WO2020253839A1 - Monomère d'oxétane contenant du polysilicium photodurcissable pouvant être mélangé ainsi que sa préparation et son application - Google Patents

Monomère d'oxétane contenant du polysilicium photodurcissable pouvant être mélangé ainsi que sa préparation et son application Download PDF

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WO2020253839A1
WO2020253839A1 PCT/CN2020/097175 CN2020097175W WO2020253839A1 WO 2020253839 A1 WO2020253839 A1 WO 2020253839A1 CN 2020097175 W CN2020097175 W CN 2020097175W WO 2020253839 A1 WO2020253839 A1 WO 2020253839A1
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compound
formula
alkyl
integer
reaction
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孙芳
马浩钦
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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment

Definitions

  • the technical field of the present invention is the field of light-curable materials, and specifically relates to a polysilicon-containing oxetane monomer that can be mixed with light-curable.
  • 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 free radical light curing system has the advantages of fast curing speed and easy adjustment of performance, but also has the problems of serious shrinkage, low precision, and poor adhesion.
  • the development of cationic curing system is relatively late. It has the advantages of small volume shrinkage, strong adhesion, wear resistance, high hardness, etc. It is especially suitable for laser rapid prototyping technology (stereolithography) that requires high precision and optical discs that require strong adhesion and wear resistance. It also has the disadvantages of slow curing speed, few types of oligomers and reactive diluents, high price, and difficult adjustment of cured product performance, which limits its practical application.
  • Oxycycloalkane monomers belong to cationic light curing system monomers. 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. However, while UV curing has developed rapidly with the advantages of energy saving, environmental protection and high efficiency, people have proposed higher standards for the heat resistance, water repellency, surface stain resistance, corrosion resistance and fingerprint resistance of photocurable materials. Claim. Consumers are increasingly demanding the appearance of products.
  • the surface is also required to have anti-fingerprint and stain-resistant performance, that is, it is not easy to leave fingerprints and other traces on the surface of the product during use, or it is easy to leave traces Be wiped clean.
  • photocurable monomers that can meet the aforementioned requirements, have fast curing speed and easily adjustable performance, and there is no such photocurable monomer on the market, so development is urgently needed.
  • the inventors of the present invention have conducted extensive and in-depth research on oxetane cationic photopolymerizable monomers in order to discover a new type of photocurable monomers.
  • the body After curing, the body not only has the advantages of good tensile properties, excellent hydrophobic properties, anti-staining, anti-fingerprint, anti-chemical corrosion, and strong anti-aging properties, but also has fast curing speed and easy adjustment of performance.
  • the present inventors discovered that the hybrid light-curable monomer compound obtained by combining the organosiloxane with the oxetane moiety and the acrylate group has the aforementioned advantages.
  • one object of the present invention is to provide a hybrid photocurable polysilicon-containing oxetane monomer, which not only contains cationic photocurable oxetane groups, but also contains polysilicon Siloxane chain and free radical light-curable acrylate group.
  • the monomer with such a structure not only has good tensile properties after light curing, excellent hydrophobic properties, anti-staining, anti-fingerprint, anti-chemical corrosion, strong anti-aging properties, good heat resistance, but also has fast curing speed and easy adjustment of performance. This broadens the application range of the light curing system.
  • Another object of the present invention is to provide a method for preparing the hybrid light-curable polysilicon-containing oxetane monomer of the present invention.
  • the preparation process is simple and feasible, the conditions are mild, the raw materials are readily available, and the price is low.
  • Another object of the present invention is to provide a photocurable composition comprising the hybrid photocurable 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 1-10;
  • z is an integer of 0-10;
  • p is an integer of 1-6;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy or A C 1 -C 12 alkyl group with one or more heteroatoms independently selected from N, O and S inserted between two carbon atoms;
  • 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; as well as
  • R 9 is H or C 1 -C 12 alkyl.
  • n is an integer of 1-15, preferably an integer of 1-12;
  • n is an integer of 1-6, preferably an integer of 2-4;
  • z is an integer of 1-6, preferably an integer of 0-3;
  • p is an integer of 1-4, preferably an integer of 1-3;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or A C 1 -C 6 alkyl group with one or more heteroatoms selected from NR b , O, and S inserted between two carbon atoms, wherein R b is H or C 1 -C 4 alkyl, preferably R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are the same or different and are independently a phenyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or one interposed between two carbon atoms Or more C 1 -C 4 alkyl groups independently selected from heteroatoms of NR b , O, and S, wherein R b is H or C 1 -C 4 alkyl; and/or
  • R 8 is H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy, Preferably H or C 1 -C 4 alkyl; and/or
  • R 9 is H or C 1 -C 6 alkyl, preferably H or C 1 -C 4 alkyl.
  • n is an integer from 1-12;
  • n 2, 3 or 4;
  • z 0, 1, 2 or 3;
  • p 1, 2 or 3;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 1 -C 4 alkyl groups; and/or
  • R 8 is H or C 1 -C 4 alkyl
  • R 9 is H or C 1 -C 4 alkyl, especially H or methyl.
  • n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined in any one of items 1-4,
  • p and R 8 are as defined in any one of items 1 to 4, and X is halogen, such as fluorine, chlorine, bromine or iodine,
  • n, m, z, p, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are defined in any one of items 1-4;
  • R 9 is as defined in any one of items 1-4, and Y is halogen, such as fluorine, chlorine, bromine or iodine.
  • the reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a basic catalyst.
  • the basic catalyst is preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably ,
  • the molar ratio of the compound of formula (II) to the basic catalyst is 1:1-1:5; 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
  • the reaction between the compound of formula (II) and the compound of formula (III) is first carried out at the freezing temperature, and then the temperature is increased to 25-60°C, preferably to 35-60°C; preferably, the reaction at the freezing temperature proceeds to 0.5 -3 hours, preferably 0.5-1 hour; and/or, continue the reaction for 6-24 hours after raising the temperature, preferably 8-24 hours.
  • the reaction between the compound of formula (IV) and the compound of formula (V) is carried out in the presence of a basic catalyst.
  • the basic catalyst is preferably triethylamine, potassium carbonate or any mixture thereof, and more preferably, the compound of formula (IV) and the catalyst
  • the molar ratio of is 1:1-1:3 (the example does not use a basic catalyst); and/or
  • the molar ratio of the compound of formula (IV) to the compound of formula (IV) is 1:1-1:1.2; and/or
  • the reaction between the compound of formula (IV) and the compound of formula (IV) is first carried out at freezing temperature, and then the temperature is raised to 25-60°C, preferably to 25-35°C; preferably, the reaction at the freezing point temperature is carried out 0.5 -3 hours, preferably 0.5-1 hour; and/or continue the reaction for 6-24 hours, preferably 8-12 hours after raising the temperature.
  • 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 change of double bond conversion rate of compound 1 prepared in Example 1 with irradiation time.
  • Example 2 is a graph showing the change of the oxetane ring conversion rate of Compound 1 prepared in Example 1 with the irradiation time.
  • n is an integer from 1-50;
  • n is an integer of 1-10;
  • z is an integer of 0-10;
  • p is an integer of 1-6;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 6 -C 10 aryl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy or A C 1 -C 12 alkyl group with one or more heteroatoms independently selected from N, O and S inserted between two carbon atoms;
  • 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; as well as
  • R 9 is H or C 1 -C 12 alkyl.
  • the compound of formula (I) contains both a cationic photocurable oxetane structure, a radical photocurable acrylate structure part, and a polysiloxane structure part.
  • the compound with such a structure has the advantages of both cationic curing and free radical curing. It not only has fast curing speed and easy adjustment of performance, but also has the advantages of small volume shrinkage, strong adhesion, wear resistance and high hardness. In addition, it has tensile properties after light curing. Good, excellent hydrophobic performance, stain resistance, fingerprint resistance, chemical corrosion resistance, strong anti-aging performance, 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 group refers to a monovalent branched or unbranched saturated hydrocarbon group having nm, for example 1-12, preferably 1-6, particularly preferably 1-4 carbon atoms .
  • C n -C m alkyl groups mention may be made of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1 -Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,
  • C 6 -C m aryl group refers to a monocyclic, bicyclic or multicyclic aromatic hydrocarbon group containing 6 to m carbon atoms, for example, 6 to 10 carbon atoms.
  • C 6 -C m aryl groups mention may be made of phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methyl ethyl phenyl, diethyl phenyl, Methyl ⁇ propylphenyl, naphthyl, etc.; preferably phenyl or naphthyl, especially phenyl.
  • C n -C m alkoxy refers to a C n -C m alkyl group corresponding to any carbon atom of the open chain C n -C m alkane bonded with an oxygen atom as a linking group C n -C m alkyl, for example C 1 -C 12 alkoxy, more preferably C 1 -C 6 alkoxy, especially preferably C 1 -C 4 alkoxy.
  • C n -C m alkoxy groups mention may be made of methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy Group, isopentyloxy, hexyloxy and its isomers.
  • C n -C m haloalkyl refers to a C n -C m alkyl group substituted with one or more identical or different halogen atoms, such as C 1 -C 12 haloalkyl, preferably C 1 -C 6 haloalkyl, C 1 -C 4 haloalkyl is particularly preferred.
  • haloalkyl groups here, mention may be made of monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, 1-chloromethylethyl, monochlorobutyl, 1 -Chloromethylpropyl, 2-chloromethylpropyl, 1,1-dichloromethylethyl, monochloropentyl, 1-chloromethylbutyl, 2-chloromethylbutyl, 3-chloro Methylbutyl, 2,2-dichloromethylpropyl, 1-chloroethylpropyl, monochlorohexyl, 1,1-dichloromethylpropyl, 1,2-dichloromethylpropyl, 1-chloromethylpentyl, 2-chloromethylpentyl, 3-chloromethylpentyl, 4-chloromethylpentyl, 1,1-dichloromethylbutyl, 1,
  • C n -C m haloalkoxy refers to a C n -C m alkoxy group substituted by one or more identical or different halogen atoms, such as C 1 -C 12 haloalkoxy, more preferably C 1 -C 6 haloalkoxy, especially C 1 -C 4 haloalkoxy.
  • C n -C m halogenated alkoxy groups mention may be made of monochloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 2-chloroisopropoxy, 4-chloro-n-butoxy , 3-chloro-sec-butoxy, 2-chloro-tert-butoxy, 5-chloropentyloxy, 4-chloroisopentyloxy, 6-chlorohexyloxy and its isomers.
  • hydroxyalkyl C n -C m alkyl means any carbon atom in the C n -C m alkyl corresponding open-chain alkanes C n -C m hydroxyl group bonded to a C n -C m Alkyl groups, such as C 1 -C 6 hydroxyalkyl groups, particularly preferably C 1 -C 4 hydroxyalkyl groups, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, hydroxybutyl, hydroxypentyl, Hydroxyhexyl and its isomers.
  • n is usually an integer of 1-50, preferably an integer of 1-15, and particularly preferably an integer of 1-12, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
  • m is usually an integer of 1-10, preferably an integer of 1-6, particularly preferably an integer of 2-4, such as 2, 3, or 4.
  • z is usually an integer of 0-10, preferably an integer of 1-6, and particularly preferably an integer of 0-3, such as 0, 1, 2 or 3.
  • p is usually an integer of 1-6, preferably an integer of 1-4, particularly preferably an integer of 1-3, such as 1, 2, or 3.
  • 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 alkoxy or C 1 -C 12 alkyl with one or more heteroatoms independently selected from NR b , O, S inserted between two carbon atoms, wherein R b is H or C 1- C 4 alkyl.
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different and are independently C 6 -C 10 aryl, C 1 -C 6 alkyl, C 1 -C 6 An alkoxy group or a C 1 -C 6 alkyl group with one or more heteroatoms selected from NR b , O, and S inserted between two carbon atoms, wherein R b is H or a C 1 -C 4 alkyl group.
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different, and are independently phenyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or A C 1 -C 4 alkyl group with one or more heteroatoms independently selected from NR b , O, and S inserted between two carbon atoms, wherein R b is H or a C 1 -C 4 alkyl group.
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 1 -C 4 alkyl groups.
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently H, phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, S-butyl, t-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s-butoxy or t-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.
  • R 9 is usually H or C 1 -C 12 alkyl.
  • R 9 is H or C 1 -C 6 alkyl. It is particularly preferred that R 9 is H or C 1 -C 4 alkyl.
  • R 9 can be H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, especially H or methyl.
  • n is an integer of 1-12;
  • n 2, 3 or 4;
  • z 0, 1, 2 or 3;
  • p 1, 2 or 3;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different, and are independently C 1 -C 4 alkyl groups;
  • R 8 is H or C 1 -C 4 alkyl
  • R 9 is H or C 1 -C 4 alkyl, especially H or methyl.
  • the compound of formula (I) is one or more compounds selected from the following group:
  • n, m, z, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined for the compound of formula (I),
  • p and R 8 are as defined for the compound of formula (I), and X is halogen, such as fluorine, chlorine, bromine or iodine,
  • n, m, z, p, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are as defined for the compound of formula (I);
  • R 9 is as defined for the compound of formula (I), and Y is halogen, such as fluorine, chlorine, bromine or iodine.
  • step (1) the reaction between the terminal hydroxyl group in the compound of formula (II) and the halogen in the compound of formula (III) belongs to a type of reaction known in the art, and the reaction produces hydrogen halide.
  • this reaction is carried out in the presence of a basic catalyst.
  • a basic catalyst suitable for this reaction sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof can be mentioned.
  • the amount of catalyst is also conventional.
  • the molar ratio of the compound of formula (II) to the basic catalyst is 1:1 to 1:5.
  • 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 corresponding basic 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 (IV).
  • 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 1.0 to 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 1:1-1:1.2.
  • the compound of formula (II) and a basic catalyst are dissolved in a solvent, the temperature is lowered to the freezing point (about 0°C), and then the compound of formula (III) is added.
  • the resulting reaction mixture is first heated to the freezing temperature ( (Approximately 0°C) the reaction is stirred for 0.5-3 hours, preferably 0.5-1 hour, and then the temperature is increased to 25-60°C, preferably to 35-60°C. After the temperature is raised, the reaction is usually continued for 6-24 hours, preferably for 8-24 hours. Of course, the reaction is advantageously carried out under stirring. After the reaction is completed, the compound of formula (IV) can be obtained through conventional post-treatment.
  • This post-treatment usually includes extraction or washing (for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and vacuum distillation to further remove the solvent. If you want to obtain a higher purity product, you can also recrystallization or column chromatography to separate impurities.
  • extraction or washing for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water
  • filtration or centrifugation to remove solid impurities
  • rotary evaporation to remove the solvent
  • vacuum distillation to further remove the solvent.
  • step (2) the reaction between the terminal hydroxyl group in the compound of formula (IV) and the acid halide in the compound of formula (V) belongs to a type of reaction known in the art, and the reaction produces hydrogen halide.
  • the reaction is carried out in the presence of a catalyst.
  • a catalyst suitable for this reaction triethylamine, potassium carbonate or any mixture thereof can be mentioned.
  • the amount of catalyst is also conventional.
  • the molar ratio of the compound of formula (IV) to the 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 catalyst and does not participate in the reaction between the compound of formula (IV) and the compound of formula (V), preferably
  • the solvent also facilitates the precipitation of the product, that is, the compound of formula (I).
  • an organic solvent is generally used, and toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile, or any mixtures thereof are preferably used.
  • the amount of solvent is also conventional.
  • the amount of solvent is 1.0 to 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 (IV) is 1:1-1:1.2.
  • the compound of formula (IV) and the catalyst are dissolved in a solvent, the temperature is lowered to the freezing point (about 0°C), and then a solution of the compound of formula (V) in the solvent is added.
  • the resulting reaction mixture is stirred at freezing temperature (about 0°C) for 0.5-3 hours, preferably 0.5-1 hour, then the temperature is raised to 25-60°C, preferably to 25-35°C, and the reaction is continued for 6-24 hours, preferably 8-12 hours.
  • the reaction is advantageously carried out under stirring.
  • the compound of formula (I) can be obtained through conventional post-treatment.
  • This post-treatment usually includes extraction or washing (for example, washing with water, which advantageously uses water-absorbing compounds such as magnesium sulfate or sodium sulfate to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and vacuum distillation to further remove the solvent. If you want to obtain a higher purity product, you can also recrystallization or column chromatography to separate impurities.
  • the compound of formula (I) of the present invention is a polysilicon-containing oxetane monomer that can be mixed with light curing. It has a fast curing speed, good tensile properties after light curing, excellent hydrophobic properties, stain resistance, and Fingerprint, chemical corrosion resistance, strong anti-aging performance, good heat resistance.
  • the synthetic method is simple and feasible, and the conditions are mild; the raw materials are easily available and the price is low.
  • a photocurable composition comprising the compound of formula (I) of the present invention as a polymerizable monomer.
  • the photocurable composition usually contains a cationic photoinitiator for ring-opening polymerization (a photoinitiator that can initiate cationic polymerization) and a free radical photoinitiator (which can initiate free radicals). Photoinitiator for polymerization).
  • the cationic photoinitiator for ring-opening polymerization initiates the ring-opening polymerization of the oxetane structure in the compound of formula (I) under ultraviolet light irradiation, and the free radical photoinitiator initiates the formula (I) under ultraviolet light irradiation Polymerization of olefinic double bonds in compounds.
  • the photocurable composition can also contain other monomers containing vinyl ether double bonds, alicyclic epoxy groups, oxiranyl groups or oxetanyl groups and other cationic photocurable groups, low Polymers, such as 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (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
  • free radical photoinitiators there are usually 2-isopropylthioxanthone (ITX), 2-hydroxy-2-methyl-1-phenylacetone (1173), 1-hydroxycyclohexylphenyl ketone ( 184), 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone (907), 2,4,6-trimethylbenzyl Acyl-diphenylphosphine oxide (TPO), 2,4,6-trimethylbenzoylphenyl phosphonate (TPO-L), 2-dimethylamino-2-benzyl-1-[4 -(4-morpholinyl)phenyl]-1-butanone (IHT-PI 910), 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1 -Acetone (659), methyl benzoylformate (MBF), etc.
  • IHT-PI 910 2-isopropylthioxanthone
  • the amount of photoinitiator is conventional.
  • the content of the cationic photoinitiator for ring-opening polymerization is usually 0.5-5%, preferably 1-3%.
  • the content of the free radical photoinitiator is usually 0.5-3%, preferably 1-2%.
  • 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, the curing speed is fast, the performance is easy to adjust, and after curing, it has good tensile properties, excellent hydrophobic properties, stain resistance, and fingerprint resistance. , Anti-chemical corrosion, strong anti-aging performance, good heat resistance.
  • Example 1 was repeated, but 22 mmol of acryloyl chloride was replaced by 22 mmol of methacryloyl chloride.
  • the resulting final product was characterized by hydrogen nuclear magnetic spectroscopy and silicon spectroscopy and identified as compound 2, sometimes referred to as BODSi-2 hereinafter.
  • the purpose of this example is to illustrate the photopolymerization properties of the compounds of the present invention.
  • the asymmetric deformation vibration absorption peak of the COC bond of the oxetanyl group is located at 980 cm -1
  • Fig. 1 is a graph showing the change of double bond conversion rate with irradiation time
  • Fig. 2 is a graph showing the change of double bond conversion rate with irradiation time
  • each of the compounds 2-6 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 heterocyclic ring of the monomer will increase with the increase of the initiator concentration, and the maximum conversion rate of the quaternary oxygen heterocyclic ring of the monomer has reached at least 60%.
  • the maximum conversion rate of carbon double bonds reached at least 75%.
  • 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 15:85, based on E4221 and compound 1
  • the total weight of each of -6 is 3.0wt% 810 and 1.5wt% ITX as initiators, and they are mixed uniformly to obtain a photosensitive liquid.
  • OCA20 German dataphysics company
  • 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 film of compound 1-6 was 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 at a test temperature of 25°C and a test speed of 50 mm/min. At the same time, use the same method to prepare a blank E4221 cured film as a reference.
  • Instron-1211 electronic tensile machine Instron-1211, Instron, USA
  • the tensile strength of the pure E4221 light-cured film is 7.02MPa, and the elongation at break is 7.5%; and after adding 15% of compound 1, the tensile strength of the cured film of E4221 reaches 11.9MPa and the elongation at break is 15.7. %.
  • the tensile strength of the cured film obtained by additionally adding one of the compounds 2-6 all exceeded 11.0 MPa, and the elongation at break all exceeded 15.2%. Therefore, the compound of the present invention can significantly improve the tensile properties of the cured film.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Medicinal Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)

Abstract

La présente invention concerne un composé représenté par la formule (I), les variables n, m, z, p, R2, R3, R4, R5, R6, R7, R8 et R9 étant telles que définies dans la description. Le composé représenté par la formule (I) non seulement présente, après photodurcissement, de bonnes propriétés de traction, d'excellentes propriétés hydrophobes, et des propriétés anti-coloration, anti-empreintes digitales et anti-corrosion chimique, de bonnes propriétés anti-vieillissement, et une bonne résistance à la chaleur, mais il présente également une vitesse de durcissement rapide et un ajustement de performance aisé, élargissant ainsi l'éventail d'application d'un système photodurcissable. La présente invention concerne en outre la préparation du composé représenté par la formule (I), une composition photodurcissable contenant le composé représenté par la formule (I), et un matériau photodurci obtenu par photopolymérisation de la composition photodurcissable.
PCT/CN2020/097175 2019-06-21 2020-06-19 Monomère d'oxétane contenant du polysilicium photodurcissable pouvant être mélangé ainsi que sa préparation et son application WO2020253839A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
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US5463084A (en) * 1992-02-18 1995-10-31 Rensselaer Polytechnic Institute Photocurable silicone oxetanes
US5747172A (en) * 1995-08-30 1998-05-05 General Electric Company Ultraviolet and electron beam curable propenyl-ether silicone release compositions
JP2002030268A (ja) * 2000-07-14 2002-01-31 Kansai Paint Co Ltd 内装材の表面汚染防止方法
WO2004094435A2 (fr) * 2003-04-16 2004-11-04 Rensselaer Polytechnic Institute Monomeres et oligomeres de siloxane
CN101448917B (zh) * 2006-04-10 2013-04-10 新日本石油株式会社 具有改进的粘附性的液晶组合物、包含该组合物的液晶薄膜和配备有该薄膜的液晶显示器件
US20160060398A1 (en) * 2014-09-02 2016-03-03 Solip Tech Co., Ltd. Method of manufacturing cationic polymerization resin with enhanced uv stability and cationic polymerization resin manufactured by the same

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FR2805273B1 (fr) * 2000-02-18 2006-08-11 Rhodia Chimie Sa Traitement de surface de materiau plastique avec une composition a fonctions reactives polymerisable et/ou reticulable
CN107621752B (zh) * 2016-07-13 2019-11-12 常州强力先端电子材料有限公司 一种混杂型光敏树脂及其制备方法
CN106279241A (zh) * 2016-07-16 2017-01-04 北京化工大学 一种含硅氧烷结构的单官能度丙烯酸酯单体及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5463084A (en) * 1992-02-18 1995-10-31 Rensselaer Polytechnic Institute Photocurable silicone oxetanes
US5747172A (en) * 1995-08-30 1998-05-05 General Electric Company Ultraviolet and electron beam curable propenyl-ether silicone release compositions
JP2002030268A (ja) * 2000-07-14 2002-01-31 Kansai Paint Co Ltd 内装材の表面汚染防止方法
WO2004094435A2 (fr) * 2003-04-16 2004-11-04 Rensselaer Polytechnic Institute Monomeres et oligomeres de siloxane
CN101448917B (zh) * 2006-04-10 2013-04-10 新日本石油株式会社 具有改进的粘附性的液晶组合物、包含该组合物的液晶薄膜和配备有该薄膜的液晶显示器件
US20160060398A1 (en) * 2014-09-02 2016-03-03 Solip Tech Co., Ltd. Method of manufacturing cationic polymerization resin with enhanced uv stability and cationic polymerization resin manufactured by the same

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