WO2022267991A1 - Agent de couplage de thioéther oxétane silane et son procédé de préparation - Google Patents

Agent de couplage de thioéther oxétane silane et son procédé de préparation Download PDF

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WO2022267991A1
WO2022267991A1 PCT/CN2022/099402 CN2022099402W WO2022267991A1 WO 2022267991 A1 WO2022267991 A1 WO 2022267991A1 CN 2022099402 W CN2022099402 W CN 2022099402W WO 2022267991 A1 WO2022267991 A1 WO 2022267991A1
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compound
formula
alkylene
alkyl
alkyleneoxy
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PCT/CN2022/099402
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Chinese (zh)
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孙芳
杨宗鑫
邹应全
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湖北固润科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C 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
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • 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
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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 invention relates to the field of photocurable materials, in particular to a thioether-based oxetane silane coupling agent.
  • the present invention also relates to a preparation method of the silane coupling agent, a photocurable composition containing the silane coupling agent and a photocurable material obtained from the photocurable composition.
  • Photopolymerization technology is the process of using light to initiate the conversion of liquid oligomers or monomers with active substances into solid products. Compared with traditional thermal polymerization technology, photopolymerization can achieve efficient and pollution-free production without using volatile organic solvents, saving a lot of energy. It is estimated that energy costs can be reduced by 20-25% by switching from thermal to photopolymerization. Photopolymerization technology is regarded as a green process because of its unique low energy consumption requirements, fast curing, solvent-free formula, no pollution, room temperature treatment and environmental protection, so it is widely used in the fields of photocuring coatings, adhesives and ink printing. Wide range of applications.
  • silane coupling agent can improve the performance of materials, but the silane coupling agent will be free in the photopolymerization system, affecting the overall performance of the product and causing environmental pollution. Therefore, people hope to develop a silane coupling agent with little or no free, so as to improve the overall performance of the product and reduce the environmental pollution of the product.
  • the preparation process of silane coupling agents that can be industrially produced at present requires heating and the use of a large amount of solvents, and the reaction time is long, which leads to the disadvantages of high energy consumption, low production efficiency and pollution to the environment. With the increasing awareness of global environmental protection, the development of green chemical reactions and processes has become a major trend in the development of the modern chemical industry. Therefore, it is urgent to provide an environmentally friendly and efficient method for preparing silane coupling agents.
  • the inventors of the present invention have conducted extensive and in-depth research on silane coupling agents in order to find a new type of oxetane silane coupling agent.
  • the inventors found that the thioether-based oxetanylsilane coupling agent of the present invention will be fixed in the system after photocuring, with little or no dissociation, and it also has the advantages of good tensile properties and strong adhesion.
  • an object of the present invention is to provide a thioether-based oxetane silane coupling agent.
  • the thioether-based oxetane silane coupling agent will be fixed in the system after photocuring, with little or no dissociation, and it also has the advantages of good tensile performance and strong adhesion.
  • Another object of the present invention is to provide a method for preparing a thioether-based oxetane silane coupling agent.
  • the preparation method is simple, environmentally friendly, efficient, solvent-free, and high in yield.
  • Another object of the present invention is to provide a photocurable composition comprising the thioether-based oxetane silane coupling agent according to the present invention.
  • Another object of the present invention is to provide a photocurable material obtained from the photocurable composition of the present invention.
  • Another object of the present invention is to provide the use of the compound of formula (I) of the present invention in photocurable coatings, adhesives, inks and photoresists.
  • R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 6 alkyl or C 1 -C 6 alkoxy, and at least two of R 1 , R 2 , R 3 are C 1 -C 6 alkoxy;
  • R 4 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;
  • L is a direct bond or a divalent linking group with 1-20 carbon atoms
  • L 2 is a direct bond or a divalent linking group having 1-30 carbon atoms.
  • R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 3 alkyl or C 1 -C 3 alkoxy, and at least two of R 1 , R 2 , R 3 are C 1 - C 3 alkoxy.
  • R 4 is H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkane Oxygen or C 1 -C 4 haloalkoxy.
  • L 1 is a direct bond, C 1 -C 20 alkylene, C 1 -C 20 alkyleneoxy, one or more independently selected from C 2 -C 20 alkylene separated by non-adjacent heteroatoms of NR a , O, S, or C 2 - C 20 alkyleneoxy, wherein R a is H or C 1 -C 4 alkyl;
  • L 2 is a direct bond, C 1 -C 30 alkylene, C 1 -C 30 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 30 alkylene, or C 2 -C 30 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 15 alkylene and L 22 is a direct bond or C 1 -C 15 alkylene.
  • R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 6 alkyl or C 1 -C 6 alkoxy, and at least two of R 1 , R 2 , R 3 are C 1 -C 6 alkoxy;
  • R 4 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;
  • L 1 is a direct bond, C 1 -C 11 alkylene, C 1 -C 11 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 11 alkylene, or C 2 -C 11 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; and
  • L 2 is a direct bond, C 1 -C 8 alkylene, C 1 -C 8 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 8 alkylene, or C 2 -C 8 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 5 alkylene and L 22 is a direct bond or C 1 -C 3 alkylene;
  • R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 6 alkyl or C 1 -C 6 alkoxy, and at least two of R 1 , R 2 , R 3 are C 1 -C 6 alkoxy;
  • R 4 is H or C 1 -C 4 alkyl
  • L 1 is a direct bond, C 1 -C 6 alkylene, C 1 -C 6 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 6 alkylene, or C 2 -C 6 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; and
  • L 2 is a direct bond, C 1 -C 6 alkylene, C 1 -C 6 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 6 alkylene, or C 2 -C 6 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 4 alkylene and L 22 is a direct bond or C 1 -C 2 alkylene.
  • R and L are as defined for any one of items 1-6 ;
  • L 1 , R 1 , R 2 and R 3 are as defined for any one of items 1-6.
  • L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 15 alkylene and L 22 is a direct bond or C 1 -C 15 alkylene, preferably L 21 is C 1 -C 5 alkylene and L 22 is a direct bond or C 1 -C 3 alkylene.
  • L 21 is C 1 -C 15 alkylene, preferably C 1 -C 5 alkylene
  • X is halogen, such as fluorine, chlorine, bromine or iodine
  • L 22 is a direct bond or a C 1 -C 15 alkylene group, preferably a direct bond or a C 1 -C 3 alkylene group, and R 4 is as defined for item 7.
  • reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a basic catalyst, preferably sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, More preferably, the molar ratio of the compound of formula (II) to the basic catalyst is 1:1-1:3;
  • reaction between the compound of formula (II) and the compound of formula (III) is carried out at 80-120°C, preferably at 100-120°C;
  • reaction between the compound of formula (II) and the compound of formula (III) is carried out for 6-15 hours, preferably 8-12 hours.
  • reaction of the compound of formula (IV) and the compound of formula (V) is under the mercury lamp of 50-500mw/cm -2 in light intensity;
  • the molar ratio of the compound of formula (IV) to the compound of formula (V) is 1:0.7-1:1.5;
  • reaction between the compound of formula (IV) and the compound of formula (V) is carried out at 0-40°C, preferably at 10-30°C;
  • reaction between the compound of formula (IV) and the compound of formula (V) is carried out for 5-60 minutes, preferably 20-40 minutes.
  • a photocurable composition comprising a compound of formula (I) according to any one of items 1-6 as a polymerizable monomer.
  • FIG. 1 is a graph showing the conversion of E4221 in a system containing compound 1 prepared in Example 1 as a function of irradiation time.
  • FIG. 2 is a curve diagram of the conversion rate of Compound 1 in the system containing Compound 1 prepared in Example 1 as a function of irradiation time.
  • Fig. 3 is a graph showing the mechanical properties of a blank E4221 cured film and a cured film containing different amounts of compound 1 prepared in Example 1.
  • a numerical range is used to indicate a range in which the numerical values described before and after are taken as the minimum value and the maximum value, respectively.
  • R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 6 alkyl or C 1 -C 6 alkoxy, and at least two of R 1 , R 2 , R 3 are C 1 -C 6 alkoxy;
  • R 4 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;
  • L is a direct bond or a divalent linking group with 1-20 carbon atoms
  • L 2 is a direct bond or a divalent linking group having 1-30 carbon atoms.
  • the raw materials for preparing the compound of formula (I) of the present invention are easy to obtain, and can be prepared by a green, simple, solvent-free and heating-free reaction, and the compound of formula (I) of the present invention will be fixed in the system after photocuring, and will not dissociate , does not pollute the environment, and has the advantages of good tensile properties and strong adhesion.
  • the prefix "C n -C m " indicates in each case that the number of carbon atoms contained in the group is nm.
  • Halogen refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferred that the halogen includes bromine, chlorine or a combination thereof.
  • C n -C m alkyl refers to a branched or unbranched saturated hydrocarbon group having nm, such as 1-12, preferably 1-6, particularly preferably 1-4 carbon atoms, such as Methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methyl Butyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2- Dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethyl Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,
  • the C 1 -C 6 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl and isomers thereof.
  • C 1 -C 4 Alkyl can be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl groups and their isomers.
  • C n -C m alkoxy refers to a C n -C m alkyl corresponding to any carbon atom of an open chain C n -C m alkane bonded with an oxygen atom as a linking group C n -C m alkyl, such as C 1 -C 12 alkoxy, more preferably C 1 -C 6 alkoxy, especially preferably C 1 -C 4 alkoxy.
  • C 1 -C 6 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentyloxy, isopentyloxy group, hexyloxy group and its isomers.
  • C 1 -C 4 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and its isomers body.
  • C n -C m haloalkyl refers to C n -C m alkyl substituted by one or more same or different halogen atoms, such as C 1 -C 12 haloalkyl, preferably C 1 -C 6 Haloalkyl, particularly preferably C 1 -C 4 haloalkyl.
  • Cn- Cm haloalkyl groups mention may be made of monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, 1-chloromethylethyl, monochlorobutyl Base, 1-chloromethylpropyl, 2-chloromethylpropyl, 1,1-dichloromethylethyl, 1-chloropentyl, 1-chloromethylbutyl, 2-chloromethylbutyl, 3-chloromethylbutyl, 2,2-dichloromethylpropyl, 1-chloroethylpropyl, monochlorohexyl, 1,1-dichloromethylpropyl, 1,2-dichloromethyl Propyl, 1-chloromethylpentyl, 2-chloromethylpentyl, 3-chloromethylpentyl, 4-chloromethylpentyl, 1,1-dichloromethylbutyl, 1,
  • C n -C m haloalkoxy refers to C n -C m alkoxy substituted by one or more same or different halogen atoms, such as C 1 -C 12 haloalkoxy, more preferably C 1 -C 6 haloalkoxy, especially preferably C 1 -C 4 haloalkoxy.
  • C n -C m haloalkoxy mention may be made of monochloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 2-chloroisopropoxy, 4-chloro-n-butoxy , 3-chloro-sec-butoxy, 2-chloro-tert-butoxy, 5-chloropentyloxy, 4-chloroisoamyloxy, 6-chlorohexyloxy and its isomers.
  • C n -C m hydroxyalkyl refers to a C n -C m that has a hydroxyl group bonded to any carbon atom of an open chain C n -C m alkane corresponding to a C n -C m alkyl group.
  • Alkyl such as C 1 -C 6 hydroxyalkyl, especially preferably C 1 -C 4 hydroxyalkyl, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, hydroxybutyl, hydroxypentyl, Hydroxyhexyl and its isomers.
  • C 1 -C 30 alkylene as used herein includes C 1 -C 26 alkylene, C 1 -C 18 alkylene, C 1 -C 12 alkylene, C 1 -C 6 alkylene, C 2 -C 26 alkylene, C 2 -C 18 alkylene, C 2 -C 12 alkylene, C 2 -C 6 alkylene, C 3 -C 26 alkylene, C 3 -C 18 alkylene Alkyl, C 3 -C 12 alkylene or C 3 -C 6 alkylene.
  • C 1 -C 30 alkyleneoxy as used herein includes C 1 -C 26 alkyleneoxy, C 1 -C 18 alkyleneoxy, C 1 -C 12 alkyleneoxy, C 1 -C 6 alkylene Alkoxy, C 2 -C 26 Alkyleneoxy, C 2 -C 18 Alkyleneoxy, C 2 -C 12 Alkyleneoxy, C 2 -C 6 Alkyleneoxy, C 3 -C 26 Alkylene Alkoxy, C 3 -C 18 alkyleneoxy, C 3 -C 12 alkyleneoxy or C 3 -C 6 alkyleneoxy.
  • R 1 , R 2 , and R 3 are the same or different, and are independently C 1 -C 6 alkyl, C 1 -C 6 alkoxy, and among R 1 , R 2 , and R 3 at least Two, preferably all, are C 1 -C 6 alkoxy.
  • R 1 , R 2 , and R 3 are the same or different, and are independently C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and at least two of R 1 , R 2 , and R 3 , preferably all C 1 -C 4 alkoxy groups.
  • R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 3 alkoxy, and at least two, preferably all, of R 1 , R 2 , and R 3 are C 1 -C 3 alkoxy base.
  • R 1 , R 2 , and R 3 are the same or different, and are independently methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy, isopropoxy, and At least two, preferably all, of R 1 , R 2 and R 3 are independently methoxy, ethoxy, n-propoxy or isopropoxy.
  • R 4 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 4 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 4 is H or C 1 -C 4 alkyl.
  • R4 can be H, chloro, bromo, methyl, ethyl, n - propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy , isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxy-sec-butyl or hydroxy tert-butyl.
  • L is a direct bond or a divalent linking group with 1-20 carbon atoms, for example with 1-16, 1-11, 1-8, 1-6, 1-4 or 1- 3, or a divalent linking group of 2-16, 2-11, 2-8, 2-6 or 2-4 carbon atoms.
  • L 1 is a direct bond, C 1 -C 20 alkylene, C 1 -C 20 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 20 alkylene group spaced by heteroatoms, or a C 2 -C 20 alkylene group spaced by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
  • non-adjacent heteroatom means that there is a non-adjacent heteroatom between two carbon atoms, for example, two carbon atoms of the divalent linking group.
  • an ethylene group interrupted by O can be represented as: -CH2 - O-CH2-.
  • L 1 is a direct bond, C 1 -C 11 alkylene, C 1 -C 11 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 11 alkylene group interrupted by heteroatoms, or a C 2 -C 11 alkyleneoxy group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
  • L 1 is a direct bond, C 1 -C 6 alkylene, C 1 -C 6 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 6 alkylene group interrupted by heteroatoms, or a C 2 -C 6 alkyleneoxy group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
  • L is a direct bond or a divalent linking group with 1-30 carbon atoms, for example with 1-20, 1-16, 1-11, 1-8, 1-6, 1- 4 or 1-3, or 2-20, 2-16, 2-11, 2-8, 2-6 or 2-4 divalent linking groups of carbon atoms.
  • L 2 is a direct bond, C 1 -C 30 alkylene, C 1 -C 30 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 30 alkylene group separated by heteroatoms, or a C 2 -C 30 alkylene group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 15 alkylene (eg C 1 -C 10 alkylene) and L 22 is a direct bond Or C 1 -C 15 alkylene (eg C 1 -C 10 alkylene).
  • L 2 is a direct bond, -O-, C 1 -C 8 alkylene, C 1 -C 8 alkyleneoxy, one or more independently selected from NR a , O, S C 2 -C 8 alkylene separated by non-adjacent heteroatoms, or C 2 -C 8 alkyleneoxy separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S , wherein R a is H or C 1 -C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 5 alkylene and L 22 is a direct bond or C 1 -C 3 alkylene alkyl.
  • L 2 is a direct bond, C 1 -C 6 alkylene, C 1 -C 6 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 6 alkylene group interrupted by heteroatoms, or a C 2 -C 6 alkyleneoxy group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 4 alkylene and L 22 is a direct bond or C 1 -C 2 alkylene.
  • each variable in the compound of formula (I) has the following definitions:
  • R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 6 alkyl or C 1 -C 6 alkoxy, and at least two of R 1 , R 2 , R 3 are C 1 -C 6 alkoxy;
  • R 4 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;
  • L 1 is a direct bond, C 1 -C 11 alkylene, C 1 -C 11 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 11 alkylene, or C 2 -C 11 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; and
  • L 2 is a direct bond, -O-, C 1 -C 8 alkylene, C 1 -C 8 alkyleneoxy, replaced by one or more non-adjacent heteroatoms independently selected from NR a , O, S Interrupted C 2 -C 8 alkylene, or C 2 -C 8 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 5 alkylene and L 22 is a direct bond or C 1 -C 3 alkylene;
  • each variable in the compound of formula (I) has the following definitions:
  • R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 6 alkyl or C 1 -C 6 alkoxy, and at least two of R 1 , R 2 , R 3 are C 1 -C 6 alkoxy;
  • R 4 is H or C 1 -C 4 alkyl
  • L 1 is a direct bond, C 1 -C 6 alkylene, C 1 -C 6 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 6 alkylene, or C 2 -C 6 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; and
  • L 2 is a direct bond, C 1 -C 6 alkylene, C 1 -C 6 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 6 alkylene, or C 2 -C 6 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 4 alkylene and L 22 is a direct bond or C 1 -C 2 alkylene.
  • each variable in the compound of formula (I) has the following definitions:
  • R 1 , R 2 , and R 3 are the same or different, and are independently C 1 -C 6 alkyl or C 1 -C 6 alkoxy, and at least two, preferably all, of R 1 , R 2 , and R 3 is C 1 -C 6 alkoxy;
  • R 4 is H or C 1 -C 4 alkyl
  • L 1 is a direct bond, C 1 -C 6 alkylene or C 1 -C 6 alkyleneoxy
  • L 2 is a direct bond, C 1 -C 6 alkylene, C 1 -C 6 alkyleneoxy, C 2 -C 6 alkylene interrupted by one or more non-adjacent oxygen atoms, or separated by one or C 2 -C 6 alkyleneoxy group separated by multiple non-adjacent oxygen atoms; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 4 alkylene and L 22 is a direct bond or C 1 -C 2 alkylene.
  • the compound of formula (I) is one or more compounds selected from the group consisting of:
  • R 4 and L 2 are as defined above for the compound of formula (I);
  • L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 15 alkylene and L 22 is a direct bond or C 1 -C 15 alkylene, preferably L 21 is C 1 -C 5 alkylene and L 22 are direct bonds or C 1 -C 3 alkylene.
  • the compound of formula (IV) is prepared as follows:
  • L 21 is C 1 -C 15 alkylene, preferably C 1 -C 5 alkylene
  • X is halogen, such as fluorine, chlorine, bromine or iodine
  • L 22 is a direct bond or a C 1 -C 15 alkylene group, preferably a direct bond or a C 1 -C 3 alkylene group, and R 4 is as defined above for the compound of formula (I).
  • the reaction of the terminal hydroxyl group in the compound of formula (III) with the halogen in the compound of formula (II) belongs to the type of reaction known in the art, and the reaction produces hydrogen halide.
  • the reaction is carried out in the presence of a catalyst.
  • suitable catalysts for this reaction mention may be made of basic catalysts such as sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof.
  • the amount of catalyst used is also conventional.
  • the molar ratio of the compound of formula (III) to the catalyst is 1:1-1:5, preferably 1:1-1:3.
  • the reaction of the compound of formula (III) with the compound of formula (II) is usually carried out in a solvent.
  • a solvent there is no special limitation, as long as the compound of formula (III), compound of formula (II) and corresponding catalyst can be dissolved and the reaction between the compound of formula (III) and compound of formula (II) can not be participated in, preferably
  • the solvent also facilitates the precipitation of the product, the compound of formula (IV).
  • an organic solvent is usually used, preferably toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile or any mixture thereof.
  • the amount of solvent used is also conventional, generally speaking, the amount of solvent used is 1.0-3 times the total weight of the compound of formula (III) and compound of formula (II).
  • the compound of formula (III) and the compound of formula (II) are usually used in approximately equimolar amounts.
  • the molar ratio of the compound of formula (III) to the compound of formula (II) is 1:0.7-1:1.5 or 1:1-1:1.5, or 1:1-1:1.2.
  • the compound of formula (II) and compound of formula (III) and the catalyst are usually dissolved in a solvent, and then react at 50-150°C, preferably at 60-130°C for 8-24 hours, preferably react 9-15 Hour.
  • the reaction is advantageously carried out with stirring.
  • the compound of formula (IV) can be obtained through conventional post-treatment.
  • the post-treatment usually includes extraction or washing (such as washing with water, after which water-absorbing compounds such as magnesium sulfate or sodium sulfate are advantageously used to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove solvents, and vacuum distillation to further remove solvents. If a higher purity product is to be obtained, impurities can also be separated by recrystallization or column chromatography.
  • the mercapto group in the compound of formula (V) and the unsaturated carbon-carbon double bond in the compound of formula (IV) undergo Click reaction.
  • the reaction is performed under irradiation with a mercury lamp.
  • the reaction of the compound of formula (IV) with the compound of formula (V) can usually be carried out without solvent. This reaction can be done without a catalyst.
  • the amount of the compound of formula (IV) and the compound of formula (V) is usually used in an approximately equimolar amount, for example, the molar ratio of the compound of formula (IV) to the compound of formula (V) can be 1:0.7-1:5 or 1:1- 1:5, preferably 1:1-1:3.
  • the compound of formula (IV) and compound of formula (V) are usually mixed uniformly first, and then the mixture is exposed under a mercury lamp for a period of time to obtain the compound of formula (I).
  • the intensity of the mercury lamp used for exposure is typically 50-500 mW/cm 2 . Exposure times are typically 10-60 minutes.
  • the wavelength of the mercury lamp is usually 365nm.
  • the reaction temperature between the compound of formula (IV) and the compound of formula (V) is usually 0-40°C, preferably 10-30°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 10-60 minutes, preferably 20-40 minutes. Of course, the reaction is advantageously carried out with stirring. After the reaction is completed, the product of the compound of formula (I) can be obtained through conventional post-treatment.
  • the compound of formula (I) of the present invention is a cationic light-curable silane coupling agent, which can also be fixed in the system after cationic light-curing, with little or no freeing, and has good tensile properties and strong adhesion Etc.
  • a photocurable composition comprising the compound of formula (I) of the present invention as a coupling agent.
  • the photocurable composition may also include a cationic photoinitiator for ring-opening polymerization (a photoinitiator capable of initiating cationic polymerization) and optionally other photoinitiators containing cationic photocurable groups.
  • a cationic photoinitiator for ring-opening polymerization a photoinitiator capable of initiating cationic polymerization
  • optionally other photoinitiators containing cationic photocurable groups include cationic photoinitiator for ring-opening polymerization (a photoinitiator capable of initiating cationic polymerization) and optionally other photoinitiators containing cationic photocurable groups.
  • Groups such as vinyl ether double bonds, alicyclic epoxy, oxiranyl or oxetanyl monomers, oligomers, such as 3,4-epoxycyclohe
  • the amount of the compound of formula (I) of the present invention may be at least 0.5 mol%, at least 1 mol%, at least 2 mol%, for example 0.5-12 mol%, based on the total amount of polymerized monomers, Or 0.5-10mol%, or 1-10mol%.
  • the photocurable composition of the present invention may be a photocurable coating composition, a photocurable ink composition, a photoresist composition, and the like. After the composition is cured, the obtained cured product has good tensile properties and strong adhesion.
  • iodonium salts and sulfonium salts are commonly used.
  • the iodonium salt photoinitiator and the sulfonium salt photoinitiator have the following general formulas (A) and (B) respectively
  • R a , R b , R c , R d , R e are each independently unsubstituted C 6 -C 10 aryl, or are selected from halogen, nitro, carbonyl, C 1 -C 12 alkyl, C 1 C 6 -C 10 aryl substituted by substituents of -C 12 alkoxy, phenylthio, phenyl and substituted phenyl, preferably phenyl or naphthyl, or selected from halogen, nitro, C 1 - C 6 alkyl and substituted phenyl or naphthyl substituted by substituents of phenyl, wherein the substituted phenyl contains one or more substituents selected from halogen, nitro, C 1 -C 6 alkyl and C 1 -C 6 alkoxy radicals; and
  • Y and Z are non-nucleophilic anions, such as trifluoromethanesulfonate, BF 4 - , ClO 4 - , PF 6 - , AsF 6 - , SbF 6 - .
  • a photoinitiator one or more selected from the group consisting of 4-(phenylthio)phenyl diphenylsulfonium hexafluorophosphate, 4-(phenylthio)phenyl ⁇ Diphenylsulfonium hexafluoroantimonate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexafluorophosphate Fluoroantimonate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone Keto-10-sulfonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate
  • the photocurable composition of the present invention may also contain a sensitizer.
  • a sensitizer mention may be made, for example, of 2-isopropylthioxanthone.
  • the amount of photoinitiator used is conventional. Based on the total molar amount of polymerized monomers in the photocurable composition of the present invention, the content of the photoinitiator is generally 0.5-5 mol%, preferably 1-3 mol%.
  • a photocurable material obtained from the photocurable composition of the present invention is obtained by photocuring the photocurable composition of the invention.
  • the light-curing material has the advantages of good tensile performance and strong adhesion.
  • the compounds of formula (I) according to the invention can also be used in photocurable coatings, adhesives, inks and photoresists. Accordingly, the present invention also relates to the use of compounds of formula (I) in photocurable coatings, adhesives, inks and photoresists.
  • the purpose of this example is to illustrate the photopolymerizable properties of the compounds of the present invention.
  • a mixture of photoinitiator diphenyliodonium hexafluorophosphate (810) and 2-isopropylthioxanthone (ITX, sensitizer) in a molar ratio of 2:1 was used as the photoinitiation system, and real-time infrared
  • the method of (RT-IR) tested the photopolymerization kinetics of compound 1, and investigated the influence of different contents on the photopolymerization performance of E4221.
  • the vibrational absorption peak of the COC of the three-membered oxygen heterocycle of the monomer E4221 used is located at 750 cm -1
  • the vibration absorption peak of the COC of the four-membered oxygen heterocycle of compound 1 as a polymerized monomer is 980 cm - 1 .
  • the photocurable liquid composed of the initiator is evenly spread on the potassium bromide salt sheet (use a narrow tube to dip a little photocurable liquid on the potassium bromide salt sheet, and then spread it evenly), and irradiate the liquid sample with a high-pressure mercury lamp 900s, in which the main emission wavelength of the mercury lamp is 365nm, and it has an optical fiber with a diameter of 5mm.
  • the distance between one end of the optical fiber and the test sample is 10 cm, and the radiation intensity is 20 mW cm -2 .
  • the purpose of this example is to illustrate that the compounds of the present invention can improve the tensile properties of photocured films.
  • the films were cured and tested for tensile properties.
  • the tensile properties are based on the international standard ISO 1184-1983 "Determination of tensile properties of plastic films", and passed the E44.304 electronic universal testing machine test. Test conditions: temperature 25°C, humidity 60%, test speed 1mm ⁇ min -1 . At the same time, use the same method to prepare a blank E4221 cured film as a reference. The results are shown in Figure 3 and Table 2.
  • the purpose of this example is to illustrate that the compounds of the present invention can improve the adhesion of photocured films.
  • Coat the photosensitive liquid on a 25mm ⁇ 25mm substrate (see Table 3), and after curing under a mercury lamp, cut the coating into a square of 10 ⁇ 10 with 100 grids, stick the adhesive tape on the cut-out area and tear it off Adhesive tape, detect the peeling off of the coating at the cross-cut.
  • Adhesion is divided into 6 grades according to the shedding of the coating at the position of the hundred grids. No shedding is 0, and the shedding ratio is within 5%, 5-15%, 15-35%, 35-65%, and 65% or more, respectively. Divided into 1 to 5 grades.
  • the compounds of the present invention can improve the adhesion of photocured films.

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Abstract

La présente invention concerne un agent de couplage de thioéther oxétane silane, son procédé de préparation, une composition photodurcissable le comprenant, et un matériau photodurcissable obtenu à partir de la composition photodurcissable. L'agent de couplage de thioéther oxétane selon la présente invention peut être fixé dans un système après photodurcissement, et est moins libre ou même pas libre, et l'agent de couplage au silane présente en outre les avantages d'une bonne propriété de traction, d'une forte adhérence, etc.
PCT/CN2022/099402 2021-06-21 2022-06-17 Agent de couplage de thioéther oxétane silane et son procédé de préparation WO2022267991A1 (fr)

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