷氧基，其中R a为H或C 1-C 4烷基。 -L is C 2 -C 30 alkylene, C 2 -C 30 alkyleneoxy, C 2 -C 30 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S Alkylene, or C 2 -C 30 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkane base.
在本发明的一个优选实施方案中，In a preferred embodiment of the invention,
m为1-20；m is 1-20;
R 1为C 1-C 12烷基或者C 1-C 12烷氧基； R 1 is C 1 -C 12 alkyl or C 1 -C 12 alkoxy;
R 2、R 3、R 4、R 5相同或不同，并独立地为C 6-C 10芳基、C 1-C 12烷基、C 1-C 12 烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 12烷基，或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 12烷氧基，其中R a为H或C 1-C 4烷基，以及 R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and are independently represented by one or more C 2 -C 12 alkyl separated by non-adjacent heteroatoms selected from NR a , O, S, or C separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S 2 -C 12 alkoxy, wherein R a is H or C 1 -C 4 alkyl, and
L为直接键、C 1-C 30亚烷基、C 1-C 30亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷氧基，其中R a为H或C 1-C 4烷基。 L is a direct bond, C 1 -C 30 alkylene, C 1 -C 30 alkyleneoxy, C 2 - separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S C 30 alkylene, or C 2 -C 30 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
在本发明的一个优选实施方案中，式(I)化合物中的各变量具有如下定义：In a preferred embodiment of the invention, each variable in the compound of formula (I) has the following definitions:
m为1-9；m is 1-9;
R 1为C 1-C 4烷基或者C 1-C 4烷氧基； R 1 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy;
R 2、R 3、R 4、R 5相同或不同，并独立地为苯基、C 1-C 4烷基、C 1-C 4烷氧基或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 1-C 4烷基，其中R a为H或C 1-C 4烷基； R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or one or more independently selected from NR a , C 1 -C 4 alkyl separated by non-adjacent heteroatoms of O, S, wherein R a is H or C 1 -C 4 alkyl;
R 6为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基；以及 R 6 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; as well as
L为L 1-O-L 2，其中L 1和L 2相互独立地为具有1-20，优选1-15个碳原子的二价连接基团，更优选C 1-C 15亚烷基。 L is L 1 -OL 2 , wherein L 1 and L 2 are independently a divalent linking group having 1-20, preferably 1-15 carbon atoms, more preferably C 1 -C 15 alkylene.
在本发明的一个优选实施方案中，In a preferred embodiment of the invention,
m为1-12；m is 1-12;
R 1为C 1-C 4烷基或者C 1-C 4烷氧基； R 1 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy;
R 2、R 3、R 4、R 5相同或不同，并独立地为苯基、C 1-C 4烷基、C 1-C 4烷氧基或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 1-C 4烷基，其中R a为H或C 1-C 4烷基； R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or one or more independently selected from NR a , C 1 -C 4 alkyl separated by non-adjacent heteroatoms of O, S, wherein R a is H or C 1 -C 4 alkyl;
R 6为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基；以及 R 6 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; as well as
L为L 1-O-L 2，其中L 1和L 2相互独立地为C 1-C 15亚烷基。 L is L 1 -OL 2 , wherein L 1 and L 2 are independently C 1 -C 15 alkylene.
在本发明的一个优选实施方案中，In a preferred embodiment of the invention,
m为3-9；m is 3-9;
R 1为C 1-C 4烷基； R 1 is C 1 -C 4 alkyl;
R 2、R 3、R 4、R 5相同或不同，并独立地为C 1-C 4烷基； R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently C 1 -C 4 alkyl;
R 6为H或C 1-C 4烷基，尤其是H或乙基，以及 R 6 is H or C 1 -C 4 alkyl, especially H or ethyl, and
L为L 1-O-L 2，其中L 1和L 2相互独立地为C 1-C 6亚烷基。 L is L 1 -OL 2 , wherein L 1 and L 2 are independently C 1 -C 6 alkylene.
在本发明的另一实施方案中，式(Ⅰ)化合物为一种或多种选自下组的化合物：In another embodiment of the present invention, the compound of formula (I) is one or more compounds selected from the group consisting of:
Figure PCTCN2022099400-appb-000012
Figure PCTCN2022099400-appb-000012
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，According to a second aspect of the present invention, there is provided a method for preparing the compound of formula (I) of the present invention,
包括：include:
使得式(VI)化合物与式(Ⅶ)化合物反应得到式(I)化合物Make the compound of formula (VI) react with the compound of formula (VII) to obtain the compound of formula (I)
Figure PCTCN2022099400-appb-000013
Figure PCTCN2022099400-appb-000013
其中L和R 6如上对式(I)化合物所定义。 wherein L and R 6 are as defined above for the compound of formula (I).
Figure PCTCN2022099400-appb-000014
Figure PCTCN2022099400-appb-000014
其中m、R 1、R 2、R 3、R 4和R 5如上对式(I)化合物所定义。 wherein m, R 1 , R 2 , R 3 , R 4 and R 5 are as defined above for the compound of formula (I).
在本发明的一个实施方案中，式(I)化合物中的L为L 1-O-L 2，其中L 1和L 2如上所定义，优选C 1-C 15亚烷基，更优选C 1-C 6亚烷基。式(VI)化合物可通过如下步骤制备： In one embodiment of the present invention, L in the compound of formula (I) is L 1 -OL 2 , wherein L 1 and L 2 are as defined above, preferably C 1 -C 15 alkylene, more preferably C 1 -C 6 alkylene. The compound of formula (VI) can be prepared by the following steps:
(1)使式(Ⅱ)化合物：(1) make formula (II) compound:
Figure PCTCN2022099400-appb-000015
Figure PCTCN2022099400-appb-000015
与式(Ⅲ)化合物反应，React with the compound of formula (III),
Figure PCTCN2022099400-appb-000016
Figure PCTCN2022099400-appb-000016
其中L 1为具有1-20，优选1-15个碳原子的二价连接基团，更优选C 1-C 15亚烷基，尤其是C 1-C 6亚烷基，并且X为卤素，例如氟、氯、溴或碘， wherein L is a divalent linking group having 1-20 , preferably 1-15 carbon atoms, more preferably C 1 -C 15 alkylene, especially C 1 -C 6 alkylene, and X is halogen, such as fluorine, chlorine, bromine or iodine,
得到式(Ⅳ)化合物Obtain the compound of formula (Ⅳ)
Figure PCTCN2022099400-appb-000017
Figure PCTCN2022099400-appb-000017
其中L 1如对式(III)化合物所定义； Wherein L is as defined for the compound of formula (III);
以及as well as
(2)使式(Ⅳ)化合物与式(Ⅴ)化合物反应得到式(Ⅵ)化合物(2) react the compound of formula (Ⅳ) with the compound of formula (Ⅴ) to obtain the compound of formula (Ⅵ)
Figure PCTCN2022099400-appb-000018
Figure PCTCN2022099400-appb-000018
其中L 2为具有1-20，优选1-15个碳原子的二价连接基团，更优选C 1-C 15亚烷基，尤其是C 1-C 6亚烷基和R 6如上对式(I)化合物所定义，并且X为卤素，例如氯、溴或碘。 wherein L 2 is a divalent linking group having 1-20, preferably 1-15 carbon atoms, more preferably a C 1 -C 15 alkylene group, especially a C 1 -C 6 alkylene group and R 6 is as above for the formula (I) Compounds are defined and X is halogen such as chlorine, bromine or iodine.
在步骤(1)中，式(Ⅱ)化合物中的酚羟基与式(Ⅲ)化合物中的卤素的反应属于本领域已知的反应类型，反应产生卤化氢。通常而言，该反应在碱性催化剂存在下进行。作为适合该反应的碱性催化剂，可以提及氢化钠、氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物。催化剂的用量也是常规的。通常而言，式(Ⅱ)化合物与碱性催化剂的摩尔用量比为1:1-1:5，优选1:1-1:3。式(Ⅱ)化合物与式(Ⅲ)化合物的反应通常在溶剂中进行。作为溶剂的类型，没有特别的限制，只要能将式(Ⅱ)化合物、式(Ⅲ)化合物和相应碱性催化剂溶解并且不参与式(Ⅱ)化合物与式(Ⅲ)化合物之间的反应即可，优选该溶剂还有利于产物，即式(Ⅳ)化合物析出。作为该溶剂，通常使用有机溶剂，优选使用甲苯、丙酮、丁酮、甲苯、四氢呋喃、环己烷、1,4-二氧六环、二氯甲烷、乙腈或其任意混合物。溶剂的用量也是常规的，通常而言，溶剂的用量为式(Ⅱ)化合物和式(Ⅲ)化合物总重量的1.0-3倍。式(Ⅱ)化合物和式(Ⅲ)化合物的用量通常以大致等摩尔量使用。有利的是，式(Ⅱ)化合物与式(Ⅲ)化合物的用量摩尔比为1:0.75-1:1.5，或1:1-1:1.3。为了实现上述反应，通常将式(Ⅱ)化合物溶解在溶剂中，加入碱性催化剂，然后加入式(Ⅲ)化合物，加料完毕之后将所得反应混合物搅拌均匀，然后升温至30-120℃，优选升温至40-70℃。升温后通常继续反应3-16小时，优选继续反应4-10小时。当然，反应有利地在搅拌下进行。反应完毕之后，通过常规后处理，即获得式(Ⅳ)化合物。该后处理通常包括萃取或洗涤(例如用水洗涤，水洗涤之后有利地采用吸水化合物比如硫酸镁或硫酸钠除水)、过滤或离心除去固体杂质，旋蒸除去溶剂，减压蒸馏进一步除去溶剂。如果要获得更高纯度的产物，还可重结晶或柱层析法获得产物。In step (1), the reaction of the phenolic hydroxyl group in the compound of formula (II) with the halogen in the compound of formula (III) belongs to the type of reaction known in the art, and the reaction produces hydrogen halide. Generally, the reaction is carried out in the presence of a basic catalyst. As basic catalysts suitable for this reaction, mention may be made of sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof. The amount of catalyst used is also conventional. Generally speaking, the molar ratio of the compound of formula (II) to the basic catalyst is 1:1-1:5, preferably 1:1-1:3. The reaction of the compound of formula (II) with the compound of formula (III) is usually carried out in a solvent. As the type of solvent, there is no special limitation, as long as the compound of formula (II), compound of formula (III) and corresponding basic catalyst can be dissolved and the reaction between the compound of formula (II) and compound of formula (III) can not be participated in. , preferably the solvent is also conducive to the precipitation of the product, that is, the compound of formula (IV). As the solvent, an organic solvent is usually used, preferably toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile or any mixture thereof. The amount of solvent used is also conventional, generally speaking, the amount of solvent used is 1.0-3 times the total weight of the compound of formula (II) and compound of formula (III). The compound of formula (II) and the compound of formula (III) are usually used in approximately equimolar amounts. Advantageously, the molar ratio of the compound of formula (II) to that of formula (III) is 1:0.75-1:1.5, or 1:1-1:1.3. In order to realize the above reaction, the compound of formula (II) is usually dissolved in a solvent, a basic catalyst is added, and then the compound of formula (III) is added. After the addition is complete, the resulting reaction mixture is stirred evenly, and then the temperature is raised to 30-120° C., preferably to 40-70°C. After the temperature is raised, the reaction is usually continued for 3-16 hours, preferably for 4-10 hours. Of course, the reaction is advantageously carried out with stirring. After the reaction is completed, the compound of formula (IV) can be obtained through conventional post-treatment. The post-treatment usually includes extraction or washing (such as washing with water, after which water-absorbing compounds such as magnesium sulfate or sodium sulfate are advantageously used to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove solvents, and vacuum distillation to further remove solvents. If a higher purity product is to be obtained, the product can also be obtained by recrystallization or column chromatography.
在步骤(1)中，式(II)化合物中的苯环上的-CH 2-CH＝CH 2中的双键的位置 在碱性催化剂存在下可发生改变，可以形成-CH＝CH-CH 3。 In step (1), the position of the double bond in -CH 2 -CH=CH 2 on the benzene ring in the compound of formula (II) can be changed in the presence of a basic catalyst to form -CH=CH-CH 3 .
在步骤(2)中，式(Ⅳ)化合物中的端羟基与式(Ⅴ)化合物中的卤素的反应是已知的，反应产生卤化氢。通常而言，该反应在催化剂存在下进行。作为适合该反应的催化剂，可以提及氢化钠、氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物。催化剂的用量也是常规的。通常而言，式(Ⅳ)化合物与催化剂的摩尔用量比为1:1-1:5，优选1:1-1:3。式(Ⅳ)化合物与式(Ⅴ)化合物的反应通常在溶剂中进行。作为溶剂的类型，没有特别的限制，只要能将式(Ⅳ)化合物、式(Ⅴ)化合物和相应催化剂溶解并且不参与式(Ⅳ)化合物与式(Ⅴ)化合物之间的反应即可，优选该溶剂还有有利于产物，即式(Ⅵ)化合物析出。作为该溶剂，通常使用有机溶剂，优选使用甲苯、丙酮、丁酮、甲苯、四氢呋喃、环己烷、1,4-二氧六环、二氯甲烷、乙腈或其任意混合物。溶剂的用量也是常规的，通常而言，溶剂的用量为式(Ⅳ)化合物和式(Ⅴ)化合物总重量的1.0-3倍。式(Ⅳ)化合物和式(Ⅴ)化合物的用量通常以大致等摩尔量使用。有利的是，式(Ⅳ)化合物与式(Ⅳ)化合物摩尔比为1:0.75-1:1.5，或1:1-1:1.2。为了实现上述反应，通常将式(Ⅳ)化合物和催化剂溶解在溶剂中，然后加入式(Ⅴ)化合物在溶剂中的溶液，加料完毕之后升温至40-100℃，优选升温至60-90℃。升温后通常继续反应3-24小时，优选继续反应4-10小时。当然，反应有利地在搅拌下进行。反应完毕之后，通过常规后处理，即获得式(Ⅵ)化合物。该后处理通常包括萃取或洗涤(例如用水洗涤，水洗涤之后有利地采用吸水化合物比如硫酸镁或硫酸钠除水)、过滤或离心除去固体杂质，旋蒸除去溶剂，减压蒸馏进一步除去溶剂。如果要获得更高纯度的产物，还可重结晶或柱层析法分离杂质。In step (2), the reaction of the terminal hydroxyl group in the compound of formula (IV) with the halogen in the compound of formula (V) is known to produce hydrogen halide. Generally speaking, the reaction is carried out in the presence of a catalyst. As suitable catalysts for this reaction, mention may be made of sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof. The amount of catalyst used is also conventional. Generally speaking, the molar ratio of the compound of formula (IV) to the catalyst is 1:1-1:5, preferably 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. As the type of solvent, there is no special limitation, as long as the compound of formula (IV), compound of formula (V) and corresponding catalyst can be dissolved and do not participate in the reaction between the compound of formula (IV) and compound of formula (V), preferably The solvent also facilitates the precipitation of the product, namely the compound of formula (VI). As the solvent, an organic solvent is usually used, preferably toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile or any mixture thereof. The amount of solvent used is also conventional, generally speaking, the amount of solvent used is 1.0-3 times the total weight of the compound of formula (IV) and compound of formula (V). The compound of formula (IV) and the compound of formula (V) are usually used in approximately equimolar amounts. Advantageously, the molar ratio of the compound of formula (IV) to the compound of formula (IV) is 1:0.75-1:1.5, or 1:1-1:1.2. In order to realize the above reaction, the compound of formula (IV) and the catalyst are usually dissolved in a solvent, and then the solution of the compound of formula (V) in the solvent is added. After the addition, the temperature is raised to 40-100° C., preferably to 60-90° C. After the temperature is raised, the reaction is usually continued for 3-24 hours, preferably for 4-10 hours. Of course, the reaction is advantageously carried out with stirring. After the reaction is completed, the compound of formula (VI) can be obtained through conventional post-treatment. The post-treatment usually includes extraction or washing (such as washing with water, after which water-absorbing compounds such as magnesium sulfate or sodium sulfate are advantageously used to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove solvents, and vacuum distillation to further remove solvents. If a higher purity product is to be obtained, impurities can also be separated by recrystallization or column chromatography.
在式(VI)化合物与式(VII)化合物的反应中，式(Ⅶ)化合物的硅原子上含有氢原子，因此，式(Ⅶ)化合物可称作含氢硅油。式(Ⅶ)化合物中硅原子键合的氢原子与式(Ⅵ)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，基于含氢硅油的重量，催化剂的用量为2-500ppm，优选10-300ppm。式(Ⅵ)化合物与式(Ⅶ)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(Ⅵ)化合物、式(Ⅶ)化合物和催化剂溶解并 且不参与式(Ⅵ)化合物与式(Ⅶ)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、二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(Ⅵ)化合物和式(Ⅶ)化合物总重量的1.5-3倍。式(Ⅵ)化合物和式(Ⅶ)化合物的用量通常以大致等摩尔量使用。有利的是，式(Ⅵ)化合物与式(Ⅶ)化合物的用量摩尔比为1:0.75-1:1.5。为了实现上述反应，通常先将式(Ⅵ)化合物与催化剂溶解在溶剂中陈化一段时间后，再与式(Ⅶ)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℃陈化。陈化时间通常为30-60分钟。式(Ⅵ)化合物与式(Ⅶ)化合物之间的反应温度通常为80-110℃，优选85-100℃。式(Ⅵ)化合物与式(Ⅶ)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)化合物产物。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。In the reaction between the compound of formula (VI) and the compound of formula (VII), the silicon atom of the compound of formula (VII) contains hydrogen atoms, therefore, the compound of formula (VII) can be called hydrogen-containing silicone oil. Addition reactions of silicon-bonded hydrogen atoms in compounds of formula (VII) to unsaturated carbon-carbon double bonds in compounds of formula (VI) are of the type known in the art. Generally speaking, the reaction is carried out in the presence of a catalyst. As a catalyst suitable for this reaction, a Karstedt catalyst or a Speier catalyst is generally used. The amount of catalyst used is also conventional. Generally speaking, based on the weight of the hydrogen-containing silicone oil, the catalyst is used in an amount of 2-500 ppm, preferably 10-300 ppm. The reaction of the compound of formula (VI) with the compound of formula (VII) is usually carried out in a solvent. As the type of solvent, there is no particular limitation, as long as the compound of formula (VI), the compound of formula (VII) and the catalyst can be dissolved and it does not participate in the reaction between the compound of formula (VI) and the compound of formula (VII). The solvent also facilitates the precipitation of the product, the compound of formula (I). As the solvent, an organic solvent is usually used, preferably petroleum ether, dichloromethane, toluene, xylene 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 (VI) and compound of formula (VII). The compound of formula (VI) and the compound of formula (VII) are usually used in approximately equimolar amounts. Advantageously, the molar ratio of the compound of formula (VI) to the compound of formula (VII) is 1:0.75-1:1.5. In order to realize the above reaction, the compound of formula (VI) and the catalyst are usually dissolved in a solvent and aged for a period of time, then contacted with the compound of formula (VII), 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 elevated temperature, usually at 40-70°C. The aging time is usually 30-60 minutes. The reaction temperature between the compound of formula (VI) and the compound of formula (VII) is usually 80-110°C, preferably 85-100°C. The holding time of the reaction between the compound of formula (VI) and the compound of formula (VII) at the reaction temperature is usually 3-6 hours, preferably 3.5-5.5 hours. Of course, the reaction is advantageously carried out with stirring. After the reaction is completed, the product of the compound of formula (I) can be obtained through conventional post-treatment. The post-treatment usually includes filtration or centrifugation to remove solid impurities, rotary evaporation to remove solvent, and vacuum distillation to further remove solvent. If a higher purity product is to be obtained, it can also be recrystallized.
本发明的式(VI)化合物是新的。因此，本发明的一个方面涉及式(VI)化合物：The compounds of formula (VI) according to the invention are novel. Accordingly, one aspect of the present invention relates to compounds of formula (VI):
Figure PCTCN2022099400-appb-000019
Figure PCTCN2022099400-appb-000019
其中L和R 6如上所定义。 wherein L and R are as defined above.
在式(VI)化合物中，所述丙烯基为-CH 2-CH 2-CH 2-或-CH(CH 3)-CH 2-，优选为-CH＝CH-CH 3。 In the compound of formula (VI), the propenyl group is -CH 2 -CH 2 -CH 2 - or -CH(CH 3 )-CH 2 -, preferably -CH=CH-CH 3 .
本发明式(Ⅰ)化合物是一种阳离子光固化单体，其聚合速率快、转化率高且可促进其他阳离子单体聚合，光固化聚合之后得到的光固化材料机械性能，特别是拉伸性能好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强，耐热性好。The compound of formula (I) of the present invention is a cationic photocurable monomer, which has fast polymerization rate, high conversion rate and can promote the polymerization of other cationic monomers. The photocurable material obtained after photocuring polymerization has mechanical properties, especially tensile properties. Good, excellent hydrophobic performance, anti-stain, anti-fingerprint, anti-chemical corrosion, strong anti-aging performance, good heat resistance.
根据本发明的第三个方面，提供了一种可光固化组合物，该组合物包含本发明的式(Ⅰ)化合物作为聚合单体。该可光固化组合物除了包含本发明的式(Ⅰ) 化合物以外，还可包含开环聚合的阳离子光引发剂(可引发阳离子聚合的光引发剂)以及任选地其它含有可阳离子光固化基团如乙烯基醚双键、脂环族环氧基、环氧乙烷基或者氧杂环丁烷基的单体、低聚物，例如3,4-环氧环己基甲基3,4-环氧环己基甲酸酯(E4221)。According to a third aspect of the present invention, there is provided a photocurable composition comprising the compound of formula (I) of the present invention as a polymerizable monomer. In addition to the compound of formula (I) of the present invention, the photocurable composition may also contain a cationic photoinitiator for ring-opening polymerization (a photoinitiator capable of initiating cationic polymerization) and optionally other photoinitiators containing cationic photocurable groups Groups such as vinyl ether double bonds, alicyclic epoxy, oxiranyl or oxetanyl monomers, oligomers, such as 3,4-epoxycyclohexylmethyl3,4- Epoxycyclohexyl carboxylate (E4221).
在本发明的可光固化组合物中，基于聚合单体的总量，本发明的式(I)化合物的量可以为至少0.5mol％，至少1mol％，至少2mol％，例如0.5-12mol％，或0.5-10mol％，或1-10mol％。In the photocurable composition of the present invention, the amount of the compound of formula (I) of the present invention may be at least 0.5 mol%, at least 1 mol%, at least 2 mol%, for example 0.5-12 mol%, based on the total amount of polymerized monomers, Or 0.5-10mol%, or 1-10mol%.
本发明可光固化组合物可以为光固化涂料组合物、光固化油墨组合物、光致抗蚀组合物等。该组合物在固化后，所得固化产物拉伸性能好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强。The photocurable composition of the present invention may be a photocurable coating composition, a photocurable ink composition, a photoresist composition, and the like. After the composition is cured, the obtained cured product has good tensile properties, excellent hydrophobic properties, stain resistance, fingerprint resistance, chemical corrosion resistance and strong aging resistance.
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)As photoinitiators for ring-opening polymerization, iodonium salts and sulfonium salts are commonly used. Advantageously, the iodonium salt photoinitiator and the sulfonium salt photoinitiator have the following general formulas (A) and (B) respectively
Figure PCTCN2022099400-appb-000020
Figure PCTCN2022099400-appb-000020
其中in
R a、R b、R c、R d、R e各自独立地是未取代的C 6-C 10芳基，或者被选自卤素、硝基、羰基、C 1-C 12烷基、C 1-C 12烷氧基、苯硫基、苯基和取代苯基的取代基取代的C 6-C 10芳基，优选是苯基或萘基，或者被选自卤素、硝基、C 1-C 6烷基和取代苯基的取代基取代的苯基或萘基，其中所述取代苯基包含的取代基为一个或多个选自卤素、硝基、C 1-C 6烷基和C 1-C 6烷氧基的基团；以及 R a , R b , R c , R d , R e are each independently unsubstituted C 6 -C 10 aryl, or are selected from halogen, nitro, carbonyl, C 1 -C 12 alkyl, C 1 C 6 -C 10 aryl substituted by substituents of -C 12 alkoxy, phenylthio, phenyl and substituted phenyl, preferably phenyl or naphthyl, or selected from halogen, nitro, C 1 - C 6 alkyl and substituted phenyl or naphthyl substituted by substituents of phenyl, wherein the substituted phenyl contains one or more substituents selected from halogen, nitro, C 1 -C 6 alkyl and C 1 -C 6 alkoxy radicals; and
Y、Z是非亲核性阴离子，例如三氟甲磺酸根、BF 4 -、ClO 4 -、PF 6 -、AsF 6 -、SbF 6 -。 Y and Z are non-nucleophilic anions, such as trifluoromethanesulfonate, BF 4 - , ClO 4 - , PF 6 - , AsF 6 - , SbF 6 - .
例如，作为光引发剂，可以使用选自下组中的一种或多种:4-(苯硫基)苯基·二苯基硫鎓六氟磷酸盐、4-(苯硫基)苯基·二苯基硫鎓六氟锑酸盐、双(4-(二苯基锍)苯基)硫醚双六氟磷酸盐、双(4-(二苯基锍)苯基)硫醚双六氟锑酸盐、10-(4-联苯基)-2-异丙基噻吨酮-10-硫鎓六氟磷酸盐、10-(4-联苯基)-2-异丙基噻吨酮-10-硫鎓六氟锑酸盐、六氟磷酸二苯基碘鎓盐(810)、4-辛氧基二苯碘鎓六氟磷酸盐、4-辛氧基二苯碘鎓六氟锑酸盐、4-异丁基苯基·4'-甲基苯基 碘鎓六氟磷酸盐、4-异丁基苯基·4'-甲基苯基碘鎓六氟锑酸盐、双(4-十二烷基苯)碘鎓六氟锑酸盐、双(4-十二烷基苯)碘鎓六氟磷酸盐、双(4-叔丁基苯)碘鎓六氟磷酸盐、双(4-叔丁基苯)碘鎓六氟锑酸盐。For example, as a 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 bishexafluorophosphate Fluoroantimonate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone Keto-10-sulfonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate (810), 4-octyloxydiphenyliodonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoro Antimonate, 4-isobutylphenyl·4'-methylphenyliodonium hexafluorophosphate, 4-isobutylphenyl·4'-methylphenyliodonium hexafluoroantimonate, bis (4-dodecylbenzene)iodonium hexafluoroantimonate, bis(4-dodecylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, Bis(4-tert-butylphenyl)iodonium hexafluoroantimonate.
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2-异丙基硫杂蒽酮。The photocurable composition of the present invention may also contain a sensitizer. As a sensitizer, mention may be made, for example, of 2-isopropylthioxanthone.
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中聚合单体的总摩尔量，光引发剂的含量通常为0.5-5mol％，优选为1-3mol％。For the purposes of the present invention, the amount of photoinitiator used is conventional. Based on the total molar amount of polymerized monomers in the photocurable composition of the present invention, the content of the photoinitiator is generally 0.5-5 mol%, preferably 1-3 mol%.
根据本发明的一个方面，提供了一种由本发明的可光固化组合物得到的光固化材料。根据本发明，该材料通过将本发明的可光固化组合物光固化而获得。该光固化材料具有良好的机械性能，特别是拉伸性能，疏水性能优良，且具有抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强，耐热性好的优点。According to one aspect of the present invention, there is provided a photocurable material obtained from the photocurable composition of the present invention. According to the invention, the material is obtained by photocuring the photocurable composition of the invention. The light-curing material has good mechanical properties, especially tensile properties, excellent hydrophobic properties, and has the advantages of anti-staining, anti-fingerprint, anti-chemical corrosion, strong anti-aging performance and good heat resistance.
根据本发明的式(I)化合物还可用于光固化涂料、粘合剂、油墨和光致抗蚀剂。因此，本发明还涉及式(I)化合物在光固化涂料、粘合剂、油墨和光致抗蚀剂中的用途。The compounds of formula (I) according to the invention can also be used in photocurable coatings, adhesives, inks and photoresists. Accordingly, the present invention also relates to the use of compounds of formula (I) in photocurable coatings, adhesives, inks and photoresists.
实施例Example
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。The experimental methods used in the following examples are conventional methods unless otherwise specified.
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。The materials and reagents used in the following examples can be obtained from commercial sources unless otherwise specified.
实施例1Example 1
将200mmol丁香酚、200mL乙腈、240mmol碳酸钾和溴丙醇240mmol放入三口烧瓶中搅拌。升温至60℃，反应6h，结束反应。将得到的样品取上层清液旋蒸除去溶剂。将旋蒸后得到的液体中加入400mL乙酸乙酯，水洗三次后旋蒸除去乙酸乙酯，最后产物1-a的产率为57.4％。Put 200mmol eugenol, 200mL acetonitrile, 240mmol potassium carbonate and 240mmol bromopropanol into a three-neck flask and stir. Raise the temperature to 60°C, react for 6h, and end the reaction. The supernatant of the obtained sample was removed by rotary evaporation to remove the solvent. Add 400 mL of ethyl acetate to the liquid obtained after rotary evaporation, wash with water three times, and then remove ethyl acetate by rotary evaporation. The yield of the final product 1-a is 57.4%.
Figure PCTCN2022099400-appb-000021
Figure PCTCN2022099400-appb-000021
[1-a]: 1H NMR(400MHz,DMSO-d 6)δ6.92-6.63(m,3H),5.94(ddt,J＝8.8,7.0,6.7Hz,1H),5.13-4.95(m,2H),4.50(t,J＝5.2Hz,1H),3.98(t,J＝6.4Hz,2H),3.74(s,3H),3.56(td,J＝6.3,5.1Hz,2H),3.29(dt,J＝6.8,1.5Hz,2H),1.84(p,J＝6.3 Hz,2H)。 [1-a]: 1 H NMR (400MHz, DMSO-d 6 ) δ6.92-6.63 (m, 3H), 5.94 (ddt, J=8.8, 7.0, 6.7Hz, 1H), 5.13-4.95 (m, 2H), 4.50(t, J=5.2Hz, 1H), 3.98(t, J=6.4Hz, 2H), 3.74(s, 3H), 3.56(td, J=6.3, 5.1Hz, 2H), 3.29( dt, J = 6.8, 1.5 Hz, 2H), 1.84 (p, J = 6.3 Hz, 2H).
首先将9.6g(24mmol)NaH加入到装有10mL的四氢呋喃的三口烧瓶中搅拌。再将20mmol的1-a加到三口瓶中，之后将22mmol的3-乙基-3-氯甲基氧杂环丁烷加到反应体系中，搅拌均匀后升温至50℃冷凝回流。反应6h后结束反应。待反应液冷却后加入水猝灭反应，随后旋蒸除去溶剂。之后分别用30mL乙酸乙酯萃取3次水中的产物。收集有机层用水洗3次。取有机层溶液加入无水硫酸镁干燥过夜。最后，将干燥后的液体旋蒸除去乙酸乙酯。最后用柱层析法分离得到1-b，产率59.1％。First, 9.6 g (24 mmol) of NaH was added into a three-neck flask containing 10 mL of tetrahydrofuran and stirred. Then add 20mmol of 1-a into the three-necked flask, and then add 22mmol of 3-ethyl-3-chloromethyloxetane into the reaction system, stir evenly and heat up to 50°C to condense and reflux. After 6 hours of reaction, the reaction was terminated. After the reaction solution was cooled, water was added to quench the reaction, and then the solvent was removed by rotary evaporation. Then the product in water was extracted three times with 30 mL ethyl acetate respectively. The collected organic layer was washed 3 times with water. The organic layer solution was added to anhydrous magnesium sulfate and dried overnight. Finally, the dried liquid was rotary evaporated to remove ethyl acetate. Finally, 1-b was separated by column chromatography with a yield of 59.1%.
Figure PCTCN2022099400-appb-000022
Figure PCTCN2022099400-appb-000022
[1-b]: 1H NMR(400MHz,Chloroform-d)δ6.95-6.78(m,3H),6.43-6.25(m,1H),6.11(dq,J＝7.7,6.6Hz,1H),4.41(dd,J＝6.9,5.8Hz,4H),4.12(t,J＝6.4Hz,2H),3.87(d,J＝2.2Hz,3H),3.73-3.62(m,2H),3.56(d,J＝2.3Hz,2H),2.12(q,J＝6.1Hz,2H),1.87(dd,J＝6.6,1.7Hz,3H),1.74(qd,J＝7.5,1.7Hz,2H),0.88(t,J＝7.5Hz,3H)。 [1-b]: 1 H NMR (400MHz, Chloroform-d) δ6.95-6.78 (m, 3H), 6.43-6.25 (m, 1H), 6.11 (dq, J=7.7, 6.6Hz, 1H), 4.41(dd, J=6.9, 5.8Hz, 4H), 4.12(t, J=6.4Hz, 2H), 3.87(d, J=2.2Hz, 3H), 3.73-3.62(m, 2H), 3.56(d ,J=2.3Hz,2H),2.12(q,J=6.1Hz,2H),1.87(dd,J=6.6,1.7Hz,3H),1.74(qd,J=7.5,1.7Hz,2H),0.88 (t, J=7.5Hz, 3H).
在装有温度探头和回流冷凝管的三口烧瓶中，将含氢硅油2.06g(5mmol)(对应于式(VII)化合物，其中m＝3，R 1为正丁基，以及R 2、R 3、R 4和R 5为甲基)和0.412g 100ppm浓度的Karstedt催化剂(Karstedt催化剂，安耐吉化学)溶解在溶剂无水甲苯中，然后升温至60℃保持40min。之后向三口烧瓶中滴加化合物1-b 1.932g(6mmol)，升温至90℃，在搅拌下保持4h。离心除去固体杂质，用旋转蒸发器于温度45℃和压力0.1MPa下旋蒸，再将所得溶液于300Pa和40℃下减压蒸馏，得到产物。经核磁氢谱表征，确定为化合物1，产率为51％，下文有时称作Eugenol-Si 3。 In a three-necked flask equipped with a temperature probe and a reflux condenser, 2.06 g (5 mmol) of hydrogen-containing silicone oil (corresponding to the compound of formula (VII), wherein m=3, R 1 is n-butyl, and R 2 , R 3 , R 4 and R 5 are methyl groups) and 0.412 g of 100 ppm Karstedt catalyst (Karstedt catalyst, Anaiji Chemical) were dissolved in the solvent anhydrous toluene, and then heated to 60 ° C for 40 min. Then, 1.932 g (6 mmol) of compound 1-b was added dropwise to the three-necked flask, the temperature was raised to 90° C., and the mixture was kept under stirring for 4 h. Centrifuge to remove solid impurities, use a rotary evaporator at a temperature of 45 °C and a pressure of 0.1 MPa to rotate, and then distill the resulting solution under reduced pressure at 300 Pa and 40 °C to obtain the product. Characterized by H NMR spectrum, it was determined to be compound 1 with a yield of 51%, which is sometimes referred to as Eugenol-Si 3 hereinafter.
Figure PCTCN2022099400-appb-000023
Figure PCTCN2022099400-appb-000023
[Eugenol-Si 3]: 1H NMR(400MHz,Chloroform-d)δ7.03-6.38(m,3H),4.45(dd,J＝6.9,5.8Hz,4H),4.24-4.06(m,2H),3.89(d,J＝2.2Hz,3H),3.70(t,J＝6.1Hz,2H),3.59(s,2H),2.12-2.04(m,2H),1.94-1.86(m,2H),1.77(q,J＝7.5Hz,3H),1.41-1.28(m,4H),0.97-0.84(m,9H),0.62-0.55(m,2H),0.16-0.10(m,24H)。 [Eugenol-Si 3 ]: 1 H NMR (400MHz, Chloroform-d) δ7.03-6.38 (m, 3H), 4.45 (dd, J＝6.9, 5.8Hz, 4H), 4.24-4.06 (m, 2H) ,3.89(d,J=2.2Hz,3H),3.70(t,J=6.1Hz,2H),3.59(s,2H),2.12-2.04(m,2H),1.94-1.86(m,2H), 1.77 (q, J = 7.5Hz, 3H), 1.41-1.28 (m, 4H), 0.97-0.84 (m, 9H), 0.62-0.55 (m, 2H), 0.16-0.10 (m, 24H).
实施例2Example 2
在装有温度探头和回流冷凝管的三口烧瓶中，将含氢硅油3.17g(5mmol)(对应于式(VⅡ)化合物，其中m＝6，R 1为正丁基，以及R 2、R 3、R 4和R 5为甲基)和0.634g 100ppm浓度的Karstedt催化剂(Karstedt催化剂，安耐吉化学)溶解在溶剂无水甲苯中，然后升温至60℃保持40min。之后向三口烧瓶中滴加化合物1-b 1.932g(6mmol)，升温至90℃，在搅拌下保持4h。离心除去固体杂质，用旋转蒸发器于温度45℃和压力0.1MPa下旋蒸，再将所得溶液于300Pa和40℃下减压蒸馏，得到产物。经核磁氢谱表征，确定为化合物2，产率为90％，下文有时称作Eugenol-Si 6。 In a three-necked flask equipped with a temperature probe and a reflux condenser, 3.17 g (5 mmol) of hydrogen-containing silicone oil (corresponding to the compound of formula (VII), wherein m=6, R 1 is n-butyl, and R 2 , R 3 , R 4 and R 5 are methyl) and 0.634 g of 100 ppm concentration of Karstedt catalyst (Karstedt catalyst, Anaiji Chemical) were dissolved in the solvent anhydrous toluene, and then heated to 60 ° C for 40 min. Then, 1.932 g (6 mmol) of compound 1-b was added dropwise to the three-necked flask, the temperature was raised to 90° C., and the mixture was kept under stirring for 4 h. Centrifuge to remove solid impurities, use a rotary evaporator at a temperature of 45 °C and a pressure of 0.1 MPa to rotate, and then distill the resulting solution under reduced pressure at 300 Pa and 40 °C to obtain the product. Characterized by H NMR spectroscopy, it was determined to be compound 2 with a yield of 90%, which is sometimes referred to as Eugenol-Si 6 hereinafter.
Figure PCTCN2022099400-appb-000024
Figure PCTCN2022099400-appb-000024
[Eugenol-Si 6]: 1H NMR(400MHz,Chloroform-d)δ6.83-6.50(m,3H),4.43(dd,J＝6.9,5.8Hz,4H),4.16-4.06(m,2H),3.89(d,J＝2.2Hz,3H),3.68(t,J＝6.1Hz,2H),3.57(s,2H),2.12-2.04(m,2H),1.94-1.86(m,2H),1.75(q,J＝7.5Hz,3H),1.41-1.25(m,4H),0.95-0.82(m,9H),0.61-0.48(m,2H),0.13-0.02(m,42H)。 [Eugenol-Si 6 ]: 1 H NMR (400MHz, Chloroform-d) δ6.83-6.50 (m, 3H), 4.43 (dd, J＝6.9, 5.8Hz, 4H), 4.16-4.06 (m, 2H) ,3.89(d,J=2.2Hz,3H),3.68(t,J=6.1Hz,2H),3.57(s,2H),2.12-2.04(m,2H),1.94-1.86(m,2H), 1.75 (q, J = 7.5Hz, 3H), 1.41-1.25 (m, 4H), 0.95-0.82 (m, 9H), 0.61-0.48 (m, 2H), 0.13-0.02 (m, 42H).
实施例3Example 3
在装有温度探头和回流冷凝管的三口烧瓶中，将含氢硅油4.28g(5mmol)(对应于式(VⅡ)化合物，其中m＝9，R 1为正丁基，以及R 2、R 3、R 4和R 5为甲基)和0.856g 100ppm浓度的Karstedt催化剂(Karstedt催化剂，安耐吉化学)溶解在溶剂无水甲苯中，然后升温至60℃保持40min。之后向三口烧瓶中滴加化合物1-b 1.932g(6mmol)，升温至90℃，在搅拌下保持4h。离心除去固体杂质，用旋转蒸发器于温度45℃和压力0.1MPa下旋蒸，再将所得溶液于300Pa和40℃下减压蒸馏，得到产物。经核磁氢谱表征，确定为化合物3，产率为91％，下文有时称作Eugenol-Si 9。 In a three-necked flask equipped with a temperature probe and a reflux condenser, 4.28 g (5 mmol) of hydrogen-containing silicone oil (corresponding to the compound of formula (VII), wherein m=9, R 1 is n-butyl, and R 2 , R 3 , R 4 and R 5 are methyl) and 0.856 g of 100 ppm concentration of Karstedt catalyst (Karstedt catalyst, Anaiji Chemical) were dissolved in the solvent anhydrous toluene, and then heated to 60 ° C for 40 min. Then, 1.932 g (6 mmol) of compound 1-b was added dropwise to the three-necked flask, the temperature was raised to 90° C., and the mixture was kept under stirring for 4 h. Centrifuge to remove solid impurities, use a rotary evaporator at a temperature of 45 °C and a pressure of 0.1 MPa to rotate, and then distill the resulting solution under reduced pressure at 300 Pa and 40 °C to obtain the product. Characterized by H NMR spectroscopy, it was determined to be compound 3 with a yield of 91%, which is sometimes referred to as Eugenol-Si 9 hereinafter.
Figure PCTCN2022099400-appb-000025
Figure PCTCN2022099400-appb-000025
[Eugenol-Si 9]: 1H NMR(400MHz,Chloroform-d)δ6.98-6.52(m,3H),4.45(dd,J＝6.9,5.8Hz,4H),4.21-4.06(m,2H),3.89(d,J＝2.2Hz,3H),3.70(td,J＝6.1,2.1Hz,2H),3.59(d,J＝1.8Hz,2H),2.20-2.06(m,2H),1.94-1.83(m,2H),1.77(q,J＝7.5Hz,3H),1.43-1.26(m,4H),0.98-0.84(m,9H),0.62-0.49(m,2H),0.14-0.10(m,60H)。 [Eugenol-Si 9 ]: 1 H NMR (400MHz, Chloroform-d) δ6.98-6.52 (m, 3H), 4.45 (dd, J＝6.9, 5.8Hz, 4H), 4.21-4.06 (m, 2H) ,3.89(d,J=2.2Hz,3H),3.70(td,J=6.1,2.1Hz,2H),3.59(d,J=1.8Hz,2H),2.20-2.06(m,2H),1.94- 1.83(m,2H),1.77(q,J＝7.5Hz,3H),1.43-1.26(m,4H),0.98-0.84(m,9H),0.62-0.49(m,2H),0.14-0.10( m, 60H).
实施例4Example 4
在装有温度探头和回流冷凝管的三口烧瓶中，将含氢硅油6.5g(5mmol)(对应于式(VⅡ)化合物，其中m＝15，R 1为正丁基，以及R 2、R 3、R 4和R 5为甲基)和1.300g 100ppm浓度的Karstedt催化剂(Karstedt催化剂，安耐吉化学)溶解在溶剂无水甲苯中，然后升温至60℃保持40min。之后向三口烧瓶中滴加化合物1-b 1.932g(6mmol)，升温至90℃，在搅拌下保持4h。离心除去固体杂质，用旋转蒸发器于温度45℃和压力0.1MPa下旋蒸，再将所得溶液于300Pa和40℃下减压蒸馏，得到产物。经核磁氢谱表征，确定为化合物4，产率为92％，下文有时称作Eugenol-Si 15。 In a three-necked flask equipped with a temperature probe and a reflux condenser, 6.5 g (5 mmol) of hydrogen-containing silicone oil (corresponding to the compound of formula (VII), wherein m=15, R 1 is n-butyl, and R 2 , R 3 , R 4 and R 5 are methyl) and 1.300 g of 100 ppm concentration of Karstedt catalyst (Karstedt catalyst, Anaiji Chemical) were dissolved in the solvent anhydrous toluene, and then heated to 60 ° C for 40 min. Then, 1.932 g (6 mmol) of compound 1-b was added dropwise to the three-necked flask, the temperature was raised to 90° C., and the mixture was kept under stirring for 4 h. Centrifuge to remove solid impurities, use a rotary evaporator at a temperature of 45 °C and a pressure of 0.1 MPa to rotate, and then distill the resulting solution under reduced pressure at 300 Pa and 40 °C to obtain the product. Characterized by H NMR spectroscopy, it was determined to be compound 4 with a yield of 92%, which is sometimes referred to as Eugenol-Si 15 hereinafter.
Figure PCTCN2022099400-appb-000026
Figure PCTCN2022099400-appb-000026
[Eugenol-Si 15]: 1H NMR(400MHz,Chloroform-d)δ6.98-6.52(m,3H),4.45(dd,J＝6.9,5.8Hz,4H),4.21-4.06(m,2H),3.89(d,J＝2.2Hz,3H),3.70(td,J＝6.1,2.1Hz,2H),3.59(d,J＝1.8Hz,2H),2.20-2.06(m,2H),1.94-1.83(m,2H),1.77(q,J＝7.5Hz,3H),1.43-1.26(m,4H),0.98-0.84(m,9H),0.62-0.55(m,2H),0.14-0.10(m,96H)。 [Eugenol-Si 15 ]: 1 H NMR (400MHz, Chloroform-d) δ6.98-6.52 (m, 3H), 4.45 (dd, J＝6.9, 5.8Hz, 4H), 4.21-4.06 (m, 2H) ,3.89(d,J=2.2Hz,3H),3.70(td,J=6.1,2.1Hz,2H),3.59(d,J=1.8Hz,2H),2.20-2.06(m,2H),1.94- 1.83(m,2H),1.77(q,J＝7.5Hz,3H),1.43-1.26(m,4H),0.98-0.84(m,9H),0.62-0.55(m,2H),0.14-0.10( m, 96H).
实施例5Example 5
本实施例的目的在于说明本发明化合物的光聚合性能。光固化组合物的制备过程如下：The purpose of this example is to illustrate the photopolymerizable properties of the compounds of the present invention. The preparation process of photocurable composition is as follows:
称取适量X 1mol的上述化合物1，X 2mol的E4221(3,4-环氧环己基甲基3,4-环氧环己基甲酸酯)，X 3mol的光引发剂六氟磷酸二苯基碘鎓盐(810)和X 4mol的光敏剂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。以光固化组合物Eugenol-Si 3-3.0％为例，其各组分摩尔比例为：[化合物1(X 1)+E4221(X 2)]:810(X 3):ITX(X 4)＝3:97:3:1.5(均为摩尔比)，其中在本公开的实施例中，光固化组合物中的X 1+X 2固定为100。包含化合物2-3的光固化组合物制备方式与化合物1相一致。各光组合物中本发明化合物1、2和3(即Eugenol-Si 3、Eugenol-Si 6和Eugenol-Si 9)摩尔百分数X 1如下表1-3所示，如上所述X 1+X 2固定为100，X 3和X 4保持不变。 Weigh an appropriate amount of X 1 mol of the above compound 1, X 2 mol of E4221 (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl carboxylate), X 3 mol of photoinitiator hexafluorophosphoric acid Add diphenyliodonium salt (810) and X 4 mol photosensitizer 2-isopropylthioxanthone (ITX) into a brown bottle and stir evenly, and store in the dark. Taking the photocurable composition Eugenol-Si 3 -3.0% as an example, the molar ratio of each component is: [Compound 1(X 1 )+E4221(X 2 )]:810(X 3 ):ITX(X 4 )= 3:97:3:1.5 (both molar ratios), wherein in the embodiments of the present disclosure, X 1 +X 2 in the photocurable composition is fixed to 100. The preparation method of the photocurable composition containing compound 2-3 is consistent with that of compound 1. The mole percentage X 1 of the compounds 1, 2 and 3 of the present invention (ie Eugenol-Si 3 , Eugenol-Si 6 and Eugenol-Si 9 ) in each photocomposition is shown in Table 1-3 below, and X 1 +X 2 as mentioned above Fixed at 100, X 3 and X 4 remain the same.
以光引发剂六氟磷酸二苯基碘鎓盐(810)与2-异丙基硫杂蒽酮(ITX，增感剂)以2:1摩尔比组成的混合物作为光引发体系，采用实时红外(RT-IR)的方法测试了化合物1-3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E4221三元氧杂环的C-O-C的振动吸收峰位于750cm -1位置，作为聚合单体的化合物1-3的四元氧杂环的C-O-C的振动吸收峰为980cm -1，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(用细管蘸取一点可光固化液体，在溴化钾盐片上点一下，然后平铺均匀)，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和980cm -1处C-O-C键峰面积的变化，表征了不同环氧基团，即单体的实时转化率和聚合速率。 A mixture of photoinitiator diphenyliodonium hexafluorophosphate (810) and 2-isopropylthioxanthone (ITX, sensitizer) in a molar ratio of 2:1 was used as the photoinitiation system, and real-time infrared The (RT-IR) method was used to test the photopolymerization kinetics of compounds 1-3, and to investigate the effects of each of them on the photopolymerization performance of E4221 at different contents. The vibration absorption peak of the COC of the three-membered oxygen heterocycle of the monomer E4221 used is located at 750 cm -1 , and the vibration absorption peak of the COC of the four-membered oxygen heterocycle of compound 1-3 as a polymerized monomer is 980 cm -1 . The photocurable liquid composed of the precursor and the photoinitiator is evenly spread on the potassium bromide salt sheet (take a little photocurable liquid with a thin tube, click it on the potassium bromide salt sheet, and then spread it evenly), and irradiate it with a high-pressure mercury lamp Liquid sample 900s, in which the main emission wavelength of the mercury lamp is 365nm, and it has an optical fiber with a diameter of 5mm. The distance between one end of the optical fiber and the test sample is 10cm, and the radiation intensity is 20mW cm - 2 . By measuring the change of COC bond peak area at 750cm -1 and 980cm -1 , the real-time conversion rate and polymerization rate of different epoxy groups were characterized.
包含化合物1-3(即Eugenol-Si 3、Eugenol-Si 6和Eugenol-Si 9)的光固化组合物各自的结果分别如图1-3和表1-3所示(图和下文表中，以Eugenol-Si 3-3.0％为例，其表示配方中X 1为3.0mol％)。结果显示，化合物1-3的加入可以明显改善E4421单体的转化率和转化速率。另外，化合物1-3仅需少量添加(3-12mol％)就可以明显提高单体E4221的转化率，其最大转化率都达到了至少70％。并且由图4-6可以看出化合物1-3自身转化率均在74％左右。因此本发明化合物可以提高E4221单体的光聚合性能并且本发明化合物自身具有优异的光聚合活性。 The respective results of the photocurable compositions comprising compounds 1-3 (ie, Eugenol-Si 3 , Eugenol-Si 6 and Eugenol-Si 9 ) are shown in Figures 1-3 and Tables 1-3, respectively (in the figures and tables below, Taking Eugenol-Si 3 -3.0% as an example, it means that X 1 in the formula is 3.0 mol%). The results show that the addition of compounds 1-3 can significantly improve the conversion rate and conversion rate of E4421 monomer. In addition, only a small amount of addition (3-12mol%) of compounds 1-3 can significantly increase the conversion rate of monomer E4221, and the maximum conversion rate of them all reaches at least 70%. And it can be seen from Figures 4-6 that the conversion rates of compounds 1-3 are all about 74%. Therefore, the compound of the present invention can improve the photopolymerization performance of the E4221 monomer and the compound itself has excellent photopolymerization activity.
表1：使用化合物1(Eugenol-Si 3)的光固化组合物的900s时单体转化率 Table 1: Monomer conversion rate at 900s of the photocurable composition using compound 1 (Eugenol-Si 3 )
Figure PCTCN2022099400-appb-000027
Figure PCTCN2022099400-appb-000027
表2：使用化合物2(Eugenol-Si 6)的光固化组合物的900s时单体转化率 Table 2: Monomer conversion rate at 900s of photocurable composition using compound 2 (Eugenol-Si 6 )
Figure PCTCN2022099400-appb-000028
Figure PCTCN2022099400-appb-000028
表3：使用化合物3(Eugenol-Si 9)的光固化组合物的900s时单体转化率 Table 3: Monomer conversion rate at 900s of the photocurable composition using compound 3 (Eugenol-Si 9 )
Figure PCTCN2022099400-appb-000029
Figure PCTCN2022099400-appb-000029
实施例6Example 6
本实施例的目的在于说明本发明化合物能够改善光固化膜的表面疏水性。The purpose of this example is to illustrate that the compound of the present invention can improve the surface hydrophobicity of the photocured film.
称取适量X 1mol的上述化合物1-3(即Eugenol-Si 3、Eugenol-Si 6和Eugenol-Si 9)，X 2mol的E4221，X 3mol的光引发剂六氟磷酸二苯基碘鎓盐(810)和X 4mol的光敏剂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(X 1)：E4221(X 2):810(X 3):ITX(X 4)＝3: 97:3:1.5。在6mm×8mm×70mm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(波长365nm，光强为60mW cm -2)，照射时间900s后取出固化膜，进行水接触角测试。 Weigh an appropriate amount of X 1 mol of the above-mentioned compounds 1-3 (ie Eugenol-Si 3 , Eugenol-Si 6 and Eugenol-Si 9 ), X 2 mol of E4221, X 3 mol of photoinitiator diphenyl iodide hexafluorophosphate Onium salt (810) and X 4 mol photosensitizer 2-isopropylthioxanthone (ITX) were added into a brown bottle and stirred evenly, and stored away from light. The molar ratio of each component of the formula was: monomer (X 1 ):E4221(X 2 ):810(X 3 ):ITX(X 4 )=3:97:3:1.5. Add uniformly stirred photosensitive liquid into a polytetrafluoroethylene mold of 6mm×8mm×70mm, and then place the mold under a mercury lamp for irradiation (wavelength 365nm, light intensity 60mW cm -2 ), and take out the cured film after irradiating for 900s. A water contact angle test was performed.
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固化膜作为参比。参比和化合物1-3的结果见图7。The surface hydrophobicity of the photocured film was characterized by a DSA25 water contact angle measuring instrument, and the test temperature was 25°C. At the same time, use the same method to prepare a blank E4221 cured film as a reference. The results for reference and compounds 1-3 are shown in Figure 7.
由图7可见，当E4221聚合体系不添加本发明化合物时，固化膜的水接触角为58.4°，而额外加入化合物1-3后，固化膜的水接触角明显提高，分别达到82.4°、89.4°及94.2°。另外，额外加入化合物1-3中之一获得的固化膜的接触角均超过82°。因此，本发明化合物可以显著地提高固化膜的表面疏水性，因而抗沾污，抗指纹。It can be seen from Figure 7 that when the compound of the present invention is not added to the E4221 polymerization system, the water contact angle of the cured film is 58.4°, and after the addition of compounds 1-3, the water contact angle of the cured film is significantly increased, reaching 82.4° and 89.4° respectively. ° and 94.2°. In addition, the contact angles of the cured films obtained by additionally adding one of the compounds 1-3 all exceeded 82°. Therefore, the compound of the present invention can significantly improve the surface hydrophobicity of the cured film, thus resisting stains and fingerprints.
实施例7Example 7
按照实施例6中所述完全相同的方法分别制得化合物1-3各自的固化膜。然后采用热失重分析仪(DTG-60AH岛津企业管理(中国)有限公司)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25-700℃，升温速度为10℃/min。同时，利用同样方法制备空白E4221固化膜作为参比。其结果见图8及表4。The respective cured films of compounds 1-3 were prepared in exactly the same manner as described in Example 6. Then, the heat resistance of each photocured film was measured using a thermogravimetric analyzer (DTG-60AH Shimadzu Enterprise Management (China) Co., Ltd.). The test conditions are: under nitrogen protection, the temperature range is 25-700°C, and the heating rate is 10°C/min. At the same time, use the same method to prepare a blank E4221 cured film as a reference. The results are shown in Figure 8 and Table 4.
由表4和图8可见，加入化合物1-3中任何一种后，固化膜的初始分解温度(T 5％)及最大热失重温度第一阶段失重最快时分解温度(T max1)和第二阶段失重最快时分解温度(T max2)明显提高，因而耐热性明显被改善。 It can be seen from Table 4 and Fig. 8 that after adding any one of the compounds 1-3, the initial decomposition temperature (T 5% ) and the maximum thermal weight loss temperature of the cured film are the decomposition temperature (T max1 ) and the first stage of the fastest weight loss. The decomposition temperature (T max2 ) is obviously increased when the weight loss is the fastest in the second stage, so the heat resistance is obviously improved.
表4Table 4
体系system T 5％(℃) T 5% (°C) T max1(℃) T max1 (°C) T max2(℃) T max2 (°C)
E4221E4221 267267 379379 --
Eugenol-Si 3 Eugenol-Si 3 317317 399399 584584
Eugenol-Si 6 Eugenol-Si 6 319319 410410 587587
Eugenol-Si 9 Eugenol-Si 9 322322 413413 590590
实施例8Example 8
本实施例的目的在于说明本发明化合物能够改善光固化膜的拉伸性能。The purpose of this example is to illustrate that the compounds of the present invention can improve the tensile properties of photocured films.
按照实施例6中所述完全相同的方法分别制得化合物1-3各自的固化膜。然后 采用电子万能试验机测试(E44.304型，美特斯工业系统(中国)有限公司)依据国际标准ISO 1184-1983《塑料薄膜拉伸性能的测定》进行光固化膜的拉伸性能测试。测试温度为25℃，湿度60％，测试速度为1mm/min。同时，利用同样方法制备空白E4221固化膜作为参比。其结果见图9和表5。The respective cured films of compounds 1-3 were prepared in exactly the same manner as described in Example 6. Then, the electronic universal testing machine (E44.304, Meters Industrial Systems (China) Co., Ltd.) was used to test the tensile properties of the light-cured film according to the international standard ISO 1184-1983 "Determination of Tensile Properties of Plastic Films". The test temperature is 25°C, the humidity is 60%, and the test speed is 1mm/min. At the same time, use the same method to prepare a blank E4221 cured film as a reference. The results are shown in Figure 9 and Table 5.
由图9和表5可见，纯E4221光固化膜的拉伸强度为6.10MPa，断裂伸长率为1.7％。额外加入化合物1-3单体后，光固化膜的拉伸强度和断裂伸长率都逐渐增大。因此，本发明化合物能够明显改善固化膜的拉伸性能。It can be seen from Figure 9 and Table 5 that the tensile strength of the pure E4221 light-cured film is 6.10 MPa, and the elongation at break is 1.7%. The tensile strength and elongation at break of the light-cured film gradually increased after the addition of compound 1-3 monomers. Thus, the compounds of the present invention are able to significantly improve the tensile properties of cured films.
表5table 5
体系system 拉伸强度(MPa)Tensile strength (MPa) 断裂伸长率(％)Elongation at break (%)
E4221E4221 6.16.1 1.71.7
Eugenol-Si 3 Eugenol-Si 3 8.78.7 3.03.0
Eugenol-Si 6 Eugenol-Si 6 9.49.4 4.74.7
Eugenol-Si 9 Eugenol-Si 9 10.610.6 5.95.9

Claims (15)

  1. 下式(I)化合物：Compounds of the following formula (I):
    Figure PCTCN2022099400-appb-100001
    Figure PCTCN2022099400-appb-100001
    其中in
    m为1-50；m is 1-50;
    L为直接键或具有1-30个碳原子的二价连接基团；L is a direct bond or a divalent linking group with 1-30 carbon atoms;
    R 1、R 2、R 3、R 4、R 5相同或不同，并独立地为具有1-12碳原子的有机基团；以及 R 1 , R 2 , R 3 , R 4 , R 5 are the same or different, and are independently organic groups with 1-12 carbon atoms; and
    R 6为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基。 R 6 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.
  2. 根据权利要求1的化合物，其中A compound according to claim 1, wherein
    m为1-30；m is 1-30;
    R 1为C 1-C 12烷基或者C 1-C 12烷氧基； R 1 is C 1 -C 12 alkyl or C 1 -C 12 alkoxy;
    R 2、R 3、R 4、R 5相同或不同，并独立地为C 6-C 10芳基、C 1-C 12烷基、C 1-C 12烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 12烷基，或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 12烷氧基，以及 R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and are independently represented by one or more C 2 -C 12 alkyl separated by non-adjacent heteroatoms selected from NR a , O, S, or C separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S 2 -C 12 alkoxy, and
    L为直接键、C 1-C 30亚烷基、C 1-C 30亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷氧基， L is a direct bond, C 1 -C 30 alkylene, C 1 -C 30 alkyleneoxy, C 2 - separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S C 30 alkylene, or C 2 -C 30 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S,
    其中R a为H或C 1-C 4烷基。 Wherein R a is H or C 1 -C 4 alkyl.
  3. 根据权利要求1或2的化合物，其满足下述定义中的至少一个，优选全部：A compound according to claim 1 or 2, which satisfies at least one, preferably all, of the following definitions:
    -m为1-20，优选为2-15；- m is 1-20, preferably 2-15;
    -R 1为C 1-C 6烷基或者C 1-C 6烷氧基；R 1优选为C 1-C 4烷基或者C 1-C 4烷氧 基； -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;
    -R 2、R 3、R 4、R 5、相同或不同，并独立地为C 6-C 10芳基、C 1-C 6烷基、C 1-C 6烷氧基或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 6烷基，其中R a为H或C 1-C 4烷基；优选的是，R 2、R 3、R 4、R 5、相同或不同，并独立地为苯基、C 1-C 4烷基、C 1-C 4烷氧基或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 4烷基，其中R a为H或C 1-C 4烷基； -R 2 , R 3 , R 4 , R 5 , the same or different, and independently C 6 -C 10 aryl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or replaced by one or more C 2 -C 6 alkyl groups independently selected from NR a , O, and S with non-adjacent heteroatom intervals, wherein R a is H or C 1 -C 4 alkyl; preferably, R 2 , R 3 , R 4 , R 5 , the same or different, and independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or one or more independently selected from NR a , O, S C 2 -C 4 alkyl interspersed by non-adjacent heteroatoms, wherein R a is H or C 1 -C 4 alkyl;
    -R 6为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基； -R 6 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 ;
    -L为C 2-C 30亚烷基、C 2-C 30亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷氧基，其中R a为H或C 1-C 4烷基。 -L is C 2 -C 30 alkylene, C 2 -C 30 alkyleneoxy, C 2 -C 30 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S Alkylene, or C 2 -C 30 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkane base.
  4. 根据权利要求1的化合物，其中A compound according to claim 1, wherein
    m为1-9；m is 1-9;
    R 1为C 1-C 4烷基或者C 1-C 4烷氧基； R 1 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy;
    R 2、R 3、R 4、R 5相同或不同，并独立地为苯基、C 1-C 4烷基、C 1-C 4烷氧基或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 1-C 4烷基，其中R a为H或C 1-C 4烷基； R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or one or more independently selected from NR a , C 1 -C 4 alkyl separated by non-adjacent heteroatoms of O, S, wherein R a is H or C 1 -C 4 alkyl;
    R 6为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基；以及 R 6 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; as well as
    L为L 1-O-L 2，其中L 1和L 2相互独立地为具有1-20，优选1-15个碳原子的二价连接基团，更优选C 1-C 15亚烷基； L is L 1 -OL 2 , wherein L 1 and L 2 are independently a divalent linking group with 1-20, preferably 1-15 carbon atoms, more preferably C 1 -C 15 alkylene;
    优选的是，Preferably,
    m为3-9；m is 3-9;
    R 1为C 1-C 4烷基； R 1 is C 1 -C 4 alkyl;
    R 2、R 3、R 4、R 5相同或不同，并独立地为C 1-C 4烷基； R 2 , R 3 , R 4 , and R 5 are the same or different, and are independently C 1 -C 4 alkyl;
    R 6为H或C 1-C 4烷基，以及 R 6 is H or C 1 -C 4 alkyl, and
    L为L 1-O-L 2，其中L 1和L 2相互独立地为C 1-C 6亚烷基。 L is L 1 -OL 2 , wherein L 1 and L 2 are independently C 1 -C 6 alkylene.
  5. 根据权利要求1-4中任一项的化合物，其中式(I)化合物选自下组：The compound according to any one of claims 1-4, wherein the compound of formula (I) is selected from the group consisting of:
    Figure PCTCN2022099400-appb-100002
    Figure PCTCN2022099400-appb-100002
  6. 一种制备根据权利要求1-5中任一项的式(I)化合物的方法，包括：使得式(VI)化合物与式(VII)化合物反应得到式(I)化合物A method for preparing a compound of formula (I) according to any one of claims 1-5, comprising: reacting a compound of formula (VI) with a compound of formula (VII) to obtain a compound of formula (I)
    Figure PCTCN2022099400-appb-100003
    Figure PCTCN2022099400-appb-100003
    其中L和R 6如权利要求1-5中任一项所定义， Wherein L and R are as defined in any one of claims 1-5,
    Figure PCTCN2022099400-appb-100004
    Figure PCTCN2022099400-appb-100004
    其中m、R 1、R 2、R 3、R 4和R 5如权利要求1-5中任一项所定义。 wherein m, R 1 , R 2 , R 3 , R 4 and R 5 are as defined in any one of claims 1-5.
  7. 根据权利要求6的方法，其中L为L 1-O-L 2，其中L 1和L 2相互独立地为具有1-20，优选1-15个碳原子的二价连接基团，更优选为C 1-C 15亚烷基，尤其是C 1-C 6亚烷基。 The method according to claim 6, wherein L is L 1 -OL 2 , wherein L 1 and L 2 are independently of each other a divalent linking group having 1-20, preferably 1-15 carbon atoms, more preferably C 1 -C 15 alkylene, especially C 1 -C 6 alkylene.
  8. 根据权利要求6或7的方法，其中式(VI)的化合物通过如下步骤制备：The method according to claim 6 or 7, wherein the compound of formula (VI) is prepared by the following steps:
    (1)使式(II)化合物：(1) make formula (II) compound:
    Figure PCTCN2022099400-appb-100005
    Figure PCTCN2022099400-appb-100005
    与式(III)化合物反应，react with a compound of formula (III),
    Figure PCTCN2022099400-appb-100006
    Figure PCTCN2022099400-appb-100006
    其中L 1为具有1-20，优选1-15个碳原子的二价连接基团，更优选为C 1-C 15亚烷基，尤其是C 1-C 6亚烷基，并且X为卤素，例如氟、氯、溴或碘， wherein L is a divalent linking group having 1-20 , preferably 1-15 carbon atoms, more preferably C 1 -C 15 alkylene, especially C 1 -C 6 alkylene, and X is halogen , such as fluorine, chlorine, bromine or iodine,
    得到式(IV)化合物The compound of formula (IV) is obtained
    Figure PCTCN2022099400-appb-100007
    Figure PCTCN2022099400-appb-100007
    其中L 1如对式(III)化合物所定义； Wherein L is as defined for the compound of formula (III);
    以及as well as
    (2)使式(IV)化合物与式(V)化合物反应得到式(VI)化合物(2) make formula (IV) compound react with formula (V) compound to obtain formula (VI) compound
    Figure PCTCN2022099400-appb-100008
    Figure PCTCN2022099400-appb-100008
    其中L 2为具有1-20，优选1-15个碳原子的二价连接基团，更优选为C 1-C 15亚烷基，尤其是C 1-C 6亚烷基，R 6如权利要求1-5中任一项所定义，并且X为卤素，例如氯、溴或碘。 Wherein L 2 is a divalent linking group with 1-20, preferably 1-15 carbon atoms, more preferably C 1 -C 15 alkylene, especially C 1 -C 6 alkylene, R 6 is as claimed in as defined in any one of claims 1-5, and X is halogen, such as chlorine, bromine or iodine.
  9. 根据权利要求8的方法，其中在步骤(1)中的反应满足下述条件中的至少一个：The method according to claim 8, wherein the reaction in step (1) meets at least one of the following conditions:
    -式(II)化合物与式(III)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选是氢化钠、氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物，更优选的是，式(II)化合物与碱性催化剂的摩尔比为1∶1-1∶5；- the reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a basic catalyst, preferably sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, More preferably, the molar ratio of the compound of formula (II) to the basic catalyst is 1:1-1:5;
    -式(II)化合物与式(III)化合物的摩尔比为1∶0.75-1∶1.5；- the molar ratio of the compound of formula (II) to the compound of formula (III) is 1: 0.75-1: 1.5;
    -式(II)化合物与式(III)化合物之间的反应在30-120℃，优选40-70℃下进行；- the reaction between the compound of formula (II) and the compound of formula (III) is carried out at 30-120°C, preferably 40-70°C;
    -式(II)化合物与式(III)化合物之间的反应进行3-16小时，优选4-10小时。- The reaction between the compound of formula (II) and the compound of formula (III) is carried out for 3-16 hours, preferably 4-10 hours.
  10. 根据权利要求8或9的方法，其中在步骤(2)中的反应满足下述条件中的至少一个：The method according to claim 8 or 9, wherein the reaction in step (2) meets at least one of the following conditions:
    -式(IV)化合物与式(VI)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选是氢化钠、氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物，更优选的是，式(IV)化合物与碱性催化剂的摩尔比为1∶1-1∶5；- the reaction of the compound of formula (IV) with the compound of formula (VI) is carried out in the presence of a basic catalyst, preferably sodium hydride, 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 1:1-1:5;
    -式(IV)化合物与式(VI)化合物的摩尔比为1∶0.75-1∶1.5；- the molar ratio of the compound of formula (IV) to the compound of formula (VI) is 1: 0.75-1: 1.5;
    -式(IV)化合物与式(VI)化合物之间的反应在40-100℃，优选在60-90 ℃下进行；优选的是，反应进行3-24小时，优选4-10小时。- The reaction between the compound of formula (IV) and the compound of formula (VI) is carried out at 40-100°C, preferably at 60-90°C; preferably, the reaction is carried out for 3-24 hours, preferably 4-10 hours.
  11. 根据权利要求6-10中任一项的方法，其中式(VI)化合物与式(VII)化合物的反应满足下述条件中的至少一个：The method according to any one of claims 6-10, wherein the reaction of the compound of formula (VI) and the compound of formula (VII) satisfies at least one of the following conditions:
    -.式(VI)化合物与式(VII)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，催化剂的量基于式(VII)的重量为2-500ppm；-. The reaction of the compound of formula (VI) and the compound of formula (VII) is carried out in the presence of Karstedt catalyst or SpeIer catalyst, preferably, the amount of catalyst is 2-500ppm based on the weight of formula (VII);
    -式(VI)化合物与式(VII)化合物的摩尔比为1∶0.75-1∶1.5；- the molar ratio of the compound of formula (VI) to the compound of formula (VII) is 1: 0.75-1: 1.5;
    -式(VI)化合物与式(VII)化合物之间的反应在80-110℃，优选85-100℃下进行；- the reaction between the compound of formula (VI) and the compound of formula (VII) is carried out at 80-110°C, preferably 85-100°C;
    -式(VI)化合物与式(VII)化合物之间的反应进行3-6小时，优选3.5-5.5小时。- The reaction between the compound of formula (VI) and the compound of formula (VII) is carried out for 3-6 hours, preferably 3.5-5.5 hours.
  12. 一种可光固化组合物，包含根据权利要求1-5中任一项的式(I)化合物作为聚合单体。A photocurable composition comprising, as polymerizable monomer, a compound of formula (I) according to any one of claims 1-5.
  13. 一种由权利要求12的可光固化组合物得到的光固化材料。A photocurable material obtained from the photocurable composition of claim 12.
  14. 根据权利要求1-5中任一项的式(I)化合物在光固化涂料、粘合剂、油墨和光致抗蚀剂中的用途。Use of compounds of formula (I) according to any one of claims 1-5 in photocurable coatings, adhesives, inks and photoresists.
  15. 一种式(VI)化合物：A compound of formula (VI):
    Figure PCTCN2022099400-appb-100009
    Figure PCTCN2022099400-appb-100009
    其中L和R 6如权利要求1-5中任一项所定义。 wherein L and R are as defined in any one of claims 1-5.
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