WO2020253838A1 - 一种含双氧杂环的含硅单体及其制备和应用 - Google Patents

一种含双氧杂环的含硅单体及其制备和应用 Download PDF

Info

Publication number
WO2020253838A1
WO2020253838A1 PCT/CN2020/097174 CN2020097174W WO2020253838A1 WO 2020253838 A1 WO2020253838 A1 WO 2020253838A1 CN 2020097174 W CN2020097174 W CN 2020097174W WO 2020253838 A1 WO2020253838 A1 WO 2020253838A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
formula
reaction
iii
hours
Prior art date
Application number
PCT/CN2020/097174
Other languages
English (en)
French (fr)
Inventor
孙芳
马浩钦
邹应全
Original Assignee
湖北固润科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 湖北固润科技股份有限公司 filed Critical 湖北固润科技股份有限公司
Publication of WO2020253838A1 publication Critical patent/WO2020253838A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • 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
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

Definitions

  • the technical field to which the present invention belongs is the field of photocurable materials, and specifically relates to a silicon-containing monomer containing a dioxo heterocycle.
  • the invention also relates to a preparation method of the monomer, a photocurable composition containing the monomer and a photocurable material obtained by photocuring the photocurable composition.
  • Ultraviolet curing refers to the process in which a photoinitiator is excited to become free radicals or cations under ultraviolet radiation, thereby initiating polymerization and curing reactions between monomers to form high molecular polymers.
  • ultraviolet light curing technology Compared with thermal curing, ultraviolet light curing technology has the advantages of low environmental pollution, high film quality, and low energy consumption. Therefore, it is widely used in light-curing coatings, adhesives, and ink printing. Moreover, as the emission control of organic volatile components becomes stricter, UV curing technology will have a broader development prospect.
  • the cationic photopolymerization system Compared with the free radical photopolymerization system, the cationic photopolymerization system has the advantages of insensitive to oxygen, small volume shrinkage, strong adhesion and post-curing, so it occupies an irreplaceable important position in the field of photopolymerization.
  • Oxycycloalkane monomers can undergo cationic light curing and are the main raw materials for cationic light curing products.
  • This system not only has low viscosity, low toxicity, and fast polymerization speed, but also has excellent thermal stability and mechanical properties.
  • UV curing has developed rapidly with the advantages of energy saving, environmental protection and high efficiency, people have proposed higher standards for the heat resistance, water repellency, surface stain resistance, corrosion resistance and fingerprint resistance of photocurable materials. Claim. Consumers are increasingly demanding the appearance of products.
  • the surface is also required to have anti-fingerprint and stain-resistant performance, that is, it is not easy to leave fingerprints and other marks on the surface of the product during use, or it is easy to leave marks Be wiped clean.
  • photocurable cationic monomers there are fewer types of photocurable cationic monomers that can meet the aforementioned requirements, and more types of cationic photocurable monomers need to be developed.
  • the inventors of the present invention have conducted extensive and in-depth research on oxygen heterocyclic cationic photopolymerizable monomers in order to discover a new type of oxygen heterocyclic cationic photocurable monomers
  • the monomer has the advantages of fast light curing speed, good tensile properties after curing, excellent hydrophobic properties, anti-staining, anti-fingerprint, anti-chemical corrosion, and strong anti-aging properties.
  • the inventors found that the dioxane-containing silicon-containing monomer obtained by introducing oxacycloalkyl groups at both ends of the polysiloxane chain has the aforementioned advantages.
  • an object of the present invention is to provide a dioxane-containing silicon-containing monomer that not only contains a cationic photocurable oxacycloalkyl group, but also contains a polysiloxane chain.
  • the oxygen heterocyclic monomer with such a structure has fast light curing speed, good tensile properties after curing, excellent hydrophobic properties, anti-staining, anti-fingerprint, anti-chemical corrosion, strong anti-aging properties, and good heat resistance.
  • Another object of the present invention is to provide a method for preparing the dioxane-containing silicon-containing monomer of the present invention.
  • the preparation process is simple and feasible, mild conditions, readily available raw materials and low price.
  • Another object of the present invention is to provide a photocurable composition comprising the silicon-containing monomer containing dioxo heterocycle according to the present invention.
  • the last object of the present invention is to provide a photocurable material which is obtained by photocuring the photocurable composition of the present invention.
  • n is an integer from 1-50;
  • n is an integer of 1-10;
  • z is an integer of 0-10;
  • p and p' are the same or different, and are an integer of 1-6;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy or A C 1 -C 12 alkyl group with one or more heteroatoms independently selected from N, O, and S inserted between two carbon atoms; and
  • R 8 is H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy, or C 1 -C 6 haloalkoxy.
  • n is an integer of 1-15, preferably an integer of 1-12;
  • n is an integer of 1-6, preferably an integer of 2-4;
  • z is an integer of 1-6, preferably an integer of 0-3;
  • p and p' are the same or different, and are each independently an integer of 1-4, preferably an integer of 1-3; and/or
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or A C 1 -C 6 alkyl group with one or more heteroatoms selected from NR b , O, S inserted between two carbon atoms, wherein R b is H or a C 1 -C 4 alkyl group, preferably, R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or one of two carbon atoms A C 1 -C 4 alkyl group interposed with one or more heteroatoms independently selected from NR b , O, and S, wherein R b is H or C 1 -C 4 alkyl; and/or
  • R 8 is H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy; Preferably R 8 is H or C 1 -C 4 alkyl.
  • n is an integer of 1-12;
  • n 2, 3 or 4;
  • z 0, 1, 2 or 3;
  • p and p' are the same and are 1, 2 or 3;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 1 -C 4 alkyl groups;
  • R 8 is H or C 1 -C 4 alkyl.
  • n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined in any one of items 1-4,
  • p and R 8 are as defined for any one of items 1-4, and X is halogen, such as chlorine, bromine or iodine.
  • the reaction of the compound of formula (III) and the compound of formula (IV) is carried out in the presence of a basic catalyst.
  • the basic catalyst is preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably ,
  • the molar ratio of the compound of formula (III) to the basic catalyst is 1:2-1:10; and/or
  • the molar ratio of the compound of formula (III) to the compound of formula (IV) is 1:2-1:2.4; and/or
  • the reaction between the compound of formula (III) and the compound of formula (IV) is first carried out at freezing temperature, and then the temperature is increased to 25-60°C, preferably to 35-60°C; preferably, the reaction at the freezing temperature proceeds to 0.5 -3 hours, preferably 0.5-1 hour; and/or, continue the reaction for 6-24 hours after raising the temperature, preferably 8-24 hours.
  • n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined in any one of items 1-4,
  • p and R 8 are as defined for any one of items 1-4, and X is halogen, such as chlorine, bromine or iodine,
  • n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are as defined in any one of items 1-4;
  • Y is halogen, such as chlorine, bromine or iodine.
  • step (a)
  • the reaction of the compound of formula (III) and the compound of formula (IV) is carried out in the presence of a basic catalyst.
  • the basic catalyst is preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably ,
  • the molar ratio of the compound of formula (III) to the basic catalyst is 1:1-1:5; and/or
  • the molar ratio of the compound of formula (III) to the compound of formula (IV) is 1:1-1:1.2; and/or
  • the reaction between the compound of formula (III) and the compound of formula (IV) is first carried out at freezing temperature, and then the temperature is increased to 25-60°C, preferably to 35-60°C; preferably, the reaction at the freezing temperature proceeds to 0.5 -3 hours, preferably 0.5-1 hour; and/or, continue the reaction for 6-24 hours after raising the temperature, preferably 8-24 hours.
  • the reaction of the compound of formula (V) with the compound of formula (VI) is carried out in the presence of a basic catalyst, which is preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably ,
  • a basic catalyst which is preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably ,
  • the molar ratio of the compound of formula (V) to the basic catalyst is 1:1-1:5; and/or
  • the molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1-1:1.2; and/or
  • the reaction between the compound of formula (V) and the compound of formula (VI) is first carried out at freezing temperature, and then the temperature is increased to 25-60°C, preferably to 35-60°C; preferably, the reaction at the freezing point temperature proceeds to 0.5 -3 hours, preferably 0.5-1 hour; and/or, continue the reaction for 6-24 hours after raising the temperature, preferably 8-24 hours.
  • n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined in any one of items 1-4,
  • Y is halogen, such as chlorine, bromine or iodine
  • n, m, z, p', R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined in any one of items 1-4;
  • p and R 8 are as defined for any one of items 1-4, and X is halogen, such as chlorine, bromine or iodine.
  • step (i)
  • the reaction of the compound of formula (III) and the compound of formula (VI) is carried out in the presence of a basic catalyst, which is preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably ,
  • a basic catalyst which is preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably ,
  • the molar ratio of the compound of formula (III) to the basic catalyst is 1:1-1:5; and/or
  • the molar ratio of the compound of formula (III) to the compound of formula (VI) is 1:1-1:1.2; and/or
  • the reaction between the compound of formula (III) and the compound of formula (VI) is first carried out at freezing temperature, and then the temperature is increased to 25-60°C, preferably to 35-60°C; preferably, the reaction at the freezing temperature proceeds to 0.5 -3 hours, preferably 0.5-1 hour; and/or, continue the reaction for 6-24 hours after raising the temperature, preferably 8-24 hours.
  • the reaction of the compound of formula (Va) and the compound of formula (IV) is carried out in the presence of a basic catalyst, which is preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably ,
  • a basic catalyst which is preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably ,
  • the molar ratio of the compound of formula (Va) to the basic catalyst is 1:1-1:5; and/or
  • the molar ratio of the compound of formula (V-a) to the compound of formula (IV) is 1:1-1:1.2; and/or
  • the reaction between the compound of formula (Va) and the compound of formula (IV) is first carried out at freezing temperature, and then the temperature is increased to 25-60°C, preferably to 35-60°C; preferably, the reaction at the freezing temperature proceeds to 0.5 -3 hours, preferably 0.5-1 hour; and/or, continue the reaction for 6-24 hours after raising the temperature, preferably 8-24 hours.
  • a photocurable composition comprising the compound of formula (I) and/or (II) according to any one of items 1 to 4 as a polymerizable monomer.
  • Fig. 1 is a graph of the conversion rate of the four-membered oxygen heterocycle of Compound 1 prepared in Example 1 as a function of exposure time.
  • Example 2 is a graph of the conversion rate of the four-membered oxygen heterocyclic ring of Compound 2 prepared in Example 2 as a function of exposure time.
  • Example 3 is a graph of the conversion rate of the three-membered oxygen heterocyclic ring of Compound 2 prepared in Example 2 as a function of exposure time.
  • n is an integer from 1-50;
  • n is an integer of 1-10;
  • z is an integer of 0-10;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, interposed with one or more independently selected from N between C 1 -C 12 alkoxy or two carbon atoms, C hetero atoms O, S, of 1 -C 12 alkyl; and
  • R 8 is H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy, or C 1 -C 6 haloalkoxy.
  • the compounds of formula (I) and (II) contain both a cationic photocurable oxygen heterocyclic ring structure and a polysiloxane structure part.
  • the compound with such a structure can be cured by cationic light, and has the advantages of fast curing speed, good tensile properties after curing, excellent hydrophobic properties, anti-staining, anti-fingerprint, anti-chemical corrosion, and strong anti-aging properties.
  • the compounds of formula (I) and (II) of the present invention have smaller volume shrinkage, better adhesion and faster polymerization speed than compounds containing oxetropane rings at both ends.
  • C n -C m indicates that the number of carbon atoms contained in the group is nm.
  • Halogen refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferable that the halogen includes fluorine, chlorine or a combination thereof.
  • C n -C m alkyl group refers to a monovalent branched or unbranched saturated hydrocarbon group having nm, for example 1-12, preferably 1-6, particularly preferably 1-4 carbon atoms .
  • C n -C m alkyl groups mention may be made of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1 -Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,
  • C 6 -C m aryl group refers to a monocyclic, bicyclic or multicyclic aromatic hydrocarbon group containing 6 to m carbon atoms, for example, 6 to 10 carbon atoms.
  • C 6 -C m aryl groups mention may be made of phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methyl ethyl phenyl, diethyl phenyl, Methyl ⁇ propylphenyl, naphthyl, etc.; preferably phenyl or naphthyl, especially phenyl.
  • C n -C m alkoxy refers to a C n -C m alkyl group corresponding to any carbon atom of the open chain C n -C m alkane bonded with an oxygen atom as a linking group C n -C m alkyl, for example C 1 -C 12 alkoxy, more preferably C 1 -C 6 alkoxy, especially preferably C 1 -C 4 alkoxy.
  • C n -C m alkoxy groups mention may be made of methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy Group, isopentyloxy, hexyloxy and its isomers.
  • C n -C m haloalkyl refers to a C n -C m alkyl group substituted with one or more identical or different halogen atoms, such as C 1 -C 12 haloalkyl, preferably C 1 -C 6 haloalkyl, C 1 -C 4 haloalkyl is particularly preferred.
  • haloalkyl groups here, mention may be made of monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, 1-chloromethylethyl, monochlorobutyl, 1 -Chloromethylpropyl, 2-chloromethylpropyl, 1,1-dichloromethylethyl, monochloropentyl, 1-chloromethylbutyl, 2-chloromethylbutyl, 3-chloro Methylbutyl, 2,2-dichloromethylpropyl, 1-chloroethylpropyl, monochlorohexyl, 1,1-dichloromethylpropyl, 1,2-dichloromethylpropyl, 1-chloromethylpentyl, 2-chloromethylpentyl, 3-chloromethylpentyl, 4-chloromethylpentyl, 1,1-dichloromethylbutyl, 1,
  • C n -C m haloalkoxy refers to a C n -C m alkoxy group substituted by one or more identical or different halogen atoms, such as C 1 -C 12 haloalkoxy, more preferably C 1 -C 6 haloalkoxy, especially C 1 -C 4 haloalkoxy.
  • C n -C m halogenated alkoxy groups mention may be made of monochloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 2-chloroisopropoxy, 4-chloro-n-butoxy , 3-chloro-sec-butoxy, 2-chloro-tert-butoxy, 5-chloropentyloxy, 4-chloroisopentyloxy, 6-chlorohexyloxy and its isomers.
  • hydroxyalkyl C n -C m alkyl means any carbon atom in the C n -C m alkyl corresponding open-chain alkanes C n -C m hydroxyl group bonded to a C n -C m Alkyl groups, such as C 1 -C 6 hydroxyalkyl groups, particularly preferably C 1 -C 4 hydroxyalkyl groups, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, hydroxybutyl, hydroxypentyl, Hydroxyhexyl and its isomers.
  • n is usually an integer of 1-50, preferably an integer of 1-15, and particularly preferably an integer of 1-12, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
  • m is usually an integer of 1-10, preferably an integer of 1-6, particularly preferably an integer of 2-4, such as 2, 3 or 4, especially 2.
  • z is usually an integer of 0-10, preferably an integer of 1-6, particularly preferably an integer of 0-3, such as 0, 1, 2 or 3, especially 1.
  • p and p' are the same or different, and each independently is usually an integer of 1-6, preferably an integer of 1-4, particularly preferably an integer of 1-3, such as 1, 2 or 3. , Especially 1.
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are usually independently C 6 -C 10 aryl, C 1 -C 12 alkyl, inserted between the C 1 -C 12 alkoxy or two carbon atoms with one or more substituents independently selected from C heteroatom NR b, O, S of 1 -C 12 alkyl, wherein R b is H or C 1 -C 4 alkyl.
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different and are independently C 6 -C 10 aryl, C 1 -C 6 alkyl, C 1 -C 6 An alkoxy group or a C 1 -C 6 alkyl group with one or more heteroatoms selected from NR b , O, and S inserted between two carbon atoms, wherein R b is H or a C 1 -C 4 alkyl group.
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different, and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or A C 1 -C 4 alkyl group with one or more heteroatoms independently selected from NR b , O, and S inserted between two carbon atoms, wherein R b is H or a C 1 -C 4 alkyl group.
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 1 -C 4 alkyl groups.
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl Group, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy or tert-butoxy.
  • R 8 is usually H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1- C 6 alkoxy or C 1 -C 6 haloalkoxy.
  • R 8 is H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkoxy or C 1 -C 4 Haloalkoxy. It is particularly preferred that R 8 is H or C 1 -C 4 alkyl.
  • R 8 can be H, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy , Isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxy-sec-butyl or hydroxy Tert-butyl.
  • n is an integer of 1-12;
  • n 2, 3 or 4;
  • z 0, 1, 2 or 3;
  • p and p' are the same and are 1, 2 or 3;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 1 -C 4 alkyl groups;
  • R 8 is H or C 1 -C 4 alkyl.
  • the compound of formula (I) and formula (II) is a compound selected from the following group:
  • n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined for the compound of formula (I),
  • p and R 8 are as defined for the compound of formula (I), and X is halogen, such as chlorine, bromine or iodine.
  • step (1) the reaction of the terminal hydroxyl group in the compound of formula (III) with the halogen in the compound of formula (IV) belongs to a type of reaction known in the art, and the reaction produces hydrogen halide.
  • this reaction is carried out in the presence of a basic catalyst.
  • a basic catalyst suitable for this reaction sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof can be mentioned.
  • the amount of catalyst is also conventional.
  • the molar ratio of the compound of formula (III) to the basic catalyst is 1:2-1:10.
  • the reaction of the compound of formula (III) with the compound of formula (IV) is usually carried out in a solvent.
  • the type of solvent is not particularly limited, as long as it can dissolve the compound of formula (III), the compound of formula (IV) and the corresponding basic catalyst and does not participate in the reaction between the compound of formula (III) and the compound of formula (IV).
  • the solvent also facilitates the precipitation of the product, that is, the compound of formula (I).
  • an organic solvent is generally used, and toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile, or any mixtures thereof are preferably used.
  • the amount of solvent is also conventional.
  • the amount of solvent is 0.5-3 times the total weight of the compound of formula (III) and the compound of formula (IV).
  • the molar ratio of the compound of formula (IV) to the compound of formula (III) is usually approximately twice the molar amount.
  • the molar ratio of the compound of formula (III) to the compound of formula (IV) is 1:2-1:2.4.
  • the compound of formula (III) and a basic catalyst are dissolved in a solvent, the temperature is lowered to the freezing point (about 0°C), and then the compound of formula (IV) is added.
  • the resulting reaction mixture is first at the freezing point ( (About 0°C) and the reaction is stirred for 0.5-3 hours, preferably 0.5-1 hour, then the temperature is raised to 25-60°C, preferably to 35-60°C, and the reaction is continued for 6-24 hours, preferably 8-24 hours.
  • the reaction is advantageously carried out under stirring.
  • the compound of formula (I) can be obtained through conventional post-treatment.
  • This post-treatment usually includes extraction or washing (for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and vacuum distillation to further remove the solvent. If you want to obtain a higher purity product, you can also recrystallization or column chromatography to separate impurities.
  • extraction or washing for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water
  • filtration or centrifugation to remove solid impurities
  • rotary evaporation to remove the solvent
  • vacuum distillation to further remove the solvent.
  • n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined for the compound of formula (II),
  • p and R 8 are as defined for the compound of formula (II), and X is halogen, such as chlorine, bromine or iodine,
  • n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are as defined for the compound of formula (II);
  • Y is halogen, such as chlorine, bromine or iodine.
  • step (a) the reaction of the terminal hydroxyl group in the compound of formula (III) with the halogen in the compound of formula (IV) belongs to a type of reaction known in the art, and the reaction produces hydrogen halide.
  • this reaction is carried out in the presence of a basic catalyst.
  • a basic catalyst suitable for this reaction sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof can be mentioned.
  • the amount of catalyst is also conventional.
  • the molar ratio of the compound of formula (III) to the basic catalyst is 1:1 to 1:5.
  • the reaction of the compound of formula (III) with the compound of formula (IV) is usually carried out in a solvent.
  • the type of solvent is not particularly limited, as long as it can dissolve the compound of formula (III), the compound of formula (IV) and the corresponding basic catalyst and does not participate in the reaction between the compound of formula (III) and the compound of formula (IV).
  • the solvent also facilitates the precipitation of the product, that is, the compound of formula (V).
  • an organic solvent is generally used, and toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile, or any mixtures thereof are preferably used.
  • the amount of solvent is also conventional.
  • the amount of solvent is 0.5-3 times the total weight of the compound of formula (III) and the compound of formula (IV).
  • the molar ratio of the compound of formula (IV) to the compound of formula (III) is usually approximately equimolar.
  • the molar ratio of the compound of formula (III) to the compound of formula (IV) is 1:1-1:1.2.
  • the compound of formula (III) and a basic catalyst are dissolved in a solvent, the temperature is lowered to the freezing point (about 0°C), and then the compound of formula (IV) is added.
  • the resulting reaction mixture is first at the freezing point ( (About 0°C) and the reaction is stirred for 0.5-3 hours, preferably 0.5-1 hour, then the temperature is raised to 25-60°C, preferably to 35-60°C, and the reaction is continued for 6-24 hours, preferably 8-24 hours.
  • the reaction is advantageously carried out under stirring.
  • the compound of formula (V) can be obtained through conventional post-treatment.
  • This post-treatment usually includes extraction or washing (for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and vacuum distillation to further remove the solvent. If you want to obtain a higher purity product, you can also recrystallization or column chromatography to separate impurities.
  • extraction or washing for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water
  • filtration or centrifugation to remove solid impurities
  • rotary evaporation to remove the solvent
  • vacuum distillation to further remove the solvent.
  • step (b) the reaction between the terminal hydroxyl group in the compound of formula (V) and the halogen in the compound of formula (VI) belongs to a type of reaction known in the art, and the reaction produces hydrogen halide.
  • this reaction is carried out in the presence of a basic catalyst.
  • a basic catalyst suitable for this reaction sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof can be mentioned.
  • the amount of catalyst is also conventional.
  • the molar ratio of the compound of formula (V) to the basic catalyst is 1:1 to 1:5.
  • the reaction of the compound of formula (V) with the compound of formula (VI) is usually carried out in a solvent.
  • the type of solvent is not particularly limited, as long as it can dissolve the compound of formula (V), the compound of formula (VI) and the corresponding basic catalyst and does not participate in the reaction between the compound of formula (V) and the compound of formula (VI).
  • the solvent also facilitates the precipitation of the product, that is, the compound of formula (II).
  • an organic solvent is generally used, and toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile, or any mixtures thereof are preferably used.
  • the amount of solvent is also conventional.
  • the amount of solvent is 0.5-3 times the total weight of the compound of formula (V) and compound of formula (VI).
  • the molar ratio of the compound of formula (VI) to the compound of formula (V) is usually approximately equimolar.
  • the molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1-1:1.2.
  • the compound of formula (V) and a basic catalyst are dissolved in a solvent, the temperature is lowered to the freezing point (about 0°C), and then the compound of formula (VI) is added.
  • the resulting reaction mixture is first heated to the freezing temperature ( (About 0°C) and the reaction is stirred for 0.5-3 hours, preferably 0.5-1 hour, then the temperature is raised to 25-60°C, preferably to 35-60°C, and the reaction is continued for 6-24 hours, preferably 8-24 hours.
  • the reaction is advantageously carried out under stirring.
  • the compound of formula (II) can be obtained through conventional post-treatment.
  • This post-treatment usually includes extraction or washing (for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and vacuum distillation to further remove the solvent. If you want to obtain a higher purity product, you can also recrystallization or column chromatography to separate impurities.
  • extraction or washing for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water
  • filtration or centrifugation to remove solid impurities
  • rotary evaporation to remove the solvent
  • vacuum distillation to further remove the solvent.
  • n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined for the compound of formula (II),
  • Y is halogen, such as chlorine, bromine or iodine
  • n, m, z, p', R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined for the compound of formula (II);
  • X is halogen, such as chlorine, bromine or iodine.
  • step (i) the reaction between the terminal hydroxyl group in the compound of formula (III) and the halogen in the compound of formula (VI) belongs to a type of reaction known in the art, and the reaction produces hydrogen halide.
  • this reaction is carried out in the presence of a basic catalyst.
  • a basic catalyst suitable for this reaction sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof can be mentioned.
  • the amount of catalyst is also conventional.
  • the molar ratio of the compound of formula (III) to the basic catalyst is 1:1 to 1:5.
  • the reaction of the compound of formula (III) with the compound of formula (VI) is usually carried out in a solvent.
  • the type of solvent is not particularly limited, as long as it can dissolve the compound of formula (III), the compound of formula (VI) and the corresponding basic catalyst and does not participate in the reaction between the compound of formula (III) and the compound of formula (VI).
  • the solvent also facilitates the precipitation of the product, that is, the compound of formula (Va).
  • an organic solvent is generally used, and toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile, or any mixtures thereof are preferably used.
  • the amount of solvent is also conventional.
  • the amount of solvent is 0.5-3 times the total weight of the compound of formula (III) and compound of formula (VI).
  • the molar ratio of the compound of formula (VI) to the compound of formula (III) is usually approximately equimolar.
  • the molar ratio of the compound of formula (III) to the compound of formula (VI) is 1:1-1:1.2.
  • the compound of formula (III) and a basic catalyst are dissolved in a solvent, the temperature is lowered to the freezing point (about 0°C), and then the compound of formula (VI) is added.
  • the resulting reaction mixture is first at the freezing temperature ( (About 0°C) and the reaction is stirred for 0.5-3 hours, preferably 0.5-1 hour, then the temperature is raised to 25-60°C, preferably to 35-60°C, and the reaction is continued for 6-24 hours, preferably 8-24 hours.
  • the reaction is advantageously carried out under stirring.
  • the compound of formula (V-a) can be obtained through conventional post-treatment.
  • This post-treatment usually includes extraction or washing (for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and vacuum distillation to further remove the solvent. If you want to obtain a higher purity product, you can also recrystallization or column chromatography to separate impurities.
  • extraction or washing for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water
  • filtration or centrifugation to remove solid impurities
  • rotary evaporation to remove the solvent
  • vacuum distillation to further remove the solvent.
  • step (ii) the reaction between the terminal hydroxyl group in the compound of formula (V-a) and the halogen in the compound of formula (IV) belongs to a type of reaction known in the art, and the reaction produces hydrogen halide.
  • this reaction is carried out in the presence of a basic catalyst.
  • a basic catalyst suitable for this reaction sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof can be mentioned.
  • the amount of catalyst is also conventional.
  • the molar ratio of the compound of formula (V-a) to the basic catalyst is 1:1 to 1:5.
  • the reaction of the compound of formula (V-a) with the compound of formula (IV) is usually carried out in a solvent.
  • the type of solvent is not particularly limited, as long as it can dissolve the compound of formula (Va), the compound of formula (IV) and the corresponding basic catalyst and does not participate in the reaction between the compound of formula (Va) and the compound of formula (IV).
  • the solvent also facilitates the precipitation of the product, that is, the compound of formula (II).
  • an organic solvent is generally used, and toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile, or any mixtures thereof are preferably used.
  • the amount of solvent is also conventional.
  • the amount of solvent is 0.5-3 times the total weight of the compound of formula (V-a) and compound of formula (IV).
  • the molar ratio of the compound of formula (IV) to the compound of formula (V-a) is usually approximately equimolar.
  • the molar ratio of the compound of formula (V-a) to the compound of formula (IV) is 1:1-1:1.2.
  • the resulting reaction mixture is first heated to the freezing temperature ( (About 0°C) and the reaction is stirred for 0.5-3 hours, preferably 0.5-1 hour, then the temperature is raised to 25-60°C, preferably to 35-60°C, and the reaction is continued for 6-24 hours, preferably 8-24 hours.
  • the reaction is advantageously carried out under stirring.
  • the compound of formula (II) can be obtained through conventional post-treatment.
  • This post-treatment usually includes extraction or washing (for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and vacuum distillation to further remove the solvent. If you want to obtain a higher purity product, you can also recrystallization or column chromatography to separate impurities.
  • extraction or washing for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water
  • filtration or centrifugation to remove solid impurities
  • rotary evaporation to remove the solvent
  • vacuum distillation to further remove the solvent.
  • the compound of formula (I) and (II) of the present invention is a dioxane-containing silicon-containing monomer with fast curing speed, good tensile properties after curing, excellent hydrophobic properties, stain resistance, fingerprint resistance, and Chemical corrosion, strong anti-aging performance.
  • the synthetic method is simple and feasible, and the conditions are mild; the raw materials are easily available and the price is low.
  • a photocurable composition comprising the compound of formula (I) and/or (II) of the present invention as a polymerizable monomer.
  • the photocurable composition may also include a ring-opening polymerization photoinitiator (a photoinitiator that can initiate cationic polymerization) and other vinyl ether double bonds.
  • a ring-opening polymerization photoinitiator a photoinitiator that can initiate cationic polymerization
  • other vinyl ether double bonds such as 3,4-epoxycyclohexylmethyl 3,4- Epoxy cyclohexyl formate (E4221).
  • the photocurable composition of the present invention may be a photocurable coating composition, a photocurable ink composition, a photoresist composition, and the like. After the composition is cured, the resulting cured product has good tensile properties, excellent hydrophobic properties, 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 an unsubstituted C 6 -C 10 aryl group, or are selected from halogen, nitro, carbonyl, C 1 -C 12 alkyl, C 1 C 6 -C 10 aryl substituted with substituents of -C 12 alkoxy, thiophenyl, phenyl and substituted phenyl, preferably phenyl or naphthyl, or selected from halogen, nitro, C 1- C 6 alkyl and substituted phenyl substituted phenyl or naphthyl, wherein the substituted phenyl contains one or more substituents selected from halogen, nitro, C 1 -C 6 alkyl and C 1- C 6 alkoxy group; and
  • Y and Z are non-nucleophilic anions, such as trifluoromethanesulfonate, BF 4 — , ClO 4 — , PF 6 — , AsF 6 — , SbF 6 — .
  • one or more selected from the following group can be used: 4-(phenylthio)phenyl ⁇ diphenylsulfonium hexafluorophosphate, 4-(phenylthio)phenyl ⁇ Diphenylsulfonium hexafluoroantimonate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexa Fluorantimonate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone Ketone-10-sulfonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate (8
  • the amount of photoinitiator is conventional. Based on the photocurable composition of the present invention, the content of the photoinitiator is usually 0.5-5%, preferably 1-3%.
  • a photocurable material is provided, which is obtained by photocuring the photocurable composition of the present invention. Because the photocurable material contains the compound of formula (I) and/or (II) of the present invention as a photocurable monomer, it has good tensile properties, excellent hydrophobic properties, stain resistance, fingerprint resistance, and chemical corrosion resistance. , Strong anti-aging performance, good heat resistance and other advantages.
  • the obtained final product was characterized by hydrogen NMR spectroscopy, and it was determined to be the following compound 3.
  • the obtained final product was characterized by hydrogen NMR spectroscopy and confirmed to be the following compound 4.
  • the purpose of this example is to illustrate the photopolymerization properties of compounds 1 and 3-5 of the present invention.
  • the asymmetric deformation vibration absorption peak of the COC bond of the oxetanyl group is located at 980 cm -1 . As the curing reaction proceeds, the COC bond will open and break, and the absorption peak area at the corresponding position will also decrease.
  • the conversion rate of the four-membered oxygen heterocycle can be calculated.
  • the light source is a high-pressure mercury lamp, the emission wavelength is mainly 365nm, and the light intensity is 60mW/cm 2 .
  • the results of compound 1 are shown in Figure 1.
  • Figure 1 is a graph showing the variation of oxetane ring conversion rate with irradiation time. The results show that compound 1 has good photopolymerization properties.
  • each of the compounds 3-5 is initiating system with four concentrations of 0.75%810+0.38%ITX, 1.50%810+0.75%ITX, 3.00%810+1.50%ITX, 4.50%810+2.25%ITX
  • the conversion rate of the quaternary oxygen heterocyclic ring of the monomer will increase with the increase of the initiator concentration, and the maximum conversion rate of the quaternary oxygen heterocyclic ring of the monomer has reached at least 53% .
  • the respective concentrations of 810 and ITX are based on the respective weights of compounds 1 and 3-5. Therefore, the compound of the present invention has good photopolymerization performance.
  • the purpose of this example is to illustrate the photopolymerization performance of Compound 2 prepared in Example 2.
  • a mixture of photoinitiator diphenyliodonium hexafluorophosphate (810) and 2-isopropylthioxanthone (ITX) in a 2:1 mass ratio was used as the photoinitiator system, and the test was carried out by real-time infrared.
  • the photopolymerization performance of compound 2 under different initiator concentration The asymmetric deformation vibration absorption peak of the COC bond of the oxetanyl group is located at 980 cm -1 , and the asymmetric deformation vibration absorption peak of the COC bond of the three-membered oxygen heterocycle is located at 910 cm -1 .
  • Fig. 2 is a graph showing the change of oxetane ring conversion rate with irradiation time, and Fig.
  • 3 is a graph showing the change of oxetane ring conversion rate with irradiation time. The results show that the three-membered heterocycle can promote the polymerization of the four-membered oxygen heterocycle, and compound 2 has good photopolymerization properties.
  • the purpose of this example is to show that the compound of the present invention can improve the surface hydrophobicity of the photocurable film.
  • Compounds 1-5 were each mixed with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221) epoxy monomer in a mass ratio of 5:95, based on compound 1-5
  • the total weight of each and E44221 is 3.0wt% 810 and 1.5wt% ITX respectively as initiators and mixed uniformly to obtain a photosensitive liquid.
  • OCA20 German dataphysics company
  • the results show that when the compound of the invention is not added to the E4221 polymerization system, the water contact angle of the cured film is 62.5°, and when compound 1 or 2 is additionally added, the contact angles reach 81.5° and 87.4°, respectively.
  • the contact angles of cured films obtained by additionally adding one of Compounds 3-5 all exceeded 78.6°. Therefore, the compound of the present invention can significantly improve the surface hydrophobicity of the cured film, and thus resist stains and fingerprints.
  • Example 1-2 The purpose of this example is to illustrate that each of Compounds 1 and 2 prepared in Example 1-2 can improve the heat resistance of the cured film.
  • the cured films of Compound 1-2 were prepared in exactly the same way as in Example 9. Then a TGA 550 thermal weight loss analyzer (TGA 550, Waters Corporation, USA) was used to measure the heat resistance of each photocured film. The test conditions are: under the protection of nitrogen, the temperature range is 25-800°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 Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

一种含双氧杂环的含硅单体及其制备方法，结构式为式(Ⅰ)和(Ⅱ)，该单体不仅含有可阳离子光固化的氧杂环烷基，而且还含有聚硅氧烷链。具有如此结构的氧杂环类单体光固化速度快，固化后拉伸性能好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强，耐热性好，拓宽了光固化体系的应用范围。

Description

一种含双氧杂环的含硅单体及其制备和应用 技术领域
本发明所属技术领域为光固化材料领域，具体来说涉及一种含双氧杂环的含硅单体。本发明还涉及该单体的制备方法，包含该单体的可光固化组合物和由该可光固化组合物光固化得到的光固化材料。
背景技术
紫外光固化是指在紫外线的辐照下，光引发剂受激发变为自由基或阳离子，从而引发单体间发生聚合固化反应形成高分子聚合物的过程。与热固化相比，紫外光固化技术具有环境污染小、涂膜质量高、能量消耗低等优点，因而在光固化涂料、粘合剂和油墨印刷等领域应用广泛。并且，随着对有机挥发组分排放控制日益严格，紫外光固化技术将具有更广阔的发展前景。与自由基光聚合体系相比，阳离子光聚合体系具有对氧不敏感、体积收缩小、附着力强及可以后固化等优点，故其在光聚合领域占据着不可替代的重要地位。
氧杂环烷烃类单体可进行阳离子光固化，是阳离子光固化产品的主要原料，这种体系不仅粘度低、毒性低、聚合速度快，还具有优异的热稳定性及机械性能。然而，在紫外光固化以节能、环保、高效等优点迅速发展的同时，对于光固化材料的耐热性、拒水性、表面的抗沾污、耐腐蚀及抗指纹等方面人们提出了更高的要求。消费者对产品外观的要求日益提高，除了色彩美观以及手感舒适外，还要求表面具有抗指纹、耐沾污的性能，即使用时产品表面不易留下指纹等痕迹，或者即使留下痕迹也很容易被擦净。目前，能够满足前述要求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。
发明内容
鉴于现有技术的上述状况，本发明的发明人在氧杂环类可阳离子光聚合单体方面进行了广泛而又深入的研究，以期发现一类新型的氧杂环类可阳离子光固化单体，该单体具有光固化速度快，固化后拉伸性能好，疏水性能优良，抗 沾污，抗指纹，抗化学品腐蚀，抗老化性能强等优点。本发明人发现，在聚硅氧烷链的两端引入氧杂环烷基团获得的含双氧杂环的含硅单体具有前述优点。
因此，本发明的一个目的是提供一种含双氧杂环的含硅单体，该单体不仅含有可阳离子光固化的氧杂环烷基，而且还含有聚硅氧烷链。具有如此结构的氧杂环类单体光固化速度快，固化后拉伸性能好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强，耐热性好。
本发明的另一目的是提供一种制备本发明含双氧杂环的含硅单体的方法。该制备过程简单易行，条件温和，原料易得，价格低廉。
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含双氧杂环的含硅单体。
本发明的最后一个目的是提供一种光固化材料，该材料通过将本发明的可光固化组合物光固化而获得。
实现本发明上述目的的技术方案可以概括如下：
1.下式(I)和/或(II)化合物：
Figure PCTCN2020097174-appb-000001
其中
n为1-50的整数；
m为1-10的整数；
z为0-10的整数；
p和p’相同或不同，并且为1-6的整数；
R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 6-C 10芳基、C 1-C 12烷基、C 1-C 12烷氧基或者两个碳原子之间插有一个或多个独立地选自N、O、S的杂原子 的C 1-C 12烷基；以及
R 8为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基。
2.根据第1项的化合物，其中
n为1-15的整数，优选为1-12的整数；和/或
m为1-6的整数，优选为2-4的整数；和/或
z为1-6的整数，优选为0-3的整数；和/或
p和p’相同或不同，并且各自独立地为1-4的整数，优选为1-3的整数；和/或
R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 6-C 10芳基、C 1-C 6烷基、C 1-C 6烷氧基或者两个碳原子之间插有一个或多个选自NR b、O、S的杂原子的C 1-C 6烷基，其中R b为H或C 1-C 4烷基，优选的是，R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为苯基、C 1-C 4烷基、C 1-C 4烷氧基或者两个碳原子之间插有一个或多个独立地选自NR b、O、S的杂原子的C 1-C 4烷基，其中R b为H或C 1-C 4烷基；和/或
R 8为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基；优选R 8为H或C 1-C 4烷基。
3.根据第1项的化合物，其中
n为1-12的整数；
m为2、3或4；
z为0、1、2或3；
p和p’相同，且为1、2或3；
R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 1-C 4烷基；以及
R 8为H或C 1-C 4烷基。
4.根据第1项的化合物，其为一种或多种选自化合物1-5的化合物。
5.一种制备根据第1-4项中任一项的式(I)化合物的方法，包括：
(1)使式(III)化合物
Figure PCTCN2020097174-appb-000002
其中n、m、z、R 2、R 3、R 4、R 5、R 6和R 7如对第1-4项中任一项所定义，
与式(IV)化合物反应，得到式(I)化合物
Figure PCTCN2020097174-appb-000003
其中p和R 8如对第1-4项中任一项所定义，并且X为卤素，例如氯、溴或碘。
6.根据第5项的方法，其中在步骤(1)中，
式(III)化合物与式(IV)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选是氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物，更优选的是，式(III)化合物与碱性催化剂的摩尔比为1:2-1:10；和/或
式(III)化合物与式(IV)化合物的摩尔比为1:2-1:2.4；和/或
式(III)化合物与式(IV)化合物之间的反应先在冰点温度下进行，然后升温至25-60℃，优选升温至35-60℃反应；优选的是，冰点温度下的反应进行0.5-3小时，优选0.5-1小时；和/或，升温后继续反应6-24小时，优选8-24小时。
7.一种制备根据第1-4项中任一项的式(II)化合物的方法，包括：
(a)使式(III)化合物
Figure PCTCN2020097174-appb-000004
其中n、m、z、R 2、R 3、R 4、R 5、R 6和R 7如对第1-4项中任一项所定义，
与式(IV)化合物反应，
Figure PCTCN2020097174-appb-000005
其中p和R 8如对第1-4项中任一项所定义，并且X为卤素，例如氯、溴或碘，
得到式(V)化合物，
Figure PCTCN2020097174-appb-000006
其中n、m、z、R 2、R 3、R 4、R 5、R 6、R 7和R 8如对第1-4项中任一项所定义；
以及
(b)使式(V)化合物与式(VI)化合物反应，得到式(II)化合物
Figure PCTCN2020097174-appb-000007
其中p’如对第1-4项中任一项所定义，以及Y为卤素，例如氯、溴或碘。
8.根据第7项的方法，其中在步骤(a)中，
式(III)化合物与式(IV)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选是氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物，更优选的是，式(III)化合物与碱性催化剂的摩尔比为1:1-1:5；和/或
式(III)化合物与式(IV)化合物的摩尔比为1:1-1:1.2；和/或
式(III)化合物与式(IV)化合物之间的反应先在冰点温度下进行，然后升温至25-60℃，优选升温至35-60℃反应；优选的是，冰点温度下的反应进行0.5-3小时，优选0.5-1小时；和/或，升温后继续反应6-24小时，优选8-24小时。
9.根据第7或8项的方法，其中在步骤(b)中，
式(V)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(V)化合物与碱性催化剂的摩尔比为1:1-1:5；和/或
式(V)化合物与式(VI)化合物的摩尔比为1:1-1:1.2；和/或
式(V)化合物与式(VI)化合物之间的反应先在冰点温度下进行，然后升温至25-60℃，优选升温至35-60℃反应；优选的是，冰点温度下的反应进行0.5-3小时，优选0.5-1小时；和/或，升温后继续反应6-24小时，优选8-24小时。
10.一种制备根据第1-4项中任一项的式(II)化合物的方法，包括：
(i)使式(III)化合物
Figure PCTCN2020097174-appb-000008
其中n、m、z、R 2、R 3、R 4、R 5、R 6和R 7如对第1-4项中任一项所定义，
与式(VI)化合物反应，
Figure PCTCN2020097174-appb-000009
其中p’如对第1-4项中任一项所定义，以及Y为卤素，例如氯、溴或碘，
得到式(V-a)化合物，
Figure PCTCN2020097174-appb-000010
其中n、m、z、p’、R 2、R 3、R 4、R 5、R 6和R 7如对第1-4项中任一项所定义；
以及
(ii)使式(V-a)化合物与式(IV)化合物反应，得到式(II)化合物
Figure PCTCN2020097174-appb-000011
其中p和R 8如对第1-4项中任一项所定义，并且X为卤素，例如氯、溴或碘。
11.根据第10项的方法，其中在步骤(i)中，
式(III)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(III)化合物与碱性催化剂的摩尔比为1:1-1:5；和/或
式(III)化合物与式(VI)化合物的摩尔比为1:1-1:1.2；和/或
式(III)化合物与式(VI)化合物之间的反应先在冰点温度下进行，然后升温至25-60℃，优选升温至35-60℃反应；优选的是，冰点温度下的反应进行0.5-3小时，优选0.5-1小时；和/或，升温后继续反应6-24小时，优选8-24小时。
12.根据第10或11项的方法，其中在步骤(ii)中，
式(V-a)化合物与式(IV)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选是氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物，更优选的是，式(V-a)化合物与碱性催化剂的摩尔比为1:1-1:5；和/或
式(V-a)化合物与式(IV)化合物的摩尔比为1:1-1:1.2；和/或
式(V-a)化合物与式(IV)化合物之间的反应先在冰点温度下进行，然后升温至25-60℃，优选升温至35-60℃反应；优选的是，冰点温度下的反应进行0.5-3小时，优选0.5-1小时；和/或，升温后继续反应6-24小时，优选8-24小时。
13.根据第5-12项中任一项，其中X为氯，和Y为溴。
14.一种可光固化组合物，包含根据第1-4项中任一项的式(I)和/或(II)化合物作为聚合单体。
15.一种光固化材料，该材料通过将根据第14项的可光固化组合物光固化而获得。
附图说明
图1是实施例1制备的化合物1的四元氧杂环转化率随曝光时间的曲线图。
图2是实施例2制备的化合物2的四元氧杂环转化率随曝光时间的曲线图。
图3是实施例2制备的化合物2的三元氧杂环转化率随曝光时间的曲线图。
具体实施方式
根据本发明的一个方面，提供了一种下式(I)和/或(II)化合物：
Figure PCTCN2020097174-appb-000012
其中
n为1-50的整数；
m为1-10的整数；
z为0-10的整数；
p和p’相同或不同，并且为1-6的整数；R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 6-C 10芳基、C 1-C 12烷基、C 1-C 12烷氧基或者两个碳原子之间插有一个或多个独立地选自N、O、S的杂原子的C 1-C 12烷基；以及
R 8为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基。
在本发明中，式(I)和(II)化合物既包含可阳离子光固化的氧杂环结构，又包含聚硅氧烷结构部分。具有如此结构的化合物可进行阳离子光固化，具有光固化速度快，固化后拉伸性能好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强等优点。另外，本发明式(I)和(II)化合物相比于两端均含有氧杂环丙烷环的化合物具有更小的体积收缩、更佳的附着力和更快的聚合速度。
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。
“卤素”是指氟、氯、溴和碘。在本发明中，优选的是，卤素包括氟、氯或其组合。
本文所用的术语“C n-C m烷基”是指具有n-m个，例如1-12个，优选1-6个，特别优选1-4个碳原子的一价支化或未支化饱和烃基。作为C n-C m烷基的实例，可以提及甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1- 二甲基乙基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、己基、1,1-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基、庚基、辛基、2-乙基己基、壬基、癸基、十一烷基、十二烷基及其异构体。
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。
本文所用的术语“C n-C m烷氧基”是指在C n-C m烷基对应的开链C n-C m烷烃的任何碳原子上键合有一个氧原子作为连接基团的C n-C m烷基，例如C 1-C 12烷氧基，更优选C 1-C 6烷氧基，尤其优选C 1-C 4烷氧基。作为C n-C m烷氧基的实例，可以提及甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、2-丁氧基、叔丁氧基、戊氧基、异戊氧基、己氧基及其异构体。
本文所用的术语“C n-C m卤代烷基”是指被一个或多个相同或不同的卤素原子取代的C n-C m烷基，例如C 1-C 12卤代烷基，优选C 1-C 6卤代烷基，特别优选C 1-C 4卤代烷基。作为这里的卤代烷基的实例，可以提及一氯甲基、一氯乙基、二氯乙基、三氯乙基、一氯丙基、1-氯甲基乙基、一氯丁基、1-氯甲基丙基、2-氯甲基丙基、1,1-二氯甲基乙基、一氯戊基、1-氯甲基丁基、2-氯甲基丁基、3-氯甲基丁基、2,2-二氯甲基丙基、1-氯乙基丙基、一氯己基、1,1-二氯甲基丙基、1,2-二氯甲基丙基、1-氯甲基戊基、2-氯甲基戊基、3-氯甲基戊基、4-氯甲基戊基、1,1-二氯甲基丁基、1,2-二氯甲基丁基、1,3-二氯甲基丁基、2,2-二氯甲基丁基、2,3-二氯甲基丁基、3,3-二氯甲基丁基、1-氯乙基丁基、2-氯乙基丁基、1,1,2-三氯甲基丙基、1,2,2-三氯甲基丙基、1-氯乙基-1-甲基丙基、1-乙基-2-氯甲基丙基及其异构体。
本文所用的术语“C n-C m卤代烷氧基”是指被一个或多个相同或不同的卤素原子取代的C n-C m烷氧基，例如C 1-C 12卤代烷氧基，更优选C 1-C 6卤代烷氧基，尤其优选C 1-C 4卤代烷氧基。作为C n-C m卤代烷氧基的实例，可以提及一氯甲氧基、2- 氯乙氧基、3-氯丙氧基、2-氯异丙氧基、4-氯正丁氧基、3-氯仲丁氧基、2-氯叔丁氧基、5-氯戊氧基、4-氯异戊氧基、6-氯己氧基及其异构体。
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。
在本发明化合物中，n通常为1-50的整数，优选为1-15的整数，特别优选为1-12的整数，例如为1、2、3、4、5、6、7、8、9、10、11或12。
在本发明化合物中，m通常为1-10的整数，优选为1-6的整数，特别优选为2-4的整数，例如为2、3或4，尤其是2。
在本发明化合物中，z通常为0-10的整数，优选为1-6的整数，特别优选为0-3的整数，例如为0、1、2或3，尤其是1。
在本发明化合物中，p和p’相同或不同，并且各自独立地通常为1-6的整数，优选为1-4的整数，特别优选为1-3的整数，例如为1、2或3，尤其是1。
在本发明式(I)和(II)化合物中，R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并通常独立地为C 6-C 10芳基、C 1-C 12烷基、C 1-C 12烷氧基或者两个碳原子之间插有一个或多个独立地选自NR b、O、S的杂原子的C 1-C 12烷基，其中R b为H或C 1-C 4烷基。优选的是，R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 6-C 10芳基、C 1-C 6烷基、C 1-C 6烷氧基或者两个碳原子之间插有一个或多个选自NR b、O、S的杂原子的C 1-C 6烷基，其中R b为H或C 1-C 4烷基。特别优选的是，R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为苯基、C 1-C 4烷基、C 1-C 4烷氧基或者两个碳原子之间插有一个或多个独立地选自NR b、O、S的杂原子的C 1-C 4烷基，其中R b为H或C 1-C 4烷基。尤其是R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 1-C 4烷基。例如，R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为苯基、甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基或叔丁氧基。
在本发明式(I)和(II)化合物中，R 8通常为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基。优选的是，R 8为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基。 特别优选的是，R 8为H或C 1-C 4烷基。例如，R 8可以为H、氯、溴、甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、叔丁氧基、羟甲基、羟乙基、羟正丙基、羟异丙基、羟正丁基、羟仲丁基或羟叔丁基。
在本发明式(I)和(II)化合物的一些优选实施方案中，
n为1-12的整数；
m为2、3或4；
z为0、1、2或3；
p和p’相同，且为1、2或3；
R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 1-C 4烷基；以及
R 8为H或C 1-C 4烷基。
在本发明的另一实施方案中，式(I)和式(II)化合物为选自下组的化合物：
Figure PCTCN2020097174-appb-000013
根据本发明的第二个方面，提供了一种制备本发明式(I)化合物的方法，包 括：
(1)使式(III)化合物
Figure PCTCN2020097174-appb-000014
其中n、m、z、R 2、R 3、R 4、R 5、R 6和R 7如对式(I)化合物所定义，
与式(IV)化合物反应，得到式(I)化合物
Figure PCTCN2020097174-appb-000015
其中p和R 8如对式(I)化合物所定义，并且X为卤素，例如氯、溴或碘。
在步骤(1)中，式(III)化合物中的端羟基与式(IV)化合物中的卤素的反应属于本领域已知的反应类型，反应产生卤化氢。通常而言，该反应在碱性催化剂存在下进行。作为适合该反应的碱性催化剂，可以提及氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物。催化剂的用量也是常规的。通常而言，式(III)化合物与碱性催化剂的摩尔用量比为1:2-1:10。式(III)化合物与式(IV)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(III)化合物、式(IV)化合物和相应碱性催化剂溶解并且不参与式(III)化合物与式(IV)化合物之间的反应即可，优选该溶剂还有有利于产物，即式(I)化合物析出。作为该溶剂，通常使用有机溶剂，优选使用甲苯、丙酮、丁酮、甲苯、四氢呋喃、环己烷、1,4-二氧六环、二氯甲烷、乙腈或其任意混合物。溶剂的用量也是常规的，通常而言，溶剂的用量为式(III)化合物和式(IV)化合物总重量的0.5-3倍。式(IV)化合物与式(III)化合物的用量摩尔比通常为大致两倍摩尔量。有利的是，式(III)化合物与式(IV)化合物的用量摩尔比为1:2-1:2.4。为了实现上述反应，通常将式(III)化合物和碱性催化剂溶解在溶剂中，降温至冰点(约0℃)，然后加入式(IV)化合物，加料完毕之后将所得反应混合物先在冰点温度(约0℃)搅拌反应0.5-3小时，优选0.5-1小时，然后升温至25-60℃，优选升温至35-60℃，继续 反应6-24小时，优选8-24小时。当然，反应有利地在搅拌下进行。反应完毕之后，通过常规后处理，即获得式(I)化合物。该后处理通常包括萃取或洗涤(例如用水洗涤，水洗涤之后有利地采用吸水化合物比如硫酸镁或硫酸钠除水)、过滤或离心除去固体杂质，旋蒸除去溶剂，减压蒸馏进一步除去溶剂。如果要获得更高纯度的产物，还可重结晶或柱层析法分离杂质。
根据本发明的第三个方面，提供了一种制备本发明式(II)化合物的方法，包括：
(a)使式(III)化合物
Figure PCTCN2020097174-appb-000016
其中n、m、z、R 2、R 3、R 4、R 5、R 6和R 7如对式(II)化合物所定义，
与式(IV)化合物反应，
Figure PCTCN2020097174-appb-000017
其中p和R 8如对式(II)化合物所定义，并且X为卤素，例如氯、溴或碘，
得到式(V)化合物，
Figure PCTCN2020097174-appb-000018
其中n、m、z、R 2、R 3、R 4、R 5、R 6、R 7和R 8如对式(II)化合物所定义；以及
(b)使式(V)化合物与式(VI)化合物反应，得到式(II)化合物
Figure PCTCN2020097174-appb-000019
其中p’如对式(II)化合物所定义，以及Y为卤素，例如氯、溴或碘。
在步骤(a)中，式(III)化合物中的端羟基与式(IV)化合物中的卤素的反应属于本领域已知的反应类型，反应产生卤化氢。通常而言，该反应在碱性催化剂存在下进行。作为适合该反应的碱性催化剂，可以提及氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物。催化剂的用量也是常规的。通常而言，式(III)化合物与碱性催化剂的摩尔用量比为1:1-1:5。式(III)化合物与式(IV)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(III)化合物、式(IV)化合物和相应碱性催化剂溶解并且不参与式(III)化合物与式(IV)化合物之间的反应即可，优选该溶剂还有有利于产物，即式(V)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(III)化合物和式(IV)化合物总重量的0.5-3倍。式(IV)化合物与式(III)化合物的用量摩尔比通常为大致等摩尔量。有利的是，式(III)化合物与式(IV)化合物的用量摩尔比为1:1-1:1.2。为了实现上述反应，通常将式(III)化合物和碱性催化剂溶解在溶剂中，降温至冰点(约0℃)，然后加入式(IV)化合物，加料完毕之后将所得反应混合物先在冰点温度(约0℃)搅拌反应0.5-3小时，优选0.5-1小时，然后升温至25-60℃，优选升温至35-60℃，继续反应6-24小时，优选8-24小时。当然，反应有利地在搅拌下进行。反应完毕之后，通过常规后处理，即获得式(V)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。
在步骤(b)中，式(V)化合物中的端羟基与式(VI)化合物中的卤素的反应属于本领域已知的反应类型，反应产生卤化氢。通常而言，该反应在碱性催化剂存在下进行。作为适合该反应的碱性催化剂，可以提及氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物。催化剂的用量也是常规的。通常而言，式(V)化合物与碱性催化剂的摩尔用量比为1:1-1:5。式(V)化合物与式(VI)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(V)化合物、式(VI)化合物和相应碱性催化剂溶解并且不参与式(V)化合物与式(VI)化合物之 间的反应即可，优选该溶剂还有有利于产物，即式(II)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(V)化合物和式(VI)化合物总重量的0.5-3倍。式(VI)化合物与式(V)化合物的用量摩尔比通常为大致等摩尔量。有利的是，式(V)化合物与式(VI)化合物的用量摩尔比为1:1-1:1.2。为了实现上述反应，通常将式(V)化合物和碱性催化剂溶解在溶剂中，降温至冰点(约0℃)，然后加入式(VI)化合物，加料完毕之后将所得反应混合物先在冰点温度(约0℃)搅拌反应0.5-3小时，优选0.5-1小时，然后升温至25-60℃，优选升温至35-60℃，继续反应6-24小时，优选8-24小时。当然，反应有利地在搅拌下进行。反应完毕之后，通过常规后处理，即获得式(II)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。
根据本发明的第四个方面，提供了一种制备本发明式(II)化合物的方法，包括：
(i)使式(III)化合物
Figure PCTCN2020097174-appb-000020
其中n、m、z、R 2、R 3、R 4、R 5、R 6和R 7如对式(II)化合物所定义，
与式(VI)化合物反应，
Figure PCTCN2020097174-appb-000021
其中p’如对式(II)化合物所定义，以及Y为卤素，例如氯、溴或碘，
得到式(V-a)化合物，
Figure PCTCN2020097174-appb-000022
其中n、m、z、p’、R 2、R 3、R 4、R 5、R 6和R 7如对式(II)化合物所定义；以及
(ii)使式(V-a)化合物与式(IV)化合物反应，得到式(II)化合物
Figure PCTCN2020097174-appb-000023
其中p和R 8如对式(II)化合物所定义，并且X为卤素，例如氯、溴或碘。
在步骤(i)中，式(III)化合物中的端羟基与式(VI)化合物中的卤素的反应属于本领域已知的反应类型，反应产生卤化氢。通常而言，该反应在碱性催化剂存在下进行。作为适合该反应的碱性催化剂，可以提及氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物。催化剂的用量也是常规的。通常而言，式(III)化合物与碱性催化剂的摩尔用量比为1:1-1:5。式(III)化合物与式(VI)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(III)化合物、式(VI)化合物和相应碱性催化剂溶解并且不参与式(III)化合物与式(VI)化合物之间的反应即可，优选该溶剂还有有利于产物，即式(V-a)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(III)化合物和式(VI)化合物总重量的0.5-3倍。式(VI)化合物与式(III)化合物的用量摩尔比通常为大致等摩尔量。有利的是，式(III)化合物与式(VI)化合物的用量摩尔比为1:1-1:1.2。为了实现上述反应，通常将式(III)化合物和碱性催化剂溶解在溶剂中，降温至冰点(约0℃)，然后加入式(VI)化合物，加料完毕之后将所得反应混合物先在冰点温度(约0℃)搅拌反应0.5-3小时，优选0.5-1小时，然后升温至25-60℃，优选升温至35-60℃，继续反应6-24小时，优选8-24小时。当然，反应有利地在搅拌下进行。反应完毕之后，通过常规后处理，即获得式(V-a)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。
在步骤(ii)中，式(V-a)化合物中的端羟基与式(IV)化合物中的卤素的反应属于本领域已知的反应类型，反应产生卤化氢。通常而言，该反应在碱性催化剂存在下进行。作为适合该反应的碱性催化剂，可以提及氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物。催化剂的用量也是常规的。通常而言，式(V-a)化合物与碱性催化剂的摩尔用量比为1:1-1:5。式(V-a)化合物与式(IV)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(V-a)化合物、式(IV)化合物和相应碱性催化剂溶解并且不参与式(V-a)化合物与式(IV)化合物之间的反应即可，优选该溶剂还有有利于产物，即式(II)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(V-a)化合物和式(IV)化合物总重量的0.5-3倍。式(IV)化合物与式(V-a)化合物的用量摩尔比通常为大致等摩尔量。有利的是，式(V-a)化合物与式(IV)化合物的用量摩尔比为1:1-1:1.2。为了实现上述反应，通常将式(V-a)化合物和碱性催化剂溶解在溶剂中，降温至冰点(约0℃)，然后加入式(IV)化合物，加料完毕之后将所得反应混合物先在冰点温度(约0℃)搅拌反应0.5-3小时，优选0.5-1小时，然后升温至25-60℃，优选升温至35-60℃，继续反应6-24小时，优选8-24小时。当然，反应有利地在搅拌下进行。反应完毕之后，通过常规后处理，即获得式(II)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。
在本发明的一些优选实施方案中，其中X为氯，和Y为溴。
本发明式(I)和(II)化合物一种含双氧杂环的含硅单体，该单体固化速度快，固化后拉伸性能较好，疏水性能优良，抗玷污，抗指纹，抗化学品腐蚀，抗老化性能强。合成方法简单易行，条件温和；原料易得，价格低廉。
因此，根据本发明的第三个方面，提供了一种可光固化组合物，该组合物 包含本发明的式(I)和/或(II)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)化合物和(II)化合物以外，还可包含开环聚合光引发剂(可引发阳离子聚合的光引发剂)以及其它含有乙烯基醚双键、脂环族环氧基、环氧乙烷基或者氧杂环丁烷基等可阳离子光固化基团的单体、低聚物，例如3,4-环氧环己基甲基3,4-环氧环己基甲酸酯(E4221)。
本发明可光固化组合物可以为光固化涂料组合物、光固化油墨组合物、光致抗蚀组合物等。该组合物在固化后，所得固化产物拉伸性能较好，疏水性能优良，抗玷污，抗指纹，抗化学品腐蚀，抗老化性能强。
作为开环聚合的阳离子光引发剂，常用的有碘鎓盐和硫鎓盐。有利的是，所述碘鎓盐光引发剂和硫鎓盐光引发剂分别具有如下通式(A)和(B)
Figure PCTCN2020097174-appb-000024
其中
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
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 —。
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、2-异丙基硫杂蒽酮(ITX)。
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，光引发剂的含量通常为0.5-5％，优选为1-3％。
根据本发明的最后一个方面，提供了一种光固化材料，该材料通过将本发明的可光固化组合物光固化而获得。该光固化材料由于包含本发明式(I)和/或(II)化合物作为可光固化单体的缘故，具有拉伸性能较好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强，耐热性好等优点。
实施例
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1
在装有滴液漏斗、温度探头和回流冷凝管的三口烧瓶中，加入18.6g(20mmol)双羟基硅油(对应于式(III)化合物，其中n＝8，m＝2，z＝1，以及R 2、R 3、R 4、R 5、R 6和R 7为甲基)和30mL甲苯，冰水浴下搅拌，转速设定300r/min，加入8.92g(160mmol)氢氧化钾，之后缓慢滴加5.65g(44mmol)3-乙基-3-氯甲基氧杂环丁烷，滴加完毕后，在冰水浴温度下反应30min，然后撤去冰水浴，60℃油浴再反应24小时，结束反应。反应物用蒸馏水反复洗涤，取上层清液，离心除去固体杂质。用旋转蒸发仪于温度45℃和压力0.1MPa下旋蒸除去大部分溶剂，再将溶液于300Pa和40℃下减压蒸馏，得到产物。经核磁氢谱表征，确定为如下化合物1，该化合物有时会表示为BOSi。 1H NMR(400MHz,CDCl 3)δ:0.07-0.17(m,60H),0.56(m,4H),0.92(t,J＝7.5Hz,6H),1.76-1.50(m,4H),1.87(q,J＝7.5Hz,4H),3.46(t,J＝7.0Hz,4H),3.58-3.54(m,4H),3.77-3.73(m,4H),3.82(s,4H),4.44(s,8H).
Figure PCTCN2020097174-appb-000025
实施例2
在装有滴液漏斗、温度探头和回流冷凝管的三口烧瓶中，加入18.6g(20mmol)双羟基硅油(对应于式(III)化合物，其中n＝8，m＝2，z＝1，以及R 2、R 3、R 4、R 5、R 6和R 7为甲基)和30mL甲苯，冰水浴下搅拌，转速设定300r/min，加入4.46g(80mmol)氢氧化钾，之后缓慢滴加2.83g(22mmol)3-乙基-3-氯甲基氧杂环丁烷，滴加完毕后，在冰水浴温度下反应30min，然后撤去冰水浴，60℃油浴再反应24小时，结束反应。反应物用蒸馏水反复洗涤，取上层清液，离心除去固体杂质。用旋转蒸发仪于温度45℃和压力0.1MPa下旋蒸除去大部分溶剂，再将溶液于300Pa和40℃下减压蒸馏，得到产物。经核磁氢谱表征，确定为如下化合物2a。 1H NMR(400MHz,CDCl3)δ:0.07-0.17(m,60H),0.61(t,J＝7.0Hz,4H),0.83(t,J＝7.5Hz,3H),1.42(m,4H),1.69(q,J＝7.5Hz,2H),3.35(m,4H),3.52(m,6H),3.70(m,2H),3.79(s,2H),4.39-4.14(m,1H),5.4(m,1H).
Figure PCTCN2020097174-appb-000026
在装有滴液漏斗、温度探头和回流冷凝管的三口烧瓶中，加入20.56g(20mmol)化合物2a和30mL甲苯，冰水浴下搅拌，转速设定300r/min，加入4.46g(80mmol)氢氧化钾粉末，之后缓慢滴加3.01g(22mmol)环氧溴丙烷，反应30min后，撤去冰水浴，60℃油浴再反应24小时，结束反应。反应物用蒸馏水反复洗涤，取上层清液，离心除去固体杂质。用旋转蒸发仪于温度45℃和压力0.1MPa下旋蒸除去大部分溶剂，再将溶液于300Pa和40℃下减压蒸馏，得到产物。经核磁氢谱表征，确定为如下化合物2，该化合物有时会表示为BOTSi。 1H NMR(400MHz,CDCl3)δ:0.07-0.17(m,60H),0.58(t,J＝7.0Hz，4H),0.92(t,J＝7.5Hz,3H),1.56(m,4H),1.87(q,J＝7.5Hz,2H),2.61-2.38(m,2H),2.74(m,H),3.61-3.36(m,16H),3.79(s,4H),4.44-4.14(m,4H).
Figure PCTCN2020097174-appb-000027
实施例3
在装有滴液漏斗、温度探头和回流冷凝管的三口烧瓶中，加入18.6g(20mmol)双羟基硅油(对应于式(III)化合物，其中n＝8，m＝2，z＝1，以及R 2、R 3、R 4、R 5、R 6和R 7为甲基)和30mL甲苯，冰水浴下搅拌，转速设定300r/min，加入4.46g(80mmol)氢氧化钾粉末，之后缓慢滴加3.01g(22mmol)环氧溴丙烷，滴加完毕后，在冰水浴温度下反应30min，然后撤去冰水浴，60℃油浴再反应24小时，结束反应。反应物用蒸馏水反复洗涤，取上层清液，离心除去固体杂质。用旋转蒸发仪于温度45℃和压力0.1MPa下旋蒸除去大部分溶剂，再将溶液于300Pa和40℃下减压蒸馏，得到产物。经核磁氢谱表征，确定为如下化合物2b。 1H NMR(400MHz,CDCl3)δ:0.07-0.17(m,60H),0.61(t,J＝7.0Hz，4H),1.56(m,4H),2.61-2.38(m,2H),2.74(m,H),3.70-3.38(m,14H),5.4(m,1H).
Figure PCTCN2020097174-appb-000028
在装有滴液漏斗、温度探头和回流冷凝管的三口烧瓶中，加入19.72g(20mmol)化合物2b和30mL甲苯，冰水浴下搅拌，转速设定300r/min，加入42.23g(40mmol)氢氧化钾粉末，之后缓慢滴加2.83g(22mmol)3-乙基-3-氯甲基氧杂环丁烷，反应30min后，撤去冰水浴，60℃油浴再反应24小时，结束反应。反应物用蒸馏水反复洗涤，取上层清液，离心除去固体杂质。用旋转蒸发仪于温度45℃和压力0.1MPa下旋蒸除去大部分溶剂，再将溶液于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
实施例4
重复实施例1，但是将实施例1中的双羟基硅油替换为这样的双羟基硅油，其对应于式(III)化合物，其中n＝1，m＝2，z＝1，以及R 2、R 3、R 4、R 5、R 6和R 7为甲基。得到的终产物经核磁氢谱表征，确定为如下化合物3。 1H NMR(400MHz,CDCl3)δ:0.07-0.17(m,12H),0.56(m,4H),0.92(t,J＝7.5Hz,6H),1.76-1.50(m,4H),1.87(q,J＝7.5Hz,4H),3.46(t,J＝7.0Hz,4H),3.58-3.54(m,4H),3.77-3.73(m,4H),3.82(s,4H),4.44(s,8H).
Figure PCTCN2020097174-appb-000029
实施例5
重复实施例1，但是将实施例1中的双羟基硅油替换为这样的双羟基硅油，其对应于式(III)化合物，其中n＝15，m＝2，z＝1，以及R 2、R 3、R 4、R 5、R 6和R 7为甲基。得到的终产物经核磁氢谱表征，确定为如下化合物4。 1H NMR(400MHz,CDCl3)δ:0.07-0.17(m,102H),0.56(m,4H),0.92(t,J＝7.5Hz,6H),1.76-1.50(m,4H),1.87(q,J＝7.5Hz,4H),3.46(t,J＝7.0Hz,4H),3.58-3.54(m,4H),3.77-3.73(m,4H),3.82(s,4H),4.44(s,8H).
Figure PCTCN2020097174-appb-000030
实施例6
在装有滴液漏斗、温度探头和回流冷凝管的三口烧瓶中，加入18.6g(20mmol)双羟基硅油(对应于式(III)化合物，其中n＝8，m＝2，z＝1，以及R 2、R 3、R 4、R 5、R 6和R 7为甲基)和30mL甲苯，冰水浴下搅拌，转速设定300r/min，加入8.92g(160mmol)氢氧化钾，之后缓慢滴加3.87g(44mmol)3-羟甲基氧杂环丁烷，滴加完毕后，在冰水浴温度下反应30min，然后撤去冰水浴，60℃油浴再反应24小时，结束反应。反应物用蒸馏水反复洗涤，取上层清液，离心除去固体杂质。用旋转蒸发仪于温度45℃和压力0.1MPa下旋蒸除去大部分溶剂，再将溶液于300Pa和40℃下减压蒸馏，得到产物。经核磁氢谱表征，确定为如下化合物5。 1H NMR(400MHz,CDCl 3)δ:0.07-0.17(m,60H),0.56(m,4H),1.76-1.50(m,4H),,2.92(s,2H),3.46(t,J＝7.0Hz,4H),3.58-3.54(m,4H),3.77-3.73(m,4H),3.82(s,4H),4.44(s,8H).
Figure PCTCN2020097174-appb-000031
实施例7
本实施例的目的在于说明本发明化合物1和3-5的光聚合性能。
以光引发剂六氟磷酸二苯基碘鎓盐(810)与2-异丙基硫杂蒽酮(ITX)以2:1质量比组成的混合物作为光引发体系，采用实时红外(RT-IR)的方法测试了化合物1和3-5在不同引发剂浓度下的光聚合性能。氧杂环丁烷基的C-O-C键不对称变形振动吸收峰位于980cm -1，随着固化反应的进行，C-O-C键会开环断裂，对应位置吸收峰面积也随之减小。通过RT-IR监测红外吸收峰的面积大小变化，可以计算出四元氧杂环的转化率。光源为高压汞灯，发射波长主要为365nm，光强为60mW/cm 2。化合物1的结果如图1所示。图1是氧杂环丁烷环转化率随辐照时间的变化曲线图。结果显示，化合物1具有良好的光聚合性能。另外，化合物3-5中的每一种在0.75％810+0.38％ITX、1.50％810+0.75％ITX、3.00％810+1.50％ITX、4.50％810+2.25％ITX这四个浓度的引发体系下在高压汞灯辐照600秒以后，其单体的四元氧杂环的转化率会随引发剂浓度的提高而增大，其四元氧杂环的最大转化率都达到了至少53％。其中810和ITX各自的浓度均基于化合物1和3-5各自的重量。因此本发明化合物具有良好的光聚合性能。
实施例8
本实施例的目的在于说明实施例2所制备的化合物2的光聚合性能。
以光引发剂六氟磷酸二苯基碘鎓盐(810)与2-异丙基硫杂蒽酮(ITX)以2:1质量比组成的混合物作为光引发体系，采用实时红外的方法测试了化合物2在不同引发剂浓度下的光聚合性能。氧杂环丁烷基的C-O-C键不对称变形振动吸收峰位于980cm -1，三元氧杂环的C-O-C键不对称变形振动吸收峰位于910cm -1，随着固化反应的进行，C-O-C键会开环断裂，对应位置吸收峰面积也随之减小。通过RT-IR监测红外吸收峰的面积大小变化，可以分别计算出四元氧杂环、三元氧杂环的转化率。光源为高压汞灯，发射波长主要为365nm，光强为60mW/cm 2。化合物2的结果如图2和图3所示。图2是氧杂环丁烷环转化率随辐照时间的变化曲线图，图3是氧杂环丙烷环转化率随辐照时间的变化曲线图。结果显示，三元杂环会对四元氧杂环的聚合起到促进作用，化合物2具有良好的光聚合性能。
实施例9
本实施例的目的在于说明本发明化合物能够改善光固化膜的表面疏水性。
将化合物1-5各自与3,4-环氧环己基甲基3,4-环氧环己基甲酸酯(E4221)环氧单体以5：95的质量比混合，以基于化合物1-5各自与E44221的总重量分别为3.0wt％810和1.5wt％ITX作引发剂，混合均匀，得到感光液。将所得感光液均匀铺展在70mm×8mm×6mm的硅胶模具中，在60mW/cm 2的高压汞灯下曝光900s，得到固化完全的膜。然后采用OCA20型水接触角测定仪(OCA20型，德国dataphysics公司)对各固化膜的表面疏水性进行测试，测试温度为25℃。同时，利用同样方法制备空白E4221固化膜作为参比。
结果显示，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62.5°，而额外加入化合物1或2后，接触角分别达到81.5°及87.4°。另外，额外加入化合物3-5中之一获得的固化膜的接触角均超过78.6°。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。
实施例10
本实施例的目的在于说明实施例1-2所制备的化合物1和2各自能够改善固化膜的耐热性。
按照实施例9中所述完全相同的方法分别制得化合物1-2各自的固化膜。然后采用TGA 550型热失重分析仪(TGA 550，美国沃特世公司)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25-800℃，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。其结果见表1。
结果显示，加入化合物1或2后，固化膜的初始分解温度(T 5％)及最大热失重温度T max1和T max2明显提高，因而耐热性明显被改善。
表1
Figure PCTCN2020097174-appb-000032

Claims (15)

  1. 下式(I)和/或(II)化合物：
    Figure PCTCN2020097174-appb-100001
    其中
    n为1-50的整数；
    m为1-10的整数；
    z为0-10的整数；
    p和p’相同或不同，并且为1-6的整数；
    R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 6-C 10芳基、C 1-C 12烷基、C 1-C 12烷氧基或者两个碳原子之间插有一个或多个独立地选自N、O、S的杂原子的C 1-C 12烷基；以及
    R 8为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基。
  2. 根据权利要求1的化合物，其中
    n为1-15的整数，优选为1-12的整数；和/或
    m为1-6的整数，优选为2-4的整数；和/或
    z为1-6的整数，优选为0-3的整数；和/或
    p和p’相同或不同，并且各自独立地为1-4的整数，优选为1-3的整数；和/或
    R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 6-C 10芳基、C 1-C 6烷基、 C 1-C 6烷氧基或者两个碳原子之间插有一个或多个选自NR b、O、S的杂原子的C 1-C 6烷基，其中R b为H或C 1-C 4烷基，优选的是，R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为苯基、C 1-C 4烷基、C 1-C 4烷氧基或者两个碳原子之间插有一个或多个独立地选自NR b、O、S的杂原子的C 1-C 4烷基，其中R b为H或C 1-C 4烷基；和/或
    R 8为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基，优选R 8为H或C 1-C 4烷基。
  3. 根据权利要求1的化合物，其中
    n为1-12的整数；
    m为2、3或4；
    z为0、1、2或3；
    p和p’相同，且为1、2或3；
    R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并独立地为C 1-C 4烷基；以及
    R 8为H或C 1-C 4烷基。
  4. 根据权利要求1的化合物，其为一种或多种选自下组的化合物：
    Figure PCTCN2020097174-appb-100002
    Figure PCTCN2020097174-appb-100003
  5. 一种制备根据权利要求1-4中任一项的式(I)化合物的方法，包括：
    (1)使式(III)化合物
    Figure PCTCN2020097174-appb-100004
    其中n、m、z、R 2、R 3、R 4、R 5、R 6和R 7如对权利要求1-4中任一项所定义，与式(IV)化合物反应，得到式(I)化合物
    Figure PCTCN2020097174-appb-100005
    其中p和R 8如对权利要求1-4中任一项所定义，并且X为卤素，例如氯、溴或碘。
  6. 根据权利要求5的方法，其中在步骤(1)中，
    式(III)化合物与式(IV)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选是氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物，更优选的是，式(III)化合物与碱性催化剂的摩尔比为1:2-1:10；和/或
    式(III)化合物与式(IV)化合物的摩尔比为1:2-1:2.4；和/或
    式(III)化合物与式(IV)化合物之间的反应先在冰点温度下进行，然后升温至25-60℃，优选升温至35-60℃反应；优选的是，冰点温度下的反应进行0.5-3小时，优选0.5-1小时；和/或，升温后继续反应6-24小时，优选8-24小时。
  7. 一种制备根据权利要求1-4中任一项的式(II)化合物的方法，包括：
    (a)使式(III)化合物
    Figure PCTCN2020097174-appb-100006
    其中n、m、z、R 2、R 3、R 4、R 5、R 6和R 7如对权利要求1-4中任一项所定义，与式(IV)化合物反应，
    Figure PCTCN2020097174-appb-100007
    其中p和R 8如对权利要求1-4中任一项所定义，并且X为卤素，例如氯、溴或碘，
    得到式(V)化合物，
    Figure PCTCN2020097174-appb-100008
    其中n、m、z、R 2、R 3、R 4、R 5、R 6、R 7和R 8如对权利要求1-4中任一项所定义；以及
    (b)使式(V)化合物与式(VI)化合物反应，得到式(II)化合物
    Figure PCTCN2020097174-appb-100009
    其中p’如对权利要求1-4中任一项所定义，以及Y为卤素，例如氯、溴或碘。
  8. 根据权利要求7的方法，其中在步骤(a)中，
    式(III)化合物与式(IV)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选是氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物，更优选的是，式(III)化合物与碱性催化剂的摩尔比为1:1-1:5；和/或
    式(III)化合物与式(IV)化合物的摩尔比为1:1-1:1.2；和/或
    式(III)化合物与式(IV)化合物之间的反应先在冰点温度下进行，然后升温至 25-60℃，优选升温至35-60℃反应；优选的是，冰点温度下的反应进行0.5-3小时，优选0.5-1小时；和/或，升温后继续反应6-24小时，优选8-24小时。
  9. 根据权利要求7或8的方法，其中在步骤(b)中，
    式(V)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(V)化合物与碱性催化剂的摩尔比为1:1-1:5；和/或
    式(V)化合物与式(VI)化合物的摩尔比为1:1-1:1.2；和/或
    式(V)化合物与式(VI)化合物之间的反应先在冰点温度下进行，然后升温至25-60℃，优选升温至35-60℃反应；优选的是，冰点温度下的反应进行0.5-3小时，优选0.5-1小时；和/或，升温后继续反应6-24小时，优选8-24小时。
  10. 一种制备根据权利要求1-4中任一项的式(II)化合物的方法，包括：
    (i)使式(III)化合物
    Figure PCTCN2020097174-appb-100010
    其中n、m、z、R 2、R 3、R 4、R 5、R 6和R 7如对权利要求1-4中任一项所定义，与式(VI)化合物反应，
    Figure PCTCN2020097174-appb-100011
    其中p’如对权利要求1-4中任一项所定义，以及Y为卤素，例如氯、溴或碘，得到式(V-a)化合物，
    Figure PCTCN2020097174-appb-100012
    其中n、m、z、p’、R 2、R 3、R 4、R 5、R 6和R 7如对权利要求1-4中任一项所定 义；以及
    (ii)使式(V-a)化合物与式(IV)化合物反应，得到式(II)化合物
    Figure PCTCN2020097174-appb-100013
    其中p和R 8如对权利要求1-4中任一项所定义，并且X为卤素，例如氯、溴或碘。
  11. 根据权利要求10的方法，其中在步骤(i)中，
    式(III)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(III)化合物与碱性催化剂的摩尔比为1:1-1:5；和/或
    式(III)化合物与式(VI)化合物的摩尔比为1:1-1:1.2；和/或
    式(III)化合物与式(VI)化合物之间的反应先在冰点温度下进行，然后升温至25-60℃，优选升温至35-60℃反应；优选的是，冰点温度下的反应进行0.5-3小时，优选0.5-1小时；和/或，升温后继续反应6-24小时，优选8-24小时。
  12. 根据权利要求10或11的方法，其中在步骤(ii)中，
    式(V-a)化合物与式(IV)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选是氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物，更优选的是，式(V-a)化合物与碱性催化剂的摩尔比为1:1-1:5；和/或
    式(V-a)化合物与式(IV)化合物的摩尔比为1:1-1:1.2；和/或
    式(V-a)化合物与式(IV)化合物之间的反应先在冰点温度下进行，然后升温至25-60℃，优选升温至35-60℃反应；优选的是，冰点温度下的反应进行0.5-3小时，优选0.5-1小时；和/或，升温后继续反应6-24小时，优选8-24小时。
  13. 根据权利要求5-12中任一项，其中X为氯，和Y为溴。
  14. 一种可光固化组合物，包含根据权利要求1-4中任一项的式(I)和/或(II)化合物作为聚合单体。
  15. 一种光固化材料，该材料通过将根据权利要求14的可光固化组合物光固化而获得。
PCT/CN2020/097174 2019-06-21 2020-06-19 一种含双氧杂环的含硅单体及其制备和应用 WO2020253838A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910544043.9 2019-06-21
CN201910544043.9A CN112111062A (zh) 2019-06-21 2019-06-21 一种含双氧杂环的含硅单体及其制备和应用

Publications (1)

Publication Number Publication Date
WO2020253838A1 true WO2020253838A1 (zh) 2020-12-24

Family

ID=73796510

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/097174 WO2020253838A1 (zh) 2019-06-21 2020-06-19 一种含双氧杂环的含硅单体及其制备和应用

Country Status (2)

Country Link
CN (1) CN112111062A (zh)
WO (1) WO2020253838A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113416208B (zh) * 2021-06-21 2023-06-23 湖北固润科技股份有限公司 丁香酚生物基含硅氧杂环丁烷单体及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1416447A (zh) * 2000-02-18 2003-05-07 罗狄亚化学公司 用具有反应性功能的可聚合和/或可交联有机组合物处理塑料材料表面
CN1418912A (zh) * 2001-11-13 2003-05-21 住友化学工业株式会社 含阳离子聚合化合物的组合物和由该组合物得到的涂层
EP1621570A1 (en) * 2004-07-29 2006-02-01 National Starch and Chemical Investment Holding Corporation Siloxane resins with oxetane functionality
WO2006013863A1 (ja) * 2004-08-04 2006-02-09 Toagosei Co., Ltd. ポリオルガノシロキサン及びそれを含む硬化性組成物
CN106188548A (zh) * 2016-07-16 2016-12-07 北京化工大学 一种含氧杂环丁烷结构的有机硅阳离子光固化树脂及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1416447A (zh) * 2000-02-18 2003-05-07 罗狄亚化学公司 用具有反应性功能的可聚合和/或可交联有机组合物处理塑料材料表面
CN1418912A (zh) * 2001-11-13 2003-05-21 住友化学工业株式会社 含阳离子聚合化合物的组合物和由该组合物得到的涂层
EP1621570A1 (en) * 2004-07-29 2006-02-01 National Starch and Chemical Investment Holding Corporation Siloxane resins with oxetane functionality
WO2006013863A1 (ja) * 2004-08-04 2006-02-09 Toagosei Co., Ltd. ポリオルガノシロキサン及びそれを含む硬化性組成物
CN106188548A (zh) * 2016-07-16 2016-12-07 北京化工大学 一种含氧杂环丁烷结构的有机硅阳离子光固化树脂及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHANG YA-JING, ZOU YING-QUAN: "The Development of Monomer for Cationic Photo Polymerization", INFORMATION RECORDING MATERIALS, vol. 6, no. 3, 31 December 2005 (2005-12-31), pages 17 - 26, XP055766521, DOI: 10.16009/j.cnki.cn13-1295/tq.2005.03.006 *

Also Published As

Publication number Publication date
CN112111062A (zh) 2020-12-22

Similar Documents

Publication Publication Date Title
WO2020253840A1 (zh) 含多硅的氧杂环丁烷类单体及其制备和应用
JP3403354B2 (ja) 光硬化性オキセタン組成物
AU2016232011A1 (en) Novel siloxane polymer compositions and their use
IE901940A1 (en) Novel highly reactive silicon-containing epoxides
WO2022267989A1 (zh) 丁香酚生物基含硅氧杂环丁烷单体及其制备方法
TWI582167B (zh) Containing silicon hardened composition and hardened material
WO2016066146A1 (zh) 一种含氧杂环丁烷基团的酯化合物及其制备方法
TW201439109A (zh) 含六氟異丙醇基之矽化合物及其製造方法、以及其聚合而成之高分子化合物
WO2020253838A1 (zh) 一种含双氧杂环的含硅单体及其制备和应用
TW202010819A (zh) 密封劑
US11034779B2 (en) Amide and imide photoinitiators
JP6211746B1 (ja) 樹脂組成物
WO2022267990A1 (zh) 诺卜醇生物基含硅氧杂环丁烷单体及其制备方法
WO2024067719A1 (zh) 三氟甲基有机硅氧杂环烷烃单体及其制备和应用
WO2022267991A1 (zh) 硫醚基氧杂环丁烷硅烷偶联剂及其制备方法
US7534901B2 (en) Siloxane monomers and oligomers
JP2014201534A (ja) ケイ素化合物
WO2020253839A1 (zh) 一种可混杂光固化的含多硅的氧杂环丁烷类单体及其制备和应用
WO2020230828A1 (ja) 含ケイ素ポリマー、膜形成用組成物、含ケイ素ポリマー被膜の形成方法、シリカ系被膜の形成方法、及び含ケイ素ポリマーの製造方法
JP4553647B2 (ja) カリックスレゾルシンアレーン誘導体及びその製法
CN107698477B (zh) 一种新型阳离子型光引发剂及其制备方法和应用
WO2020250736A1 (ja) 活性エネルギー線硬化型組成物
JP2020532567A (ja) スルホニウム塩光開始剤、その製造方法、それを含む光硬化性組成物及びその適用
WO2022131132A1 (ja) ジエポキシ化合物、硬化性組成物、硬化物及び光学部材
CN112898827A (zh) 一种基于含硅氧侧链二维丙烯酸酯单体的紫外光固化封装油墨及其使用方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20827070

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20827070

Country of ref document: EP

Kind code of ref document: A1