WO2020253840A1 - 含多硅的氧杂环丁烷类单体及其制备和应用 - Google Patents

含多硅的氧杂环丁烷类单体及其制备和应用 Download PDF

Info

Publication number
WO2020253840A1
WO2020253840A1 PCT/CN2020/097176 CN2020097176W WO2020253840A1 WO 2020253840 A1 WO2020253840 A1 WO 2020253840A1 CN 2020097176 W CN2020097176 W CN 2020097176W WO 2020253840 A1 WO2020253840 A1 WO 2020253840A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
formula
alkyl
integer
alkoxy
Prior art date
Application number
PCT/CN2020/097176
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 WO2020253840A1 publication Critical patent/WO2020253840A1/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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • 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
    • 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
    • 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
    • C07F7/0889—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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes

Definitions

  • the technical field to which the present invention belongs is the field of photocurable materials, and specifically relates to a polysilicon-containing oxetane monomer.
  • 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 are cationic light curing systems. Oxycycloalkane monomers are the main raw materials for high-end cationic light curing products. This system not only has low viscosity, low toxicity, and fast polymerization speed, but also has excellent thermal stability and mechanical properties.
  • the inventors of the present invention have conducted extensive and in-depth research on oxetane-based cationic photopolymerizable monomers in order to discover a new type of oxetane-based cationic photopolymerizable monomers.
  • Light-curing monomer after light-curing, the monomer has the advantages of good tensile properties, excellent hydrophobic properties, anti-staining, anti-fingerprint, etc.
  • the inventors discovered that the polysiloxane-containing oxetane monomers obtained by introducing polysiloxane chains into oxetane monomers have good tensile properties and excellent hydrophobic properties after light curing. Anti-staining, anti-fingerprint and other advantages.
  • an object of the present invention is to provide a polysilicon-containing oxetane monomer, which not only contains a cationic photocurable oxetane group, but also contains a polysiloxane chain.
  • the oxetane monomer with such a structure has good tensile properties after light 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 polysilicon-containing oxetane 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 polysilicon-containing oxetane monomer according to the present invention.
  • the last object of the present invention is to provide a photocurable material which is obtained by photocuring the photocurable composition of the present invention.
  • n is an integer from 1-50;
  • n is an integer of 0-20;
  • p is an integer of 1-6;
  • R 1 is C 1 -C 12 alkyl or C 1 -C 12 alkoxy
  • 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 inserted one or more heteroatoms independently selected from NR C atoms, a, O, S of 1 -C 12 alkyl, wherein R a is H or C 1 -C 4 alkyl group 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 1-20, preferably an integer of 2-15;
  • n is an integer of 1-8, preferably an integer of 1-5, more preferably an integer of 1-3;
  • p is an integer from 1 to 4, such as 1, 2 or 3;
  • R 1 is C 1 -C 6 alkyl or C 1 -C 6 alkoxy; R 1 is preferably C 1 -C 4 alkyl or C 1 -C 4 alkoxy; and/or
  • 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 inserted between two carbon atoms with one or more heteroatoms selected from NR a, O, S is C 1 -C 6 alkyl, wherein R a is H or C 1 -C 4 alkyl; preferably, R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently 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 a , O, S, wherein R a 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.
  • n is an integer from 1-9;
  • n is an integer of 1-5;
  • p 1, 2 or 3;
  • R 1 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy
  • 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 selected from NR a , O, S, wherein R a is H or a C 1 -C 4 alkyl group; and
  • 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;
  • n is an integer of 3-15;
  • n is an integer of 1-5;
  • p 1;
  • R 1 is 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 1 -C 4 alkyl groups;
  • R 8 is H or C 1 -C 4 alkyl.
  • n, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined in any one of items 1-4,
  • reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of Karstedt catalyst or Speier catalyst.
  • the amount of the catalyst based on the weight of the hydrogen-containing silicone oil is 2-100 ppm; and/or
  • the molar ratio of the compound of formula (II) to the compound of formula (III) is 1:1-1:1.5; and/or
  • reaction between the compound of formula (II) and the compound of formula (III) is carried out at 80-110°C, preferably 85-100°C; and/or
  • reaction between the compound of formula (II) and the compound of formula (III) is carried out for 3-6 hours, preferably 3.5-5.5 hours.
  • X is halogen, such as fluorine, chlorine, bromine or iodine,
  • the reaction between the compound of formula (IV) and the compound of formula (V) 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 (IV) to the basic catalyst is 1:1-1:3; and/or
  • the molar ratio of the compound of formula (IV) to the compound of formula (V) is 1:1-1:1.2; and/or
  • reaction between the compound of formula (IV) and the compound of formula (V) is carried out at 80-120°C, preferably 100-120°C; and/or,
  • reaction between the compound of formula (IV) and the compound of formula (V) is carried out for 6-12 hours, preferably 8-10 hours.
  • a photocurable composition comprising the compound of formula (I) according to any one of items 1 to 4 as a polymerizable monomer.
  • Fig. 1 is a graph showing the variation of the oxetane ring conversion rate of compound 1 prepared in Example 1 with the irradiation time.
  • Example 2 is a graph showing the change of the oxetane ring conversion rate of compound 2 prepared in Example 2 with irradiation time.
  • Fig. 3 is a graph showing the variation of the oxetane ring conversion rate of compound 3 prepared in Example 3 with irradiation time.
  • Figure 4 is a contact angle diagram of a blank E4221 cured film and a cured film of compound 1-3 prepared in each of Examples 1-3.
  • Figure 5 is a thermogravimetric curve diagram of a blank E4221 cured film and a cured film of Compound 1-3 prepared in Examples 1-3.
  • Fig. 6 is a graph showing mechanical properties of a blank E4221 cured film and a cured film of Compound 1-3 prepared in Examples 1-3.
  • n is an integer from 1-50;
  • n is an integer of 0-20;
  • p is an integer of 1-6;
  • R 1 is C 1 -C 12 alkyl or C 1 -C 12 alkoxy
  • 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 inserted one or more heteroatoms independently selected from NR C atoms, a, O, S of 1 -C 12 alkyl, wherein R a is H or C 1 -C 4 alkyl group 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.
  • the compound of formula (I) contains an oxetane structure and a polysiloxane structure part.
  • the compound with such a structure can be cured by cationic light, and has good tensile properties after light curing, excellent hydrophobic properties, anti-staining, anti-fingerprint, anti-chemical corrosion, strong anti-aging properties, and good heat resistance.
  • C n -C m indicates that the number of carbon atoms contained in the group is nm.
  • Halogen refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferable that the halogen includes fluorine, chlorine or a combination thereof.
  • C n -C m alkyl 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 Butyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-
  • 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 Group and its isomers.
  • 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 1 -C 6 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy, isopentoxy Group, hexyloxy 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 a C n -C m alkyl group substituted by one or more identical or different halogen atoms, such as C 1 -C 12 haloalkyl, preferably C 1 -C 6
  • the halogenated alkyl group is particularly preferably a C 1 -C 4 halogenated alkyl group.
  • C n -C m haloalkyl groups mention may be made of monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, 1-chloromethylethyl, monochlorobutane Group, 1-chloromethylpropyl, 2-chloromethylpropyl, 1,1-dichloromethylethyl, monochloropentyl, 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-dichloromethylbuty
  • C n -C m haloalkoxy refers to a C n -C m alkoxy group substituted with 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 1-20, particularly preferably an integer of 2-15, especially an integer of 3-15, such as 3, 4, 5, 6, 7, 8, or 9.
  • m is usually an integer of 0-20, preferably an integer of 1-8, particularly preferably an integer of 1-5 or 1-3, such as 1, 2, 3, 4, or 5.
  • p is usually an integer of 1-6, preferably an integer of 1-4, such as 1, 2 or 3.
  • 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. It is particularly preferred that R 1 is a C 1 -C 4 alkyl group or a C 1 -C 4 alkoxy group.
  • R 1 is C 1 -C 4 alkyl.
  • R 1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are the same or different, and are usually independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 inserted between two carbon atoms or alkoxy group having one or more heteroatoms independently selected from NR C atoms, a, O, S of 1 -C 12 alkyl, wherein R a 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 inserted between two carbon atoms or alkoxy group having one or more heteroatoms selected from NR a, O, S is C 1 -C 6 alkyl, wherein R a 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 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 a , O and S inserted between two carbon atoms, wherein R a 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 from 1-9;
  • n is an integer of 1-5;
  • p 1, 2 or 3;
  • R 1 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy
  • 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 selected from NR a , O, S, wherein R a is H or a C 1 -C 4 alkyl group; and
  • 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.
  • the compound of formula (I) is a compound selected from the group consisting of:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined for the compound of formula (I),
  • the compound of formula (II) contains a hydrogen atom on the silicon atom. Therefore, the compound of formula (II) can be referred to as hydrogen-containing silicone oil.
  • the addition reaction of the hydrogen atom bonded to the silicon atom in the compound of formula (II) with the unsaturated carbon-carbon double bond in the compound of formula (III) belongs to a reaction 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, Karstedt catalyst or Speier catalyst is generally used. The amount of catalyst is also conventional. Generally speaking, based on the weight of the hydrogen-containing silicone oil, the amount of the catalyst is 2-100 ppm by weight.
  • the reaction of the compound of formula (II) with the compound of formula (III) is usually carried out in a solvent.
  • the type of solvent is not particularly limited, as long as it can dissolve the compound of formula (II), the compound of formula (III) and the catalyst and does not participate in the reaction between the compound of formula (II) and the compound of formula (III).
  • the solvent also facilitates the precipitation of the product, that is, the compound of formula (I).
  • an organic solvent is generally used, and petroleum ether, methylene chloride, toluene, or any mixture thereof is preferably used.
  • the amount of solvent is also conventional. Generally speaking, the amount of solvent is 1.5-3 times the total weight of the compound of formula (II) and compound of formula (III).
  • the amount of the compound of formula (II) and the compound of formula (III) is usually used in approximately equimolar amounts.
  • the molar ratio of the compound of formula (II) to the compound of formula (III) is 1:1-1:1.5.
  • the compound of formula (II) and the catalyst are dissolved in a solvent for aging for a period of time, and then contacted with the compound of formula (III), and then heated to the reaction temperature for a period of time to obtain the compound of formula (I). Aging is usually carried out at elevated temperatures, usually at 40-70°C. The aging time is usually 30-60 minutes.
  • the reaction temperature between the compound of formula (II) and the compound of formula (III) is usually 80-110°C, preferably 85-100°C.
  • the retention time of the reaction between the compound of formula (II) and the compound of formula (III) at the reaction temperature is usually 3-6 hours, preferably 3.5-5.5 hours.
  • the reaction is advantageously carried out under stirring.
  • the product of the compound of formula (I) can be obtained through conventional post-treatment. This post-treatment usually includes 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, it can be recrystallized.
  • n is as defined for the compound of formula (III), and X is halogen, such as fluorine, chlorine, bromine or iodine,
  • the reaction of the hydroxyl group in the compound of formula (IV) with the halogen of the compound of formula (V) belongs to a type of reaction known in the art, and the reaction produces hydrogen halide. Generally speaking, this reaction is carried out in the presence of a basic catalyst.
  • a basic catalyst suitable for this reaction for example, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof can be mentioned.
  • the amount of catalyst is also conventional. Generally speaking, the molar ratio of the compound of formula (IV) to the basic catalyst is 1:1 to 1:3.
  • the reaction of the compound of formula (IV) with the compound of formula (V) is usually carried out in a solvent.
  • the type of solvent is not particularly limited, as long as it can dissolve the compound of formula (IV), the compound of formula (V) and the corresponding basic catalyst and does not participate in the reaction between the compound of formula (IV) and the compound of formula (V).
  • the solvent also facilitates the precipitation of the product, that is, the compound of formula (III).
  • 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 (IV) and compound of formula (V).
  • the amount of the compound of formula (IV) and the compound of formula (V) is usually used in approximately equimolar amounts.
  • the molar ratio of the compound of formula (IV) to the compound of formula (V) is 1:1-1:1.2.
  • the compound of formula (IV), the compound of formula (V) and the catalyst are usually dissolved in a solvent, and then the temperature is raised to the reaction temperature for a period of time to obtain the compound of formula (III).
  • the reaction temperature between the compound of formula (IV) and the compound of formula (V) is usually 80-120°C, preferably 100-120°C.
  • the holding time of the reaction between the compound of formula (IV) and the compound of formula (V) at the reaction temperature is usually 6-12 hours, preferably 8-10 hours.
  • the reaction is advantageously carried out under stirring.
  • the compound of formula (III) can be obtained through conventional post-treatment.
  • This post-treatment usually includes washing (for example, washing with water, after washing with water, 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 the solvent, and vacuum distillation to further remove the solvent. If you want to obtain a higher purity product, it can be recrystallized.
  • the compound of formula (I) of the present invention is a cationic light-curing monomer with good tensile properties after photo-curing polymerization, excellent hydrophobic properties, anti-staining, anti-fingerprint, anti-chemical corrosion, strong anti-aging properties, and heat resistance it is good.
  • a photocurable composition comprising the compound of formula (I) of the present invention as a polymerizable monomer.
  • the photocurable composition may also include a cationic photoinitiator for ring-opening polymerization (a photoinitiator that can initiate cationic polymerization) and optionally other vinyl ether double bonds.
  • a cationic photoinitiator for ring-opening polymerization a photoinitiator that can initiate cationic polymerization
  • optionally other vinyl ether double bonds optionally other vinyl ether double bonds.
  • Alicyclic epoxy group, oxirane group or oxetanyl group and other cationically curable monomers and oligomers 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, anti-staining, anti-fingerprint, anti-chemical corrosion, and strong anti-aging properties.
  • iodonium salts and sulfonium salts are commonly used.
  • the iodonium salt photoinitiator and the sulfonium salt photoinitiator have the following general formulas (A) and (B), respectively
  • R a , R b , R c , R d , R e are each independently an unsubstituted C 6 -C 10 aryl group, or are selected from halogen, nitro, carbonyl, C 1 -C 12 alkyl, C 1 C 6 -C 10 aryl substituted with substituents of -C 12 alkoxy, thiophenyl, phenyl and substituted phenyl, preferably phenyl or naphthyl, or selected from halogen, nitro, C 1- C 6 alkyl and substituted phenyl substituted phenyl or naphthyl, wherein the substituted phenyl contains one or more substituents selected from halogen, nitro, C 1 -C 6 alkyl and C 1- C 6 alkoxy group; and
  • Y and Z are non-nucleophilic anions, such as trifluoromethanesulfonate, BF 4 — , ClO 4 — , PF 6 — , AsF 6 — , SbF 6 — .
  • one or more selected from the following group can be used: 4-(phenylthio)phenyl ⁇ diphenylsulfonium hexafluorophosphate, 4-(phenylthio)phenyl ⁇ Diphenylsulfonium hexafluoroantimonate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexa Fluorantimonate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone Ketone-10-sulfonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate (8
  • the photocurable composition of the present invention may also contain a sensitizer.
  • a sensitizer for example, 2-isopropylthioxanthone can be mentioned.
  • the amount of photoinitiator is conventional. Based on the total weight of the photocurable composition of the present invention, the content of the photoinitiator is usually 0.5 to 5% by weight, preferably 1 to 3% by weight.
  • a photocurable material is provided, which is obtained by photocuring the photocurable composition of the present invention. Because the photocurable material contains the compound of formula (I) of the present invention as a photocurable monomer, it has good tensile properties, excellent hydrophobic properties, stain resistance, fingerprint resistance, chemical corrosion resistance, and strong aging resistance. Advantages of good heat resistance.
  • the purpose of this example is to illustrate the photopolymerization properties of the compounds of the present invention.
  • a mixture of photoinitiator diphenyliodonium hexafluorophosphate (810) and 2-isopropylthioxanthone (ITX, sensitizer) in a 2:1 mass ratio is used as the photoinitiator system, and real-time infrared
  • the (RT-IR) method tested the photopolymerization performance of each compound 1-6 under different initiator concentrations.
  • 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 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 each compound 1-3 are shown in Figure 1-3. The results show that Compound 1-3 has good photopolymerization performance.
  • each of the compounds 4-6 has an initiation system with four concentrations of 0.75%810+0.38%ITX, 1.50%810+0.75%ITX, 3.00%810+1.50%ITX, and 4.50%810+2.25%ITX
  • the conversion rate of the quaternary oxygen heterocycle of the monomer will increase with the increase of the initiator concentration, and the maximum conversion rate of the quaternary oxygen heterocycle has reached at least 50%.
  • the respective concentrations of 810 and ITX are based on the respective weight of compound 1-6. Therefore, the compound of the present invention has good photopolymerization performance.
  • the purpose of this example is to show that the compound of the present invention can improve the surface hydrophobicity of the photocurable film.
  • Compounds 1-6 were each mixed with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (E4221) epoxy monomer in a mass ratio of 5:95 to be based on E4221 and epoxy
  • the total weight of the monomers is respectively 3.0wt% 810 and 1.5wt% ITX as initiators, and they are mixed uniformly to obtain a photosensitive liquid.
  • the purpose of this example is to show that the compound of the present invention can improve the heat resistance of the cured film.
  • the cured films of Compounds 1-3 were prepared in exactly the same way as in Example 8. 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 Figure 5 and Table 1.
  • the purpose of this example is to show that the compound of the present invention can improve the tensile properties of the photocurable film.
  • the cured films of Compounds 1-3 were prepared in exactly the same way as described in Example 8. Then, an Instron-1211 electronic tensile machine (Instron-1211, Instron, USA) was used to test the tensile properties of the light-cured film. The test temperature is 25°C and the test speed is 50mm/min. At the same time, use the same method to prepare a blank E4221 cured film as a reference. The result is shown in Figure 6.
  • the tensile strength of the pure E4221 light-cured film is 7.02 MPa. After the additional monomers of Compound 1-3 are added, the tensile strength and elongation at break of the light-cured film gradually increase. Therefore, the compound of the present invention can significantly improve the tensile properties of the cured film.

Abstract

涉及式(I)化合物，其中各变量n、m、p、R1、R2、R3、R4、R5、R6、R7和R8如说明书中所定义。式(I)化合物可光聚合，光固化后具有拉伸性能好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强等优点。还涉及式(I)化合物的制备，包含式(I)化合物的可光固化组合物和由该可光固化组合物光固化得到的光固化材料。

Description

含多硅的氧杂环丁烷类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多硅的氧杂环丁烷类单体。本发明还涉及该单体的制备方法，包含该单体的可光固化组合物和由该可光固化组合物光固化得到的光固化材料。
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。氧杂环烷烃类单体属阳离子光固化体系。氧杂环烷烃类单体是高端阳离子光固化产品的主要原料，这种体系不仅粘度低、毒性低、聚合速度快，还具有优异的热稳定性及机械性能。然而，在紫外光固化以节能、环保、高效等优点迅速发展的同时，对于光固化材料的耐热性、拒水性、表面的抗沾污、耐腐蚀及抗指纹等方面人们提出了更高的要求。消费者对产品外观的要求日益提高，除了色彩美观以及手感舒适外，还要求表面具有抗指纹、耐沾污的性能，即使用时产品表面不易留下指纹等痕迹，或者即使留下痕迹也很容易被擦净。目前，能够满足前述要求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丁烷类可阳离子光聚合单体方面进行了广泛而又深入的研究，以期发现一类新型的氧杂环丁烷类可阳离子光固化单体，该单体光固化后具有拉伸性能好，疏水性能优良，抗沾污， 抗指纹等优点。本发明人发现，将聚硅氧烷链引入到氧杂环丁烷类单体中，如此获得的含多硅的氧杂环丁烷单体光固化后具有拉伸性能好，疏水性能优良，抗沾污，抗指纹等优点。
因此，本发明的一个目的是提供一种含多硅的氧杂环丁烷单体，该单体不仅含有可阳离子光固化的氧杂环丁烷基团，而且还含有聚硅氧烷链。具有如此结构的氧杂环丁烷单体光固化后拉伸性能好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强，耐热性好。
本发明的另一目的是提供一种制备本发明含多硅的氧杂环丁烷单体的方法。该制备过程简单易行，条件温和，原料易得，价格低廉。
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多硅的氧杂环丁烷单体。
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)化合物：
Figure PCTCN2020097176-appb-000001
其中
n为1-50的整数；
m为0-20的整数；
p为1-6的整数；
R 1为C 1-C 12烷基或者C 1-C 12烷氧基；
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NR a、O、S的杂原子的C 1-C 12烷基，其中R a为H或C 1-C 4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1-20的整数，优选为2-15的整数；和/或
m为1-8的整数，优选为1-5的整数，更优选为1-3的整数；和/或
p为1-4的整数，例如为1、2或3；和/或
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；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 a、O、S的杂原子的C 1-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、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 a、O、S的杂原子的C 1-C 4烷基，其中R a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。
3.根据第1项的化合物，其中
n为1-9的整数；
m为1-5的整数；
p为1、2或3；
R 1为C 1-C 4烷基或者C 1-C 4烷氧基；
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选自NR a、O、S的杂原子的C 1-C 4烷基，其中R a为H或C 1-C 4烷基；以及
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；
优选的是，
n为3-15的整数；
m为1-5的整数；
p为1；
R 1为C 1-C 4烷基；
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下组的化合物：
Figure PCTCN2020097176-appb-000002
5.一种制备根据第1-4项中任一项的式(I)化合物的方法，包括使式(II)化合 物：
Figure PCTCN2020097176-appb-000003
其中n、R 1、R 2、R 3、R 4、R 5、R 6和R 7如第1-4项中任一项所定义，
与式(III)化合物反应，
Figure PCTCN2020097176-appb-000004
其中m、p和R 8如第1-4项中任一项所定义，
得到式(I)化合物。
6.根据第5项的方法，其中
式(II)化合物与式(III)化合物的反应在Karstedt催化剂或Speier催化剂存在下进行，优选的是，催化剂基于含氢硅油的重量的用量为2-100ppm；和/或
式(II)化合物与式(III)化合物的用量摩尔比为1:1-1:1.5；和/或
式(II)化合物与式(III)化合物之间的反应在80-110℃，优选85-100℃下进行；和/或
式(II)化合物与式(III)化合物之间的反应进行3-6小时，优选3.5-5.5小时。
7.根据第5或6项的方法，其中还包括：使式(IV)化合物
Figure PCTCN2020097176-appb-000005
其中p和R 8如第1-4项中任一项所定义，
与式(V)化合物反应，
Figure PCTCN2020097176-appb-000006
其中m如第1-4项中任一项所定义，X为卤素，例如氟、氯、溴或碘，
得到式(III)化合物。
8.根据第7项的方法，其中
式(IV)化合物与式(V)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选为氢氧化钠、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用量比为1:1-1:3；和/或
式(IV)化合物与式(V)化合物的用量摩尔比为1:1-1:1.2；和/或
式(IV)化合物与式(V)化合物之间的反应在80-120℃，优选100-120℃下进行；和/或，
式(IV)化合物与式(V)化合物之间的反应进行6-12小时，优选8-10小时。
9.一种可光固化组合物，包含根据第1-4项中任一项的式(I)化合物作为聚合单体。
10.一种光固化材料，该材料通过将根据第9项的可光固化组合物光固化而获得。
附图说明
图1是实施例1所制备的化合物1的氧杂环丁烷环转化率随辐照时间的变化曲线图。
图2是实施例2所制备的化合物2的氧杂环丁烷环转化率随辐照时间的变化曲线图。
图3是实施例3所制备的化合物3的氧杂环丁烷环转化率随辐照时间的变化曲线图。
图4是空白E4221固化膜和实施例1-3各自制备的化合物1-3的固化膜的接触角图。
图5是空白E4221固化膜和实施例1-3各自制备的化合物1-3的固化膜的热重曲线图。
图6是空白E4221固化膜和实施例1-3各自制备的化合物1-3的固化膜的机械性能曲线图。
具体实施方式
根据本发明的一个方面，提供了一种下式(I)化合物：
Figure PCTCN2020097176-appb-000007
其中
n为1-50的整数；
m为0-20的整数；
p为1-6的整数；
R 1为C 1-C 12烷基或者C 1-C 12烷氧基；
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NR a、O、S的杂原子的C 1-C 12烷基，其中R a为H或C 1-C 4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)化合物包含氧杂环丁烷结构，又包含聚硅氧烷结构部分。具有如此结构的化合物可以阳离子光固化，并且光固化后拉伸性能好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强，耐热性好。
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。
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。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。
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。
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。
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1-20的整数，特别优选为2-15的整数，尤其为3-15的整数，例如为3、4、5、6、7、8或9。
在本发明化合物中，m通常为0-20的整数，优选为1-8的整数，特别优选为1-5或1-3的整数，例如为1、2、3、4或5。
在本发明化合物中，p通常为1-6的整数，优选为1-4的整数，例如为1、2或3。
在本发明化合物中，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。
在本发明化合物中，R 2、R 3、R 4、R 5、R 6、R 7相同或不同，并通常独立地为C 6-C 10芳基、C 1-C 12烷基、C 1-C 12烷氧基或者两个碳原子之间插有一个或多个独立地选自NR a、O、S的杂原子的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、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 a、O、S的杂原子的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、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 a、O、S的杂原子的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、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。
在本发明的一些优选实施方案中，
n为1-9的整数；
m为1-5的整数；
p为1、2或3；
R 1为C 1-C 4烷基或者C 1-C 4烷氧基；
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选自NR a、O、S的杂原子的C 1-C 4烷基，其中R a为H或C 1-C 4烷基；以及
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。
在本发明的另一实施方案中，式(I)化合物为选自下组的化合物：
Figure PCTCN2020097176-appb-000008
Figure PCTCN2020097176-appb-000009
根据本发明的第二个方面，提供了一种制备本发明式(I)化合物的方法，包括使式(II)化合物：
Figure PCTCN2020097176-appb-000010
其中n、R 1、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(III)化合物反应，
Figure PCTCN2020097176-appb-000011
其中m、p和R 8如对式(I)化合物所定义,
得到式(I)化合物。
式(II)化合物的硅原子上含有氢原子，因此，式(II)化合物可称作含氢硅油。式(II)化合物中硅原子键合的氢原子与式(III)化合物中的不饱和碳碳双键的加成反应属于本领域已知的反应类型。通常而言，该反应在催化剂存在下进行。作为适合该反应的催化剂，通常采用Karstedt催化剂或Speier催化剂。催化剂的用量也是常规的。通常而言，基于含氢硅油的重量，催化剂的用量为其重量的2-100ppm。式(II)化合物与式(III)化合物的反应通常在溶剂中进行。作为溶剂的类型，没有特别的限制，只要能将式(II)化合物、式(III)化合物和催化剂溶解并且不参与式(II)化合物与式(III)化合物之间的反应即可，优选该溶剂还有利于产物，即式(I)化合物析出。作为该溶剂，通常使用有机溶剂，优选使用石油醚、二氯甲烷、甲苯或其任意混合物。溶剂的用量也是常规的，通常而言，溶剂的用量为式(II)化合物和式(III)化合物总重量的1.5-3倍。式(II)化合物和式(III)化合物的用量通常以大致等摩尔量使用。有利的是，式(II)化合物与式(III)化合物的用量摩尔比为1:1-1:1.5。为了实现上述反应，通常先将式(II)化合物与催化剂溶解在溶剂中陈化一段时间后，再与式(III)化合物接触，然后升温至反应温度保持一段时间，得到式(I)化合物。陈化通常在升高的温度下进行，通常在40-70℃陈化。陈化时间通常为30-60分钟。式(II)化合物与式(III)化合物之间的反应温度通常为80-110℃，优选85-100℃。式(II)化合物与式(III)化合物之间的反应在反应温度下的保持时间通常为3-6小时，优选3.5-5.5小时。当然，反应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。
在本发明方法的另一实施方案中，还包括：使式(IV)化合物
Figure PCTCN2020097176-appb-000012
其中p和R 8如对式(III)化合物所定义，
与式(V)化合物反应，
Figure PCTCN2020097176-appb-000013
其中m如对式(III)化合物所定义,X为卤素，例如氟、氯、溴或碘，
得到式(III)化合物。
式(IV)化合物中的羟基与式(V)化合物中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，例如可以提及氢氧化钠、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(IV)化合物与碱性催化剂的摩尔用量比为1:1-1:3。式(IV)化合物与式(V)化合物的反应通常在溶剂中进行。作为溶剂的类型，没有特别的限制，只要能将式(IV)化合物、式(V)化合物和相应碱性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(III)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0.5-3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(V)化合物的用量摩尔比为1:1-1:1.2。为了实现上述反应，通常将式(IV)化合物、式(V)化合物和催化剂溶解在溶剂中，然后升温至反应温度保持一段时间，得到式(III)化合物。式(IV)化合物与式(V)化合物之间的反应温度通常为80-120℃，优选100-120℃。式(IV)化合物与式(V)化合物之间的反应在反应温度下的保持时间通常为6-12小时，优选8-10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(III)化合物。该后处理通常包括洗涤(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。
本发明式(I)化合物是一种阳离子光固化单体，光固化聚合之后拉伸性能较好，疏水性能优良，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强，耐热性好。
因此，根据本发明的第三个方面，提供了一种可光固化组合物，该组合物包含本发明的式(I)化合物作为聚合单体。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，抗沾污，抗指纹，抗化学品腐蚀，抗老化性能强。
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)
Figure PCTCN2020097176-appb-000014
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。
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。
对本发明而言，光引发剂的用量是常规的。基于本发明可光固化组合物的总重量，光引发剂的含量通常为0.5-5重量％，优选为1-3重量％。
根据本发明的最后一个方面，提供了一种光固化材料，该材料通过将本发明的可光固化组合物光固化而获得。该光固化材料由于包含本发明式(I)化合物作为可光固化单体的缘故，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，耐热性好的优点。
实施例
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1
在装有温度探头和回流冷凝管的三口烧瓶中，加入11.6g(0.1mol)3-羟甲基-3-乙基-氧杂环丁烷、14.40g(0.12mol)3-溴丙烯、30mL甲苯和11.2(0.2mol)氢氧化钾，升温至110℃，在500r/min的搅拌速率下反应10h，然后结束反应。将所得反应液用蒸馏水洗涤三次，取上层清液，离心除去固体杂质，后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，得到化合物1a，产率为50％。
Figure PCTCN2020097176-appb-000015
在装有温度探头和回流冷凝管的三口烧瓶中，将含氢硅油41.2g(0.1mol)(对应于式(II)化合物，其中n＝3，R 1为正丁基，以及R 2、R 3、R 4、R 5、R 6和R 7为甲基)和8.24g 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1a 18.72g(0.12mol)，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，下文有时称作MOSi-3。
[MOSi-3]: 1H NMR(400MHz,CDCl 3)δ0.16-0.04(m,30H),0.56(m,4H),0.92(td,J＝7.4,5.8Hz,6H),1.34(m,4H),1.61(m,2H),1.78(d,J＝7.5Hz,2H),3.44(t,J＝6.8Hz,2H),3.57(d,J＝9.8Hz,2H),4.51-4.37(m,4H).
Figure PCTCN2020097176-appb-000016
实施例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63.4g(0.1mol)(对应于式(II)化合物，其中n＝6，R 1为正丁基，以及R 2、R 3、R 4、R 5、R 6和R 7为甲基)和12.68g 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1a 18.72g(0.12mol)，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，下文有时称作MOSi-6。
[MOSi-6]: 1H NMR(400MHz,CDCl 3)δ0.14-0.04(m,48H),0.56(m,4H),0.92(td,J＝7.4,5.8Hz,6H),1.34(m,4H),1.61(m,2H),1.78(d,J＝7.5Hz,2H),3.44(t,J＝6.8Hz,2H),3.57(d,J＝9.8Hz,2H),4.51-4.37(m,4H).
Figure PCTCN2020097176-appb-000017
实施例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85.6g(0.1mol)(对应于式(II)化合物，其中n＝9，R 1为正丁基，以及R 2、R 3、R 4、R 5、R 6和R 7为甲基)和17.12g 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1a 18.72g(0.12mol)，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，下文有时称作MOSi-9。
[MOSi-9]: 1H NMR(400MHz,CDCl 3)δ0.16-0.04(m,66H),0.56(m,4H),0.92(td,J＝7.4,5.8Hz,6H),1.34(m,4H),1.61(m,2H),1.78(d,J＝7.5Hz,2H),3.44(t,J＝6.8Hz,2H),3.57(d,J＝9.8Hz,2H),4.51-4.37(m,4H).
Figure PCTCN2020097176-appb-000018
实施例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130g(0.1mol)(对应于式(II)化合物，其中n＝15，R 1为正丁基，以及R 2、R 3、R 4、R 5、R 6和R 7为甲基)和26g 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1a 18.72g(0.12mol)，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，下文有时称作MOSi-15。
[MOSi-15]: 1H NMR(400MHz,CDCl 3)δ0.16-0.04(m,102H),0.56(m,4H),0.92(td,J＝7.4,5.8Hz,6H),1.34(m,4H),1.61(m,2H),1.78(d,J＝7.5Hz,2H),3.44(t,J＝6.8Hz,2H),3.57(d,J＝9.8Hz,2H),4.51-4.37(m,4H).
Figure PCTCN2020097176-appb-000019
实施例5
在装有温度探头和回流冷凝管的三口烧瓶中，加入5.8g(0.05mol)3-羟甲基-3-乙基-氧杂环丁烷、10.62g(0.06mol)7-溴-1-庚烯、20mL甲苯和5.6g(0.1mol)氢氧化钾，升温至110℃，在500r/min的搅拌速率下反应10h，然后结束反应。将所得反应液用蒸馏水洗涤三次，取上层清液，离心除去固体杂质，后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，得到化合物5a，产率为50％。
Figure PCTCN2020097176-appb-000020
在装有温度探头和回流冷凝管的三口烧瓶中，将含氢硅油41.2g(0.1mol)(对应于式(II)化合物，其中n＝3，R 1为正丁基，以及R 2、R 3、R 4、R 5、R 6和R 7为甲基)和8.24g 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5a 25.46g(0.12mol)，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5。
1H NMR(400MHz,CDCl 3)δ0.16-0.04(m,30H),0.56(m,4H),0.92(td,J＝7.4,5.8Hz,6H),1.34(m,2H),1.43-1.50(m,4H),1.23-1.29(m,6H),1.61(m,2H),1.78(d,J＝7.5Hz,2H),3.44(t,J＝6.8Hz,2H),3.57(d,J＝9.8Hz,2H),4.51-4.37(m,4H).
Figure PCTCN2020097176-appb-000021
实施例6
在装有温度探头和回流冷凝管的三口烧瓶中，加入8.8g(0.1mol)3-羟甲基 氧杂环丁烷、14.40g(0.12mol)3-溴丙烯、20mL甲苯和11.2(0.2mol)氢氧化钾，升温至110℃，在500r/min的搅拌速率下反应10h，然后结束反应。将所得反应液用蒸馏水洗涤三次，取上层清液，离心除去固体杂质，后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，得到化合物6a，产率为50％。
Figure PCTCN2020097176-appb-000022
在装有温度探头和回流冷凝管的三口烧瓶中，将含氢硅油41.2g(0.1mol)(对应于式(II)化合物，其中n＝3，R 1为正丁基，以及R 2、R 3、R 4、R 5、R 6和R 7为甲基)和8.24g 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6a 15.36g(0.12mol)，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6。
1H NMR(400MHz,CDCl 3)δ0.16-0.04(m,30H),0.56(m,4H),0.92(td,J＝7.4,5.8Hz,3H),1.34(m,4H),1.78(d,J＝7.5Hz,2H),2.92(m,1H)3.44(t,J＝6.8Hz,2H),3.57(d,J＝9.8Hz,2H),4.51-4.37(m,4H).
Figure PCTCN2020097176-appb-000023
实施例7
本实施例的目的在于说明本发明化合物的光聚合性能。
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，增感剂)以2:1质量比组成的混合物作为光引发体系，采用实时红外(RT-IR)的方法测试了化合物1-6各自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，可以分别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。其中化合物1-3各自的结果分别如图1-3所示。结果显示，化合物1-3具有良好的光聚合性能。另外，化合物4-6中的每一种在0.75％810+0.38％ITX、1.50％810+0.75％ITX、3.00％810+1.50％ITX、4.50％810+2.25％ITX这四个浓度的引发体系下在高压汞灯辐照600秒以后，其单体的四元氧杂环转化率会随引发剂浓度的提高而增大，其四元氧杂环最大转化率都达到了至少50％。其中810和ITX各自的浓度均基于化合物1-6各自的重量。因此本发明化合物具有良好的光聚合性能。
实施例8
本实施例的目的在于说明本发明化合物能够改善光固化膜的表面疏水性。
将化合物1-6各自与3,4-环氧环己基甲基3,4-环氧环己基甲酸酯(E4221)环氧单体以5：95的质量比混合，以基于E4221与环氧单体的总重量分别为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。参比和化合物1-3的结果见图4。
由图4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62.5°，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84.2°、87.6°及91.7°。另外，额外加入化合物4-6中之一获得的固化膜的接触角均超过85°(分别为93.5°，85.6°，86.0°)。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9
本实施例的目的在于说明本发明化合物能够改善固化膜的耐热性。
按照实施例8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。其结果见图5及表1。
由表1和图5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T max1和T max2明显提高，因而耐热性明显被改善。
表1
Figure PCTCN2020097176-appb-000024
实施例10
本实施例的目的在于说明本发明化合物能够改善光固化膜的拉伸性能。
按照实施例8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Instron-1211型电子拉力机(Instron-1211型，美国Instron公司)进行光固化膜的拉伸性能测试。测试温度为25℃，测试速度为50mm/min。同时，利用同样方法制备空白E4221固化膜作为参比。其结果见图6。
由图6可见，纯E4221光固化膜的拉伸强度为7.02MPa，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。

Claims (10)

  1. 下式(I)化合物：
    Figure PCTCN2020097176-appb-100001
    其中
    n为1-50的整数；
    m为0-20的整数；
    p为1-6的整数；
    R 1为C 1-C 12烷基或者C 1-C 12烷氧基；
    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NR a、O、S的杂原子的C 1-C 12烷基，其中R a为H或C 1-C 4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1-20的整数，优选为2-15的整数；和/或
    m为1-8的整数，优选为1-5的整数，更优选为1-3的整数；和/或
    p为1-4的整数，例如为1、2或3；和/或
    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；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 a、O、S的杂原子的C 1-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、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 a、O、S的杂原子的C 1-C 4烷基，其中R a 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。
  3. 根据权利要求1的化合物，其中
    n为2-15的整数；
    m为1-5的整数；
    p为1、2或3；
    R 1为C 1-C 4烷基或者C 1-C 4烷氧基；
    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选自NR a、O、S的杂原子的C 1-C 4烷基，其中R a为H或C 1-C 4烷基；以及
    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；
    优选的是，
    n为3-15的整数；
    m为1-5的整数；
    p为1；
    R 1为C 1-C 4烷基；
    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 PCTCN2020097176-appb-100002
    Figure PCTCN2020097176-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，包括使式(II)化合物：
    Figure PCTCN2020097176-appb-100004
    其中n、R 1、R 2、R 3、R 4、R 5、R 6和R 7如权利要求1-4中任一项所定义，与式(III)化合物反应，
    Figure PCTCN2020097176-appb-100005
    其中m、p和R 8如权利要求1-4中任一项所定义，
    得到式(I)化合物。
  6. 根据权利要求5的方法，其中
    式(II)化合物与式(III)化合物的反应在Karstedt催化剂或Speier催化剂存在下进行，优选的是，催化剂基于含氢硅油的重量的用量为2-100ppm；和/或
    式(II)化合物与式(III)化合物的用量摩尔比为1:1-1:1.5；和/或
    式(II)化合物与式(III)化合物之间的反应在80-110℃，优选85-100℃下进行；和/或
    式(II)化合物与式(III)化合物之间的反应进行3-6小时，优选3.5-5.5小时。
  7. 根据权利要求5或6的方法，其中还包括：使式(IV)化合物
    Figure PCTCN2020097176-appb-100006
    其中p和R 8如权利要求1-4中任一项所定义，
    与式(V)化合物反应，
    Figure PCTCN2020097176-appb-100007
    其中m如权利要求1-4中任一项所定义，X为卤素，例如氟、氯、溴或碘，得到式(III)化合物。
  8. 根据权利要求7的方法，其中
    式(IV)化合物与式(V)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选为氢氧化钠、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用量比为1:1-1:3；和/或
    式(IV)化合物与式(V)化合物的用量摩尔比为1:1-1:1.2；和/或
    式(IV)化合物与式(V)化合物之间的反应在80-120℃，优选100-120℃下进 行；和/或，
    式(IV)化合物与式(V)化合物之间的反应进行6-12小时，优选8-10小时。
  9. 一种可光固化组合物，包含根据权利要求1-4中任一项的式(I)化合物作为聚合单体。
  10. 一种光固化材料，该材料通过将根据权利要求9的可光固化组合物光固化而获得。
PCT/CN2020/097176 2019-06-21 2020-06-19 含多硅的氧杂环丁烷类单体及其制备和应用 WO2020253840A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910543103.5A CN112111063A (zh) 2019-06-21 2019-06-21 含多硅的氧杂环丁烷类单体及其制备和应用
CN201910543103.5 2019-06-21

Publications (1)

Publication Number Publication Date
WO2020253840A1 true WO2020253840A1 (zh) 2020-12-24

Family

ID=73796398

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/097176 WO2020253840A1 (zh) 2019-06-21 2020-06-19 含多硅的氧杂环丁烷类单体及其制备和应用

Country Status (2)

Country Link
CN (1) CN112111063A (zh)
WO (1) WO2020253840A1 (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113336946B (zh) * 2021-06-21 2022-10-11 湖北固润科技股份有限公司 诺卜醇生物基含硅氧杂环丁烷单体及其制备方法
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
CN113620985B (zh) * 2021-08-13 2022-09-27 合肥工业大学 一种含硅的氧杂环丁烷衍生物及其制备方法和应用
CN115521460A (zh) * 2022-09-30 2022-12-27 湖北固润科技股份有限公司 三氟甲基有机硅氧杂环烷烃单体及其制备和应用
CN115521463A (zh) * 2022-09-30 2022-12-27 湖北固润科技股份有限公司 三氟甲基有机硅脂环族环氧单体及其制备和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10316757A (ja) * 1997-05-14 1998-12-02 Toagosei Co Ltd 光カチオン重合性有機ケイ素化合物及びその製造方法
JP2000264969A (ja) * 1999-03-16 2000-09-26 Ge Toshiba Silicones Co Ltd 縮合型シリコーン組成物、硬化物、その表面改質方法および平版
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
JP2004043609A (ja) * 2002-07-10 2004-02-12 Toagosei Co Ltd オキセタン環を有するシロキサン誘導体
KR20090081880A (ko) * 2008-01-25 2009-07-29 삼성에스디아이 주식회사 리튬이차전지 전해질용 첨가제, 이를 포함하는 유기 전해액및 상기 전해액을 채용한 리튬 전지
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010119903A1 (ja) * 2009-04-14 2010-10-21 チッソ株式会社 ガラス繊維複合化シルセスキオキサン成形体とその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10316757A (ja) * 1997-05-14 1998-12-02 Toagosei Co Ltd 光カチオン重合性有機ケイ素化合物及びその製造方法
JP2000264969A (ja) * 1999-03-16 2000-09-26 Ge Toshiba Silicones Co Ltd 縮合型シリコーン組成物、硬化物、その表面改質方法および平版
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
JP2004043609A (ja) * 2002-07-10 2004-02-12 Toagosei Co Ltd オキセタン環を有するシロキサン誘導体
KR20090081880A (ko) * 2008-01-25 2009-07-29 삼성에스디아이 주식회사 리튬이차전지 전해질용 첨가제, 이를 포함하는 유기 전해액및 상기 전해액을 채용한 리튬 전지
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

Also Published As

Publication number Publication date
CN112111063A (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
WO2022267989A1 (zh) 丁香酚生物基含硅氧杂环丁烷单体及其制备方法
US7999127B2 (en) Siloxane monomers and oligomers
JP6703118B2 (ja) シリコーン相溶性化合物
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
TWI701255B (zh) 具有耐酸性之鹼或／及自由基產生劑，以及含有該鹼或／及自由基產生劑之硬化性樹脂組成物
CN104341583B (zh) 芳族聚缩醛及其制品
CN101906114B (zh) 一种含阳离子光固化基团的硅氧化合物及其制备方法
WO2020253838A1 (zh) 一种含双氧杂环的含硅单体及其制备和应用
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
WO2024067720A1 (zh) 三氟甲基有机硅脂环族环氧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
JP4952084B2 (ja) １，４−ジヒドロ−アントラセン誘導体およびその製造方法
JP2014201534A (ja) ケイ素化合物
JP5339048B2 (ja) 光カチオン重合性を有する光重合増感剤
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
CN110317346B (zh) 树枝状荧光素钠-碘鎓盐可见光引发剂及其制备方法和应用
JP6667137B2 (ja) 光硬化性シリコーン組成物
JP5157800B2 (ja) 新規な１，４−ジヒドロアントラセン−９，１０−ジエーテル化合物
JP6861943B2 (ja) ｛（３−メチルオキセタン−３−イル）メチルオキシ｝基を有するアントラセン型化合物、その製造法及びその用途
TW201600500A (zh) 肟酯化合物以及包括該肟酯化合物的光聚合性組合物
JP6352387B2 (ja) 新規化合物、該化合物を含有する光酸発生剤及び該光酸発生剤を含有する感光性樹脂組成物
Ozcan et al. 4-methyl-4-[2-(naphthalene)-2-oxoethyl] morpholin-4-ium iodide as a water soluble photoinitiator
JP2018118935A (ja) 新規化合物、該化合物を含有する光酸発生剤、及び該光酸発生剤を含有する感光性樹脂組成物

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: 20826922

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: 20826922

Country of ref document: EP

Kind code of ref document: A1