WO2018010604A1 - 多官能度氧杂环丁烷类化合物及其制备方法 - Google Patents

多官能度氧杂环丁烷类化合物及其制备方法 Download PDF

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WO2018010604A1
WO2018010604A1 PCT/CN2017/092227 CN2017092227W WO2018010604A1 WO 2018010604 A1 WO2018010604 A1 WO 2018010604A1 CN 2017092227 W CN2017092227 W CN 2017092227W WO 2018010604 A1 WO2018010604 A1 WO 2018010604A1
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group
valent
formula
polymerizable monomer
cationically polymerizable
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PCT/CN2017/092227
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English (en)
French (fr)
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钱晓春
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常州强力先端电子材料有限公司
常州强力电子新材料股份有限公司
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Priority to EP17826940.3A priority Critical patent/EP3486238B1/en
Priority to KR1020197000419A priority patent/KR102183004B1/ko
Priority to JP2018565662A priority patent/JP6773815B2/ja
Publication of WO2018010604A1 publication Critical patent/WO2018010604A1/zh
Priority to US16/246,113 priority patent/US10906882B2/en
Priority to US17/089,931 priority patent/US11555022B2/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • 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
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • 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
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes

Definitions

  • the invention belongs to the field of organic chemistry, and particularly relates to a polyfunctional oxetane compound and a preparation method thereof.
  • the cationic photocuring system has the advantages of being unaffected by oxygen inhibition and having a small volume shrinkage.
  • the reactive diluent monomers used are mainly vinyl ether compounds, epoxy compounds and oxetane. Class of compounds.
  • the epoxy-based monomer can give a cured product having good heat resistance, adhesion, and chemical resistance, but the monomer has low reactivity.
  • the vinyl ether monomer has high polymerization activity, but its hardness, abrasion resistance, chemical resistance and the like are inferior, and it cannot be used as a protective film for a hard coating agent and various substrates.
  • oxetane monomers have high reactivity and are excellent in physical properties after curing, and thus are increasingly used in cured compositions.
  • the use of oxetane monomers in combination with epoxy monomers has become a common form of cationic photocuring systems.
  • Cipheral Patent No. CN103497691A discloses a photocurable adhesive composition for the manufacture of a polarizing plate, which is a bifunctional oxetane compound.
  • Compound a is used in combination with an epoxy compound to provide a significant improvement in the balance of adhesion and durability;
  • a bifunctional oxetane compound is disclosed in Japanese Patent No. 4003264B2 (Compound b) can significantly increase the curing speed of the cationic curing system.
  • the polyfunctionalization of oxetane monomers has attracted attention in many fields of application, such as adhesives, sealants, encapsulants, and the like, particularly those used in components and assemblies of LED devices. This is also an inevitable trend in the development of oxetane-based cationically polymerizable monomers.
  • the polyfunctional oxetane monomers reported in the existing literature still have shortcomings. The outstanding point is that the hardness, flexibility and adhesion properties of the post-cured products are difficult to be well balanced. The overall performance still needs to be further improved.
  • polyfunctional oxetane compounds having higher reactivity and superior application properties and a process for the preparation thereof.
  • These polyfunctional oxetane-based cationically polymerizable monomers are used in combination with an epoxy compound to have a high curing speed, and the cured product is excellent in hardness, flexibility, adhesion, and heat resistance.
  • the present invention first provides a polyfunctional oxetane compound having the structure represented by the general formula (I):
  • R 1 represents a C 1 -C 40 linear or branched m-valent alkyl group, a C 2 -C 20 m-valent alkenyl group, or a C 6 -C 40 m-valent aryl group, wherein -CH 2 - Optionally optionally oxygen atoms, -NH- or Substituted, provided that the two -O- are not directly linked; and optionally, one or more of the hydrogen atoms of these groups may be independently substituted with a group selected from the group consisting of an alkyl group, a halogen, and a nitro group;
  • R 2 represents a C 1 -C 20 linear or branched alkylene group, and -CH 2 - in the main chain may be optionally substituted by an oxygen atom, provided that two -O- are not directly linked, and optionally , one or more hydrogen atoms in the group may each be independently substituted with a group selected from the group consisting of an alkyl group, a halogen, and a nitro group;
  • R 3 represents hydrogen, halogen, nitro, C 1 -C 20 linear or branched alkyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 4 -C An alkylcycloalkyl group of 20 , a C 2 -C 10 alkenyl group or a C 6 -C 20 aryl group, optionally, one or more of the hydrogen atoms of these groups may be independently selected from the group consisting of an alkane Substituted by a group of a halogen, a nitro group;
  • n an integer from 1-8.
  • the compound of the above formula (I) contains two or more oxetane groups.
  • R 1 represents a C 1 -C 40 linear or branched m-valent alkyl group, a C 2 -C 10 linear or branched m-valent alkenyl group, or a C 6 -C 30 a m-valent aryl group, wherein -CH 2 - may be optionally taken up by an oxygen atom, -NH- or Substituted, provided that the two -O- are not directly linked; and optionally, one or more of the hydrogen atoms of these groups may be independently substituted with a group selected from the group consisting of an alkyl group, a halogen, and a nitro group.
  • R 1 may be selected from the following structures: a linear or branched 1-4 valent alkyl group of C 1 -C 12 , a linear or branched 1-4 valent alkenyl group of C 2 -C 6 , CH 3 -O-CH 2 CH 2 *, *CH 2 CH 2 -NH-CH 2 CH 2 *,
  • R 2 represents a C 1 -C 10 linear or branched alkylene group, and -CH 2 - in the main chain may be optionally substituted by an oxygen atom, provided that the two -O- are not directly bonded. Further preferably, R 2 represents a C 1 -C 6 straight or branched alkylene group, and -CH 2 - in the main chain may be optionally substituted by an oxygen atom, provided that two -O- are not directly linked .
  • R 3 represents hydrogen, C 1 -C 10 linear or branched alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 Alkylcycloalkyl, C 2 -C 8 alkenyl, phenyl. Further preferably, R 3 represents a C 1 -C 4 linear or branched alkyl group, or a C 4 -C 8 cycloalkylalkyl group.
  • m is preferably an integer of from 1 to 6, more preferably an integer of from 1 to 4.
  • C 1 -C 10 includes C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , "integer of 1-4" includes 1, 2, 3, 4.
  • the present invention also relates to a process for producing a polyfunctional oxetane compound represented by the above formula (I), which comprises a hydroxyl group-containing compound represented by the formula (II) and an oxygen group represented by the formula (III).
  • the heterocyclic butane alkyl epoxy compound is used as a raw material, and the product is obtained by reacting in the presence of a catalyst, and the reaction formula is as follows:
  • the catalyst used may be: an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like; an alkali metal salt of an alcohol such as sodium methoxide, potassium ethoxide, sodium t-butoxide or the like; alkali metal carbonate a salt such as sodium carbonate, potassium carbonate or the like; an alkali metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate; an alkyl metal lithium compound such as butyl lithium, phenyl lithium or the like; an amine lithium compound such as two different Lithium propylamino, lithium hexamethyldisilazide, and the like.
  • the amount of the catalyst used can be easily determined by those skilled in the art, and preferably, the amount of the catalyst is from 0.1 to 20%, more preferably from 1 to 20%, based on the mole of the compound of the formula (II).
  • the reaction system may optionally contain an organic solvent depending on the kind of the raw material.
  • the type of the solvent to be used is not particularly limited as long as it can dissolve the reaction raw material without affecting the reaction, and may be, for example, a nitrile solvent such as acetonitrile, propionitrile or benzonitrile; N,N-dimethylformamide, N,N.
  • An amide solvent such as dimethylacetamide or N-methylpyrrolidone; an ether solvent such as tetrahydrofuran or dioxane; or an aromatic solvent such as benzene, toluene or xylene.
  • These solvents may be used singly or in combination of two or more. The total amount may be appropriately adjusted depending on the homogeneity and stirring property of the reaction system, which is easily determined by those skilled in the art.
  • the reaction temperature varies depending on the kind of the raw material, and is usually 25 to 200 ° C, preferably 50 to 150 ° C.
  • the present invention provides a cationically polymerizable monomer produced by reacting a polyfunctional oxetane compound represented by the above formula (I) with epichlorohydrin, which has a structure represented by the formula (IV) :
  • R 1 , R 2 , R 3 and m have the same definitions as described in the general formula (I).
  • the method for preparing a cationically polymerizable monomer represented by the formula (IV) comprises: reacting a polyfunctional oxetane compound represented by the formula (I) with epichlorohydrin under alkaline conditions;
  • a basic compound such as an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like; an alkali metal carbonate such as sodium carbonate, potassium carbonate or the like; an alkali metal hydrogencarbonate may be added to the reaction system. Salts such as sodium hydrogencarbonate, potassium hydrogencarbonate, and the like.
  • the basic compound can facilitate the progress of the reaction, and the amount thereof can be easily determined by those skilled in the art.
  • the basic compound is used in an amount of 1 to 20 times, more preferably m-, the molar amount of the compound of the formula (I). 10 times.
  • an organic solvent may be selectively used as a carrier medium in the reaction system depending on the kind of the raw material.
  • the type of the solvent to be used is not particularly limited as long as it can dissolve the reaction raw material without affecting the reaction, and may be, for example, acetonitrile or propylene.
  • Nitrile solvent such as nitrile or benzonitrile
  • amide solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone
  • ether such as tetrahydrofuran or dioxane Solvent
  • aromatic solvent such as benzene, toluene or xylene.
  • the present invention provides a cationically polymerizable monomer obtained by reacting a compound represented by the above formula (I) with an ester compound represented by the formula (V).
  • R 4 represents an n-valent linking group
  • R 5 represents a C 1 -C 10 linear or branched alkyl group
  • n represents an integer of 1-8;
  • the condition is that the cationically polymerizable monomer has at least two oxetane groups.
  • R 4 represents a C 1 - C 20 linear or branched n-valent alkyl group, a C 2 - C 20 n-valent alkenyl group, and C 3 20 monovalent -C n cycloalkyl, n-valent C 4 -C 20 cycloalkylalkyl group, an n-valent C 4 -C 20 alkylcycloalkyl, or n-valent aryl group of C 6 -C 40;
  • -CH 2 - in these groups may be substituted by an oxygen atom or a 1,4-phenylene group, provided that two -O- are not directly bonded; optionally, one of these groups or
  • a plurality of hydrogen atoms may be independently substituted with a group selected from an alkyl group, a halogen, and a nitro group.
  • R 4 represents a C 1 -C 10 linear or branched n-valent alkyl group, a C 2 -C 10 n-valent alkenyl group, a C 3 -C 10 n-valent cycloalkyl group, C 4 -C n value of 10 cycloalkylalkyl, C n valence 4 -C 10 alkylcycloalkyl, C 6 -C n or a divalent aromatic group 20; optionally, these groups are -CH 2 - may be substituted by an oxygen atom or a 1,4-phenylene group, provided that the two -O- are not directly bonded.
  • R 4 represents a C 1 -C 8 linear or branched n-valent alkyl group, a C 7 -C 12 n-valent aryl group, or an n-valent phenyl group.
  • R 5 is selected from a linear or branched alkyl group of C 1 - C 4 , particularly a methyl group and an ethyl group.
  • n is an integer from 1 to 4.
  • ester compound represented by the formula (V) is selected from the following compounds, but is not limited to these compounds:
  • the method for producing the above cationically polymerizable monomer comprises a transesterification reaction of a polyfunctional oxetane compound represented by the formula (I) and an ester compound represented by the formula (V) in the presence of a catalyst.
  • the catalyst used in the reaction is preferably a titanate compound, more preferably 2-ethylhexyl titanate, tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate.
  • a titanate compound more preferably 2-ethylhexyl titanate, tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate.
  • the amount of the catalyst used can be readily determined by those skilled in the art.
  • the amount of the catalyst is from 0.05 to 5% by weight, more preferably from 0.1 to 2% by weight, based on the compound of the formula (I).
  • the reaction system contains an organic solvent as a carrier medium, and the type of the solvent to be used is not particularly limited as long as it can dissolve the reaction raw material without affecting the reaction, such as benzene, toluene, xylene, and the like.
  • the amount of the solvent to be used can be appropriately adjusted depending on the uniformity and agitation of the reaction system, which is easily determined by those skilled in the art.
  • the reaction temperature varies depending on the kind of the raw material, and is usually from 0 to 200 ° C, preferably from 50 to 150 ° C.
  • the product is obtained by washing with water, filtration, and distillation under reduced pressure.
  • the present invention provides a cationically polymerizable monomer obtained by reacting a compound represented by the above formula (I) with an isocyanate compound represented by the formula (VI).
  • R 6 represents a p-valent linking group, and p represents an integer of 1 to 8; provided that the cationically polymerizable monomer has at least two oxetane groups.
  • R 6 represents a C 1 - C 20 linear or branched p-valent alkyl group, a C 2 - C 20 p-valent alkenyl group, or C.
  • -CH 2 - in these groups may be substituted by an oxygen atom or 1,4-phenylene, provided that two -O- are not directly attached; optionally, one of these groups Or a plurality of hydrogen atoms may be independently substituted with a group selected from an alkyl group, a halogen, and a nitro group.
  • R 6 represents a C 1 -C 10 linear or branched p-valent alkyl group, a C 2 -C 10 p-valent alkenyl group, a C 3 -C 10 p-valent cycloalkyl group, a C 4 a p-valent cycloalkylalkyl group of -C 10 , a p-valent alkylcycloalkyl group of C 4 -C 10 , a p-valent aryl group of C 6 -C 20 ; optionally, -CH 2 - in these groups It may be substituted by an oxygen atom or a 1,4-phenylene group, provided that two -O- are not directly bonded; optionally, one or more of the hydrogen atoms of these groups may be independently substituted by an alkyl group.
  • R 6 represents a C 1 -C 8 linear or branched p-valent alkyl group, a C 6 -C 12 p-valent aryl group; optionally, -CH 2 - in these groups may be an oxygen atom or a substituted 1,4-phenylene, provided that the two are not directly linked -O-; optionally, one of these groups or more hydrogen atoms may be independently a C 1 -C 4 alkyl Substituted by the base.
  • p is an integer from 1 to 4.
  • the isocyanate compound represented by the formula (VI) is selected from the following compounds, but is not limited to these compounds:
  • the method for producing the above cationically polymerizable monomer comprises reacting a polyfunctional oxetane compound represented by the formula (I) with an isocyanate compound represented by the formula (VI) in the presence of a catalyst.
  • the catalyst is dibutyltin laurate in an amount of from 0.05 to 5% by weight, more preferably from 0.1 to 2% by weight, based on the compound of formula (I).
  • an organic solvent may be selectively used as a carrier medium in the reaction system depending on the kind of the raw material.
  • the type of the solvent to be used is not particularly limited as long as it can dissolve the reaction raw material without affecting the reaction, and may be, for example, acetonitrile or propylene.
  • Nitrile solvent such as nitrile or benzonitrile
  • amide solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone
  • ether such as tetrahydrofuran or dioxane Solvent
  • aromatic solvent such as benzene, toluene or xylene.
  • the reaction temperature varies depending on the kind of the raw material, and is usually from 0 to 100 ° C, preferably from 20 to 80 ° C.
  • the polyfunctional oxetane compound represented by the formula (I) is reacted with epichlorohydrin, an ester compound represented by the formula (V) or an isocyanate compound represented by the formula (VI).
  • the oxetane compound can exhibit similar or superior properties to the compound of the formula (I). By introducing a new functional group in the general formula (I), a better performance adjustability can be obtained to meet different system application requirements.
  • Compound 5 was prepared by the procedure of Example 1, and its structure was confirmed by GC-MS and 1 H-NMR.
  • the product 7-13 having the structure shown in Table 1 was synthesized from the corresponding reagent.
  • the application properties of the polyfunctional oxetane monomers of the present invention are evaluated by formulating exemplary photocurable compositions, including curing speed, hardness, flexibility, adhesion, heat resistance and the like.
  • TTA21 and E-51 are represented by epoxy monomers
  • PAG-202 is used as a cationic photoinitiator
  • compounds a and/or b described in the background are used as comparative polyfunctional oxetane.
  • Alkane monomer Alkane monomer.
  • the raw materials were placed in the mass parts shown in Table 2, and after mixing uniformly in the dark room, about 1 mg of the sample was weighed and spread on aluminum crucible.
  • the samples were scanned and cured using a Perkin Elmer Differential Scanning Calorimeter (DSC 8000) equipped with a mercury arc lamp UV source (OmniCure-S2000).
  • the polyfunctional oxetane monomer of the present invention is used in combination with an epoxy monomer in a cationic photocuring system, and has a fast curing speed, which is superior to the existing structural compound of the same type. b.
  • the polyfunctional oxetane monomer or compounds a and b of the present invention are mixed with the epoxy monomer TTA21 in a 1:1 mass ratio, and then the 2% initiator PAG-202 is added, and stirred and mixed in a dark room. After homogenization, the formulation was applied to a sandpaper-polished tinplate substrate with a 25# wire rod to obtain a coating having a thickness of about 25 ⁇ m, and then fully exposed in a crawler exposure machine (RW-UV.70201). The single exposure was 80 mj/cm2 and then tested after 24 hours.
  • the cured film was tested at a temperature of 23 ° C and a relative humidity of 50%.
  • the pencil hardness evaluation method specified in GB/T 6739-2006 was used as a standard, and the pencil was inserted into the test instrument and fixed with a clip to maintain the level. Place the tip of the pencil on the surface of the paint film and push it at a distance of 1 mm/s away from itself by at least 7 mm. If no scratches occur, repeat the test in the untested area and replace the pencil with a higher hardness until at least 3 mm long.
  • the hardness of the coating is indicated by the hardness of the hardest pencil which does not scratch the coating.
  • the cured film was tested at a temperature of 23 ° C and a relative humidity of 70%.
  • the outer side of the tinplate coated with the cured coating was sequentially wound in the longitudinal direction based on the GB/T1731-93 paint film flexibility test method.
  • the cured film was tested at a temperature of 23 ° C and a relative humidity of 50%.
  • the coating film is cut into a hundred grid, the cutting edge is to be cut with the substrate, and the cutting edge is sharp, and the cutting edge and the coating film are formed. 45-degree angle.
  • Use a soft brush to remove the paint scraps stick the 3M transparent tape on the lined 100 grids, and apply force to make the tape firmly adhere to the film surface and the cross-section.
  • Within 2 min hold one end of the 3M tape at a 60 degree angle and smoothly peel off the tape within 1 second and evaluate according to the following criteria.
  • Level 0 The cutting edge is completely smooth and has no shedding
  • Level 1 There is a little coating peeling off at the intersection of the incisions, but the cross-cut area is not affected by significantly more than 5%;
  • Level 2 There is a coating peeling off at the intersection of the incision and/or along the edge of the incision, which is significantly affected by more than 5%, but not significantly greater than 15%;
  • Level 3 The coating peels off partially or completely along the cutting edge with large fragments, and/or partially or completely peels off at different parts of the lattice.
  • the affected cross-cut area is significantly greater than 15%, but not significantly greater than 35%;
  • Level 4 The coating peels off along the cutting edge, and/or some of the squares are partially or completely detached, and the affected cross-cut area is significantly greater than 35%, but not significantly greater than 65%;
  • Level 5 The degree of peeling exceeds level 4.
  • the cured film was tested by differential scanning calorimeter (PE DSC 8000) under the nitrogen atmosphere at a rate of 10 ° C/min from -20 ° C to 200 ° C, at 200 ° C for 1 min, then at 10 ° C / The rate of min was cooled from 200 ° C to -20 ° C, held at -20 ° C for 1 min, and then heated from -20 ° C to 200 ° C at a rate of 10 ° C / min, thereby measuring the glass transition temperature Tg (° C.).
  • PE DSC 8000 differential scanning calorimeter
  • thermogravimetric analyzer PE STA6000
  • T thermal decomposition temperature
  • the thermal decomposition temperature T (°C) above 300 is indicated as: ⁇ ;
  • the thermal decomposition temperature T (°C) is above 250-300 and is recorded as: ⁇ ;
  • the thermal decomposition temperature T (°C) is expressed as 250 or less: ⁇ .
  • the polyfunctional oxetane compound of the present invention has a significant advantage in hardness, flexibility, adhesion, and heat resistance after being applied to a cationic photocuring system as compared with the compound a; Compared with the compound b which is closer in structure, the present invention exhibits better performance in terms of flexibility, adhesion, and heat resistance, and the overall performance is more excellent.
  • the polyfunctional oxetane compound of the invention has excellent application performance in a cationic photocuring system, has good structure and performance adjustability, and can meet different system application requirements.

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  • Organic Chemistry (AREA)
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Abstract

一组多官能度氧杂环丁烷类化合物及其制备方法。该化合物是具有如通式(I)所示结构的化合物，或者是通式（I）化合物与环氧氯丙烷、酯化合物、或异氰酸酯化合物反应得到的产物。这些多官能度氧杂环丁烷类化合物作为阳离子聚合性单体与环氧化合物配合使用时，固化速度快，固化产物的硬度、柔韧性、附着性和耐热性非常优异。

Description

多官能度氧杂环丁烷类化合物及其制备方法 技术领域
本发明属于有机化学领域，具体涉及多官能度氧杂环丁烷类化合物及其制备方法。
背景技术
在光固化领域，阳离子光固化体系具有不受氧阻聚影响、固化体积收缩小等优点，其中使用的活性稀释剂单体主要有乙烯基醚类化合物、环氧类化合物和氧杂环丁烷类化合物。
环氧类单体可以得到具有良好耐热性、粘合力和耐化学品性的固化物，但是单体反应活性较低。乙烯基醚类单体具有较高的聚合活性，但是其硬度、耐磨性、耐化学品性等性能较差，不能用作硬涂剂和各种基材的保护膜。相较而言，氧杂环丁烷类单体反应活性高，且其固化后产物物理性能优异，因而在固化组合物中的应用越来越广泛。特别是，氧杂环丁烷类单体和环氧类单体配合使用(以结合两者的优点)已成为阳离子光固化体系中的一种常用形式。
近年来，针对氧杂环丁烷类单体的研究不断深入，发现将其多官能化有利于进一步提高其应用性能。例如，中国专利CN103497691A中公开了一种用于偏振片制造的光固化粘结剂组合物，以双官能度氧杂环丁烷化合物
Figure PCTCN2017092227-appb-000001
(化合物a)与环氧化合物配合使用，在粘接性和耐久性的平衡方面有明显的提高；日本专利JP4003264B2中公开了一种双官能度氧杂环丁烷化合物
Figure PCTCN2017092227-appb-000002
(化合物b)，可以明显提高阳离子固化体系的固化速度。因此，将氧杂环丁烷类单体多官能化在许多应用领域都颇受关注，例如粘合剂、密封剂、封装剂等领域，特别是用于LED器件的部件和组件中的那些，而这也是氧杂环丁烷类阳离子聚合性单体发展的必然趋势。但是，现有文献资料中报道的多官能度氧杂环丁烷类单体仍存在不足，突出的一点便是应用后固化产物的硬度、柔韧性及附着性等性能难以得到很好的平衡，综合性能仍有待于进一步提高。
发明内容
针对现有氧杂环丁烷类单体的不足，本发明的目的在于提供具有更高反应活性和更优应用性能的多官能度氧杂环丁烷类化合物及其制备方法。这些多官能度氧杂环丁烷类阳离子聚合性单体与环氧化合物配合使用固化速度快，固化产物的硬度、柔韧性、附着性和耐热性非常优异。
为了实现上述目的，本发明首先提供一种多官能度氧杂环丁烷类化合物，其具有通式(I)所示结构：
Figure PCTCN2017092227-appb-000003
其中，
R1表示C1-C40的直链或支链的m价烷基、C2-C20的m价链烯基、或C6-C40的m价芳基，其中的-CH2-可任选地(optionally)被氧原子、-NH-或者
Figure PCTCN2017092227-appb-000004
所取代，条件是两个-O-不直接相连；并且任选地，这些基团中的一个或多个氢原子可以独立地被选自烷基、卤素、硝基的基团所取代；
R2表示C1-C20的直链或支链亚烷基，其主链中的-CH2-可任选地被氧原子取代，条件是两个-O-不直接相连，并且任选地，基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代；
R3表示氢、卤素、硝基、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C2-C10的链烯基或C6-C20的芳基，任选地，这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代；
m表示1-8的整数。
优选地，上述通式(I)化合物中含有两个以上的氧杂环丁烷基团。为此，m宜取2以上的数值；或者当m＝1时，R1中应含有至少1个氧杂环丁烷基团。
作为优选技术方案，R1表示C1-C40的直链或支链的m价烷基、C2-C10的直链或支链的m价链烯基、或C6-C30的m价芳基，其中的-CH2-可任选地被氧原子、-NH-或者
Figure PCTCN2017092227-appb-000005
所取代，条件是两个-O-不直接相连；并且任选地，这些基团中的一个或多个氢原子可以独立地被选自烷基、卤素、硝基的基团所取代。
示例性地，R1可选自下列结构：C1-C12的直链或支链的1-4价烷基、C2-C6的直链或支链的1-4价链烯基、
Figure PCTCN2017092227-appb-000006
CH3-O-CH2CH2*、
Figure PCTCN2017092227-appb-000007
*CH2CH2-NH-CH2CH2*、
Figure PCTCN2017092227-appb-000008
优选地，R2表示C1-C10的直链或支链亚烷基，其主链中的-CH2-可任选地被氧原子取代，条件是两个-O-不直接相连。进一步优选地，R2表示C1-C6的直链或支链亚烷基，其主链中的-CH2-可任选地被氧原子取代，条件是两个-O-不直接相连。
优选地，R3表示氢、C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C10的环烷基烷基、C4-C10的烷基环烷基、C2-C8的链烯基、苯基。进一步优选地，R3表示C1-C4的直链或支链烷基、或C4-C8的环烷基烷基。
m优选为1-6的整数，更优选1-4的整数。
本发明公开的内容中，除另有说明，相关术语具有本领域通常理解的含义。数值范围包括端点值和端点值之间的所有点值，例如“C1-C10”包括C1、C2、C3、C4、C5、C6、C7、C8、C9、C10，“1-4的整数”包括1、2、3、4。
相应地，本发明还涉及上述通式(I)所示多官能度氧杂环丁烷类化合物的制备方法，以通式(II)所示含羟基化合物和通式(III)所示含氧杂环丁烷基的环氧化合物为原料，在催化剂存在条件下反应得到产物，反应式如下：
Figure PCTCN2017092227-appb-000009
上述制备方法中，使用的催化剂可以是：碱金属氢氧化物，如氢氧化钠、氢氧化钾等；醇的碱金属盐，如甲醇钠、乙醇钾、叔丁醇钠等；碱金属碳酸盐，如碳酸钠、碳酸钾等；碱金属碳酸氢盐，如碳酸氢钠、碳酸氢钾等；烷基金属锂化合物，如丁基锂、苯基锂等；胺基锂化合物，如二异丙基氨基锂、六甲基二硅氨基锂等。催化剂的用量对本领域技术人员而言是容易确定的，优选地，催化剂用量为通式(II)化合物的摩尔量的0.1-20％，更优选1-20％。
根据原料种类，反应体系可任选地包含有机溶剂。对适用的溶剂种类没有特别限定，只要能够溶解反应原料且不影响反应即可，例如可以是：乙腈、丙腈、苄腈等腈类溶剂；N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮等酰胺类溶剂；四氢呋喃、二氧杂环己烷等醚类溶剂；苯、甲苯、二甲苯等芳香族溶剂。这些溶剂可以单独使用或两种以上混合使用，总用量可根据反应体系的均一性和搅拌性进行适当调节，这对本领域技术人员而言是容易确定的。
反应温度根据原料种类有所不同，通常为25-200℃，优选50-150℃。对反应压力没有特别限制，一般情况下常压即可。
反应结束后，调节pH值至中性，过滤，水洗、萃取，减压蒸馏，即可得到通式(I)所示的多官能度氧杂环丁烷类化合物。
进一步地，本发明还提供由上述通式(I)所示多官能度氧杂环丁烷类化合物与环氧氯丙烷反应生成的阳离子聚合性单体，其具有通式(IV)所示结构：
Figure PCTCN2017092227-appb-000010
其中，R1、R2、R3和m具有如通式(I)中所述的相同定义。
通式(IV)所示阳离子聚合性单体的制备方法包括：通式(I)所示多官能度氧杂环丁烷类化合物与环氧氯丙烷在碱性条件下反应；
反应式如下：
Figure PCTCN2017092227-appb-000011
通式(IV)所示阳离子聚合性单体的制备过程中，碱性条件的构建对于本领域技术人员而言是容易想到的。示例性地，可以在反应体系中添加碱性化合物，例如：碱金属氢氧化物，如氢氧化钠、氢氧化钾等；碱金属碳酸盐，如碳酸钠、碳酸钾等；碱金属碳酸氢盐，如碳酸氢钠、碳酸氢钾等。碱性化合物可促使反应顺利进行，其用量对本领域技术人员而言是容易确定的，优选地，碱性化合物的用量为通式(I)化合物的摩尔量的1-20倍，更优选m-10倍。
任选地，根据原料种类可选择性地在反应体系中使用有机溶剂作为载体介质，对适用的溶剂种类没有特别限定，只要能够溶解反应原料且不影响反应即可，例如可以是：乙腈、丙腈、苄腈等腈类溶剂；N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮等酰胺类溶剂；四氢呋喃、二氧杂环己烷等醚类溶剂；苯、甲苯、二甲苯等芳香族溶剂。这些溶剂可以单独使用或两种以上混合使用。反应温度根据原料种类有所不同，通常为25-120℃，优选30-80℃。反应结束后，可通过水洗、萃取、减压蒸馏得到产品。
进一步地，本发明还提供一种阳离子聚合性单体，由上述通式(I)所示化合物与通式(V)所示酯化合物反应而成，
Figure PCTCN2017092227-appb-000012
其中，R4表示n价连接基团，R5表示C1-C10的直链或支链的烷基，n表示1-8的整数；
条件是，阳离子聚合性单体具有至少两个氧杂环丁烷基团。
根据m和n取值的不同，该阳离子聚合性单体可以是单羟基的通式(I)化合物(即m＝1)与单酯基化合物(即n＝1，且此时通式I化合物中R1含有至少1个氧杂环丁烷基团)或多酯基化合物(即n>1)反应得到的阳离子聚合性单体，也可以是多羟基的通式(I)化合物(即m>1)与单酯基化合物或多酯基化合物反应得到的阳离子聚合性单体。
作为优选技术方案，通式(V)所示酯化合物中，R4表示C1-C20的直链或支链的n价烷基、C2-C20的n价链烯基、C3-C20的n价环烷基、C4-C20的n价环烷基烷基、C4-C20的n价烷基环烷基、或C6-C40的n价芳基；任选地，这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代，条件是两个-O-不直接相连；任选地，这些基团中的一个或多个氢原子可以独立地被选自烷基、卤素、硝基的基团所取代。
进一步优选地，R4表示C1-C10的直链或支链的n价烷基、C2-C10的n价链烯基、C3-C10的n价环烷基、C4-C10的n价环烷基烷基、C4-C10的n价烷基环烷基、或C6-C20的n价芳基；任选地，这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代，条件是两个-O-不直接相连。
更优选地，R4表示C1-C8的直链或支链的n价烷基、C7-C12的n价芳基、n价苯基。
优选地，上述酯化合物中，R5选自C1-C4的直链或支链烷基，特别是甲基和乙基。
优选地，n为1-4的整数。
示例性地，通式(V)所示酯化合物选自下列化合物，但不局限于这些化合物：
Figure PCTCN2017092227-appb-000013
上述阳离子聚合性单体的制备方法，包括：通式(I)所示多官能度氧杂环丁烷类化合物与通式(V)所示酯化合物在催化剂存在条件下进行酯交换反应。
反应中使用的催化剂优选是钛酸酯类化合物，更优选是钛酸-2-乙基己酯、钛酸四甲酯、钛酸四乙酯、钛酸四异丙酯、钛酸四丁酯、钛酸四异丁酯等中的一种或两种以上的组合。催化剂的用量对本领域技术人员而言是容易确定的，优选地，催化剂用量为通式(I)化合物的0.05-5wt％，更优选0.1-2wt％。
优选地，反应体系中包含有机溶剂以作为载体介质，对适用的溶剂种类没有特别限定，只要能够溶解反应原料且不影响反应即可，如苯、甲苯、二甲苯等。溶剂的使用量可根据反应体系的均一性和搅拌性进行适当调节，这对本领域技术人员而言是容易确定的。
反应温度根据原料种类有所不同，通常为0-200℃，优选50-150℃。反应结束后，经水洗、过滤、减压蒸馏即可得到产品。
进一步地，本发明还提供一种阳离子聚合性单体，由上述通式(I)所示化合物与通式(VI)所示的异氰酸酯化合物反应而成，
Figure PCTCN2017092227-appb-000014
其中，R6表示p价连接基团，p表示1-8的整数；条件是，所述阳离子聚合性单体具有至少两个氧杂环丁烷基团。
根据m和p取值的不同，该阳离子聚合性单体可以是单羟基的通式(I)化合物(即m＝1)与单异氰酸根化合物(即p＝1，且此时通式I化合物中R1含有至少1个氧杂环丁烷基团)或多异氰酸根化合物(即p>1)反应得到的阳离子聚合性单体，也可以是多羟基的通式(I)化合物(即m>1)与单异氰酸根化合物或多异氰酸根化合物反应得到的阳离子聚合性单体。
作为优选技术方案，通式(VI)所示的异氰酸酯化合物中，R6表示C1-C20的直链或支链的p价烷基、C2-C20的p价链烯基、C3-C20的p价环烷基、C4-C20的p价环烷基烷基、C4-C20的p价烷基环烷基、或C6-C40的p价芳基；任选地，这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代，条件是两个-O-不直接相连；任选地，这些基团中的一个或多个氢原子可以独立地被选自烷基、卤素、硝基的基团所取代。
进一步优选地，R6表示C1-C10的直链或支链的p价烷基、C2-C10的p价链烯基、C3-C10的p价环烷基、C4-C10的p价环烷基烷基、C4-C10的p价烷基环烷基、C6-C20的p价芳基；任选地，这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代，条件是两个-O-不直接相连；任选地，这些基团中的一个或多个氢原子可以独立地被烷基所取代。
更优选地，R6表示C1-C8的直链或支链的p价烷基、C6-C12的p价芳基；任选地，这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代，条件是两个-O-不直接相连；任选地，这些基团中的一个或多个氢原子可以独立地被C1-C4的烷基所取代。
优选地，p为1-4的整数。
示例性地，通式(VI)所示的异氰酸酯化合物选自下列化合物，但不局限于这些化合物：
Figure PCTCN2017092227-appb-000015
上述阳离子聚合性单体的制备方法，包括：通式(I)所示多官能度氧杂环丁烷类化合物与通式(VI)所示异氰酸酯化合物在催化剂存在条件下反应。
反应中使用的催化剂及用量对本领域的技术人员而言是容易确定的。优选地，催化剂为月桂酸二丁基锡，用量为通式(I)化合物的0.05-5wt％，更优选0.1-2wt％。
任选地，根据原料种类可选择性地在反应体系中使用有机溶剂作为载体介质，对适用的溶剂种类没有特别限定，只要能够溶解反应原料且不影响反应即可，例如可以是：乙腈、丙腈、苄腈等腈类溶剂；N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮等酰胺类溶剂；四氢呋喃、二氧杂环己烷等醚类溶剂；苯、甲苯、二甲苯等芳香族溶剂。这些溶剂可以单独使用或两种以上混合使用。溶剂的使用量可根据反应体系的均一性和搅拌性进行适当调节，这对本领域技术人员而言是容易确定的。
反应温度根据原料种类有所不同，通常为0-100℃，优选20-80℃。
通式(I)所示多官能度氧杂环丁烷类化合物与环氧氯丙烷、通式(V)所示酯化合物、或通式(VI)所示异氰酸酯化合物反应得到的均为多官能度氧杂环丁烷类化合物，能够表现出与通式(I)化合物类似或更优的性能。通过反应可在通式(I)中引入新的官能基团，从而获得更佳的性能可调性，以满足不同的体系应用需求。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
制备实施例
实施例1
Figure PCTCN2017092227-appb-000016
向装有搅拌装置、温度计、回流冷凝管的250ml四口烧瓶中依次加入102g(0.5mol)原料1、4g(0.1mol)氢氧化钠及100g甲苯，搅拌升温至80℃，滴加86g(0.5mol)原料2，1.5h滴加完，继续搅拌反应，气相跟踪至原料1含量不再变化，停止加热，调节pH至中性，过滤，水洗、萃取，减压蒸馏得到174g淡黄色粘稠液体。
产物即化合物1的结构通过GC-MS和1H-NMR得到确认。
MS(m/e)：376(M)；
1H-NMR(CDCl3，500MHz)：δ0.96(6H，m)，δ1.25(4H，s)，δ2.01(1H，d)，δ3.29(4H，s)，δ3.52-3.54(12H，m)，δ3.87(1H，m)，δ4.65(8H，s)。
实施例2
Figure PCTCN2017092227-appb-000017
向装有搅拌装置、温度计、回流冷凝管的250ml四口烧瓶中依次加入188g(0.5mol)化合物1、46g(0.5mol)环氧氯丙烷及20g(0.5mol)氢氧化钠，40℃反应12h，气相跟踪至化合物1完全消失，反应结束后，水洗、萃取，减压蒸馏，最终得到无色粘稠液体198.7g。
产物即化合物2的结构通过GC-MS和1H-NMR得到确认。
MS(m/e)：432(M)；
1H-NMR(CDCl3，500MHz)：δ0.96(6H，m)，δ1.25(4H，s)，δ2.50(2H，d)，δ2.86(1H，m)，δ3.29(4H，s)，δ3.49-3.54(15H，m)，δ4.65(8H，s)。
实施例3
Figure PCTCN2017092227-appb-000018
向装有搅拌装置、温度计、精馏塔及分水装置的四口烧瓶中加入188g(0.5mol)化合物1、33g(0.25mol)丙二酸二甲酯及200g甲苯，加热回流除去体系中的水分，降温至60℃左右后加入2.5g钛酸四乙酯，加热回流反应，调节回流比将反应生成的甲醇带出，当精馏塔塔顶温度升至110℃停止反应，降温至70℃，加入10g水搅拌1h，趁热过滤，滤液减压蒸馏得淡黄色粘稠液体197g。
产物即化合物3的结构通过GC-MS和1H-NMR得到确认。
MS(m/e)：821(M)；
1H-NMR(CDCl3，500MHz)：δ0.96(12H，m)，δ1.25(8H，m)，δ3.21(2H，s)，δ3.29(8H，s)，δ3.54-3.61(24H，m)，δ4.61-4.65(18H，m)。
实施例4
Figure PCTCN2017092227-appb-000019
向装有搅拌装置、温度计的四口烧瓶中加入188g(0.5mol)化合物1及0.1g月桂酸二丁基锡，温度控制在40℃左右，滴加42g(0.25mol)六亚甲基二异氰酸酯，滴加完保温反应至NCO值降至0.05％以下，结束反应。
产物即化合物4的结构通过GC-MS和1H-NMR得到确认。
MS(m/e)：920(M)；
1H-NMR(CDCl3，500MHz)：δ0.96(12H，m)，δ1.25-1.55(16H，m)，δ3.29(8H，s)，δ3.54-3.61(24H，m)，δ4.61-4.65(18H，m)，δ8.0(2H，m)。
实施例5
Figure PCTCN2017092227-appb-000020
参照实施例1的过程，制备化合物5，其结构通过GC-MS和1H-NMR得到确认。
MS(m/e)：406(M)；
1H-NMR(CDCl3，500MHz)：δ0.96(6H，m)，δ1.25(4H，s)，δ2.01(2H，d)，δ3.29(4H，s)，δ3.52-3.54(12H，m)，δ3.87(2H，m)，δ4.65(8H，s)。
实施例6
Figure PCTCN2017092227-appb-000021
参照实施例3的过程，由化合物5制得化合物6。
化合物6的结构通过IR得到确认。
IR(KBr)，ν/cm-1：981(s，
Figure PCTCN2017092227-appb-000022
)，1200(m，C-O-C)，1720(s，C＝O)，960.7(m,Ar-H)。
实施例7
参照实施例1-6的方法，由相应试剂合成具有表1中所示结构的产物7-13.
表1
Figure PCTCN2017092227-appb-000023
Figure PCTCN2017092227-appb-000024
性能测试
通过配制示例性光固化组合物，对本发明的多官能度氧杂环丁烷类单体的各项应用性能进行评价，包括固化速度、硬度、柔韧性、附着性、耐热性等方面。
测试过程中，以TTA21和E-51为环氧单体代表，以PAG-202为阳离子光引发剂代表，以背景技术中记载的化合物a和/或b作为对比的多官能度氧杂环丁烷类单体。
Figure PCTCN2017092227-appb-000025
Figure PCTCN2017092227-appb-000026
1、固化速度测试
按照表2中所示质量份配置原料，暗室中混合均匀后，称取约1mg样品平铺于铝坩埚。使用配有汞弧灯紫外光源(OmniCure-S2000)的Perkin Elmer差示扫描量热仪(DSC8000)对样品进行扫描，使其固化。
记录UV引发到最大固化放热的时间，以及达到90％UV固化放热量所需要的时间，更短的时间达到峰顶点和更短的时间达到90％转化是良好固化性能的表示。
测试结果汇总在表2中。
表2
Figure PCTCN2017092227-appb-000027
从表2中可以看到，本发明的多官能度氧杂环丁烷类单体与环氧单体配合使用于阳离子光固化体系后，固化速度快，优于现有的同类结构化合物即化合物b。
2、固化成膜后性能测试
将本发明的多官能度氧杂环丁烷单体或者化合物a和b分别与环氧单体TTA21以1:1质量比混合，再加入2％的引发剂PAG-202，在暗室中搅拌混合均匀后，用25#线棒将配方涂布于经砂纸打磨的马口铁片基材上，获得厚度约为25μm的涂层，然后置于履带式曝光机(RW-UV.70201)中充分曝光10次，单次曝光为80mj/cm2，然后放置24h后进行测试。
(1)硬度测试
在温度23℃、相对湿度50％的条件下对固化膜进行测试，以GB/T 6739-2006中规定的铅笔硬度评价方法为标准，将铅笔插入试验仪器中并用夹子将其固定，保持水平，铅笔的尖端放在漆膜表面上，以1mm/s的速度朝离开自己的方向推动至少7mm距离，如果未出现划痕，在未测试区域重复实验，更换较高硬度的铅笔直至出现至少3mm长的划痕为止，以没有使涂层出现划痕的最硬的铅笔的硬度表示涂层的硬度。
(2)柔韧性测试
在温度23℃，相对湿度70％的条件下对固化膜进行测试，以GB/T1731-93漆膜柔韧性测试方法为依据，将涂有固化涂层的马口铁板的外侧沿长度方向依次卷绕在10、5、4、3、2、1毫米的棒轴上，弯曲2-3s，用放大镜观察，以涂料层破坏的最小的棒轴的直径来表示紫外光固化涂层的柔韧性。
(3)附着性测试
在温度23℃，相对湿度50％的条件下对固化膜进行测试。以GB/T 9286-1998中规定的漆膜划格评价方法为标准，将涂膜切割为百格，刀尖在切割时要划及底材，并且刀尖要锋利，刀尖与涂膜成45度角。用软毛刷刷去漆屑，将3M透明胶带粘在划好的百格上，并施力使胶带牢固的粘在涂膜面及划格部位。在2min内，拿住3M胶带的一端，并呈60度角度，在1秒内平稳地撕离胶带，并按下述标准进行评价。
0级：切割边缘完全平滑无一脱落；
1级：在切口交叉处有少许涂层脱落，但交叉切割面积受影响不能明显大于5％；
2级：在切口交叉处和/或沿切口边缘有涂层脱落，受影响明显大于5％，但不能明显大于15％；
3级：涂层沿切割边缘部分或全部以大碎片脱落，和/或在格子不同部位上部分或全部剥落，受影响的交叉切割面积明显大于15％，但不能明显大于35％；
4级：涂层沿切割边缘大碎片剥落，和/或一些方格部分或全部脱落，受影响的交叉切割面积明显大于35％，但不能明显大于65％；
5级：剥落的程度超过4级。
(4)玻璃化转变温度测试
对固化膜利用差示扫描量热仪(PE DSC8000)进行测试，测试条件：氮气氛围，以10℃/min的速率从-20℃加热至200℃，在200℃保持1min，然后以10℃/min的速率从200℃冷却至-20℃，在-20℃保持1min，接着在以10℃/min的速率从-20℃加热至200℃，从而测得玻璃化转变温度Tg(℃)。
(5)热分解温度测试
对固化膜利用热失重分析仪(PE STA6000)进行热重分析。将初期无重量减少或渐渐减少部分的切线与重量发生急剧减少处的拐点的切线相交的部位的温度作为热分解温度T(℃)，并按照下述标准进行评价。
热分解温度T(℃)在300以上的记为：△；
热分解温度T(℃)在250-300以上记为：○；
热分解温度T(℃)在250以下记为：×。
评价结果汇总于表3中。
表3
Figure PCTCN2017092227-appb-000028
Figure PCTCN2017092227-appb-000029
从表3可以看到，相比于化合物a，本发明的多官能度氧杂环丁烷类化合物应用于阳离子光固化体系后，在硬度、柔韧性、附着性、耐热性优势非常明显；而相比于结构更为接近的化合物b，本发明在柔韧性、附着性、耐热性方面也表现出了更好的性能，综合性能更为优异。
综上所述，本发明的多官能度氧杂环丁烷类化合物在阳离子光固化体系中应用性能优异，具有良好的结构和性能可调性，可满足不同的体系应用需求。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (26)

  1. 一种多官能度氧杂环丁烷类化合物，其特征在于，所述化合物具有通式(I)所示结构：
    Figure PCTCN2017092227-appb-100001
    其中，
    R1表示C1-C40的直链或支链的m价烷基、C2-C20的m价链烯基或C6-C40的m价芳基，其中的-CH2-可任选地被氧原子、-NH-或者
    Figure PCTCN2017092227-appb-100002
    所取代，条件是两个-O-不直接相连；并且任选地，这些基团中的一个或多个氢原子可以独立地被选自烷基、卤素、硝基的基团所取代；
    R2表示C1-C20的直链或支链亚烷基，其主链中的-CH2-可任选地被氧原子取代，条件是两个-O-不直接相连，并且任选地，基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代；
    R3表示氢、卤素、硝基、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C2-C10的链烯基或C6-C20的芳基，任选地，这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代；
    m表示1-8的整数。
  2. 根据权利要求1所述的多官能度氧杂环丁烷类化合物，其特征在于，m取2以上的数值；或者当m＝1时，R1中含有至少1个氧杂环丁烷基团。
  3. 根据权利要求1或2所述的多官能度氧杂环丁烷类化合物，其特征在于，R1表示C1-C40的直链或支链的m价烷基、C2-C10的直链或支链的m价链烯基或C6-C30的m价芳基，其中的-CH2-可任选地被氧原子、-NH-或者
    Figure PCTCN2017092227-appb-100003
    所取代，条件是两个-O-不直接相连；并且任选地，这些基团中的一个或多个氢原子可以独立地被选自烷基、卤素、硝基的基团所取代。
  4. 根据权利要求1或2所述的多官能度氧杂环丁烷类化合物，其特征在于，R2表示C1-C10的直链或支链亚烷基，其主链中的-CH2-可任选地被氧原子取代，条件是两个-O-不直接相连；优选地，R2表示C1-C6的直链或支链亚烷基，其主链中的-CH2-可任选地被氧原子取代，条件是两个-O-不直接相连。
  5. 根据权利要求1或2所述的多官能度氧杂环丁烷类化合物，其特征在于，R3表示氢、C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C10的环烷基烷基、C4-C10的烷基环烷基、C2-C8的链烯基或苯基；优选地，R3表示C1-C4的直链或支链烷基、或C4-C8的环烷基烷基。
  6. 根据权利要求1或2所述的多官能度氧杂环丁烷类化合物，其特征在于，m为1-6的整数，优选1-4的整数。
  7. 权利要求1至6中任一项所述的多官能度氧杂环丁烷类化合物的制备方法，其特征在于，所述制备方法包括：以通式(II)所示含羟基化合物和通式(III)所示含氧杂环丁烷基的环氧化合物为原料，在催化剂存在条件下反应得到产物，反应式如下：
    Figure PCTCN2017092227-appb-100004
  8. 权利要求1至6中任一项所述的多官能度氧杂环丁烷类化合物与环氧氯丙烷反应生成的阳离子聚合性单体，其具有通式(IV)所示结构：
    Figure PCTCN2017092227-appb-100005
    其中，R1、R2、R3和m具有如通式(I)中所述的相同定义。
  9. 权利要求8所述的通式(IV)所示阳离子聚合性单体的制备方法，其特征在于，所述制备方法包括：通式(I)所示多官能度氧杂环丁烷类化合物与环氧氯丙烷在碱性条件下反应，得到所述阳离子聚合性单体；
    反应式如下：
    Figure PCTCN2017092227-appb-100006
  10. 一种阳离子聚合性单体，其特征在于，由权利要求1至6中任一项所述的通式(I)所示化合物与通式(V)所示酯化合物反应而成，
    Figure PCTCN2017092227-appb-100007
    其中，R4表示n价连接基团，R5表示C1-C10的直链或支链的烷基，n表示1-8的整数；
    条件是，所述阳离子聚合性单体具有至少两个氧杂环丁烷基团。
  11. 根据权利要求10所述的阳离子聚合性单体，其特征在于，通式(V)所示酯化合物中，R4表示C1-C20的直链或支链的n价烷基、C2-C20的n价链烯基、C3-C20的n价环烷基、C4-C20的n价环烷基烷基、C4-C20的n价烷基环烷基、C6-C40的n价芳基；任选地，这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代，条件是两个-O-不直接相连；任选地，这些基团中的一个或多个氢原子可以独立地被选自烷基、卤素、硝基的基团所取代。
  12. 根据权利要求10或11所述的阳离子聚合性单体，其特征在于，R4表示C1-C10的直链或支链的n价烷基、C2-C10的n价链烯基、C3-C10的n价环烷基、C4-C10的n价环烷基烷基、C4-C10的n价烷基环烷基、C6-C20的n价芳基；任选地，这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代，条件是两个-O-不直接相连。
  13. 根据权利要求10或11所述的阳离子聚合性单体，其特征在于，R4表示C1-C8的直链或支链的n价烷基、C7-C12的n价芳基、n价苯基。
  14. 根据权利要求10所述的阳离子聚合性单体，其特征在于，R5选自C1-C4的直链或支链烷基，优选R5选自甲基或乙基。
  15. 根据权利要求10所述的阳离子聚合性单体，其特征在于，n为1-4的整数。
  16. 权利要求10至15中任一项所述的阳离子聚合性单体的制备方法，包括：通式(I)所示多官能度氧杂环丁烷类化合物与通式(V)所示酯化合物在催化剂存在条件下进行酯交换反应。
  17. 根据权利要求16所述的制备方法，其特征在于，所述酯交换反应中使用的催化剂是钛酸酯类化合物，优选地，所述催化剂为钛酸-2-乙基己酯、钛酸四甲酯、钛酸四乙酯、钛酸四异丙酯、钛酸四丁酯、钛酸四异丁酯中的一种或两种以上的组合。
  18. 一种阳离子聚合性单体，其特征在于，由权利要求1至6中任一项所述的通式(I)所示化合物与通式(VI)所示的异氰酸酯化合物反应而成，
    Figure PCTCN2017092227-appb-100008
    其中，R6表示p价连接基团，p表示1-8的整数；条件是，所述阳离子聚合性单体具有至少两个氧杂环丁烷基团。
  19. 根据权利要求18所述的阳离子聚合性单体，其特征在于，R6表示C1-C20的直链或支链的p价烷基、C2-C20的p价链烯基、C3-C20的p价环烷基、C4-C20的p价环烷基烷基、C4-C20的p价烷基环烷基、C6-C40的p价芳基；任选地，这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代，条件是两个-O-不直接相连；任选地，这些基团中的一个或多个氢原子可以独立地被选自烷基、卤素、硝基的基团所取代。
  20. 根据权利要求18或19所述的阳离子聚合性单体，其特征在于，R6表示C1-C10的直链或支链的p价烷基、C2-C10的p价链烯基、C3-C10的p价环烷基、C4-C10的p价环烷基烷基、C4-C10的p价烷基环烷基、C6-C20的p价芳基；任选地，这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代，条件是两个-O-不直接相连；任选地，这些基团中的一个或多个氢原子可以独立地被烷基所取代。
  21. 根据权利要求18或19所述的阳离子聚合性单体，其特征在于，R6表示C1-C8的直链或支链的p价烷基、C6-C12的p价芳基；任选地，这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代，条件是两个-O-不直接相连；任选地，这些基团中的一个或多个氢原子可以独立地被C1-C4的烷基所取代。
  22. 根据权利要求18所述的阳离子聚合性单体，其特征在于，p为1-4的整数。
  23. 权利要求18至22中任一项所述的阳离子聚合性单体的制备方法，其特征在于，所述制备方法包括：通式(I)所示多官能度氧杂环丁烷类化合物与通式(VI)所示异氰酸酯化合物在催化剂存在条件下反应，得到所述阳离子聚合性单体。
  24. 根据权利要求23所述的制备方法，其特征在于，所述催化剂为月桂酸二丁基锡。
  25. 权利要求1至6中任一项所述的多官能度氧杂环丁烷类化合物、或者权利要求8、10至15和18至22中任一项所述的阳离子聚合性单体在阳离子光固化组合物中的应用。
  26. 根据权利要求25所述的应用，其特征在于，所述光固化组合物中含有环氧类单体。
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