WO2019019924A1 - Oxetane monomer compound and preparation method therefor - Google Patents

Oxetane monomer compound and preparation method therefor Download PDF

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Publication number
WO2019019924A1
WO2019019924A1 PCT/CN2018/095454 CN2018095454W WO2019019924A1 WO 2019019924 A1 WO2019019924 A1 WO 2019019924A1 CN 2018095454 W CN2018095454 W CN 2018095454W WO 2019019924 A1 WO2019019924 A1 WO 2019019924A1
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group
valent
oxetane
branched
linear
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PCT/CN2018/095454
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French (fr)
Chinese (zh)
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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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Publication of WO2019019924A1 publication Critical patent/WO2019019924A1/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
    • 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

Definitions

  • the invention belongs to the field of organic chemistry, and particularly relates to an oxetane monomer compound and a preparation method thereof.
  • Oxetane compounds are important raw materials for high-end cationic photocuring products, and their application research began in 2008.
  • the Japanese East Asian Synthetic Company disclosed a series of oxetane monomers and oligomers in WO2008110512.
  • the main products are 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-[(2-ethylhexyloxy)methyloxetane], 3,3-( Oxydimethylene)-bis-(3-ethyl)oxetane, 1,4-bis-[(3-ethyl-3-oxymethylenecyclohexyl)methyl]benzene, etc.
  • the compounds, at least one oxetane group compound, cationic initiators and auxiliaries can be used in a variety of substrates.
  • These oxetane compounds generally have the characteristics of low viscosity, low toxicity, fast polymerization speed, excellent thermal stability and mechanical properties, and are applied to a cationic curing system to accelerate the polymerization speed and improve the performance of the cured product, but such
  • the practical application of the monomer still has obvious deficiencies.
  • the outstanding performance is that the types of compounds on the market are limited, the surface can be selected to be small, the price is expensive, the curing speed is still difficult to meet the market demand, and the cured product has properties such as hardness, flexibility and adhesion.
  • the performance of the aspect is difficult to balance.
  • the object of the present invention is to provide an oxetane monomer compound which has high reactivity and is excellent in hardness, flexibility and adhesion property after being applied to a cationic photocuring system. Compared with existing similar products, it has better overall application performance.
  • an oxetane monomer compound has a structure represented by the formula (I) or an ester compound of the compound of the formula (I), and the structure of the formula (I) is as follows:
  • R 1 means from An n-valent organic residue obtained by removing n oxirane group structures, a linear or branched n-valent alkyl group selected from C 1 -C 40 , and a C 2 -C 40 n-valent alkenyl group , an n-valent cycloalkyl group of C 3 -C 40 , an n-valent cycloalkylalkyl group of C 4 -C 40 , an n-valent alkylcycloalkyl group of C 4 -C 40 , and an n-valent aromatic group of C 6 -C 40 a C 7 -C 40 n-valent arylalkyl group, Wherein -CH 2 - may be optionally substituted by -O- or -OCH 2 CH 2 - provided that the two -O- are not directly attached;
  • R 4 and R 5 are the same or different and each independently represents a C 1 -C 10 linear or branched alkylene group
  • a 1 and A 2 are the same or different and each independently represents an empty, C 1 -C 10 alkylene group or a phenylene group;
  • n 1 and m 2 represent 0 or an integer greater than 0;
  • R 2 represents -CH 2 -, -(CH 2 -CH 2 -O) m -CH 2 -, -[CH 2 -CH(CH 3 )-O) m -CH 2 -, wherein m represents 0 or greater than 0 Integer
  • R 3 represents hydrogen, halogen, nitro, C 1 -C 20 linear or branched alkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkyl, C 4 -C 20 a cycloalkylalkyl group, a C 4 -C 20 alkylcycloalkyl group, 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 alkane Substituted by a group of a halogen, a nitro group;
  • n an integer of 1-8.
  • R 1 n is selected from C monovalent straight or branched chain alkyl of 1 -C 20, C n monovalent alkenyl of 2 -C 20, C 3 - An n-valent cycloalkyl group of C 20 , an n-valent cycloalkylalkyl group of C 4 -C 20 , an n-valent alkylcycloalkyl group of C 4 -C 20 , an n-valent aryl group of C 6 -C 20 , C 7 -C 20 n-valent arylalkyl, Wherein -CH 2 - may be optionally substituted by -O- or -OCH 2 CH 2 - provided that two -O- are not directly bonded; R 4 and R 5 each independently represent C 1 -C 4 a linear or branched alkylene group, A 1 and A 2 each independently represent an empty, C 1 -C 4 alkylene group or 1,4-phenylene
  • R 1 is selected from a linear or branched n-valent alkyl group of C 2 - C 12 , a C 2 - C 8 n-valent alkenyl group, C 3 - C 10 n-valent cycloalkyl, C 4 -C 14 n-valent cycloalkylalkyl, C 4 -C 14 n-valent alkylcycloalkyl, C 6 -C 10 n-valent aryl, C 7 - An n-valent arylalkyl group of C 12 , Wherein -CH 2 - may be optionally substituted by -O-, provided that two -O- are not directly bonded; and R 4 and R 5 each independently represent a straight or branched chain of C 1 -C 4
  • the alkyl group, A 1 and A 2 each independently represents an empty, C 1 -C 4 alkylene group or 1,4-phenylene group, and m 1 and m 2 represent an integer of
  • R 2 represents -CH 2 -, -(CH 2 -CH 2 -O) m -CH 2 -, -[CH 2 -CH(CH 3 )-O] m -CH 2 -, wherein m represents 0 An integer of -10.
  • m in R 2 represents 0, 1, 2 , 3 or 4.
  • R 3 represents hydrogen, a C 1 -C 10 linear or branched alkyl group, a C 2 -C 8 alkenyl group, a C 3 -C 10 cycloalkyl group, a C 4 -C 10 cycloalkane Alkylalkyl, C 4 -C 10 alkylcycloalkyl, phenyl.
  • R 3 represents a C 1 -C 4 linear or branched alkyl group, a C 3 -C 8 cycloalkyl group, a C 4 -C 8 cycloalkylalkyl group, or a phenyl group.
  • n is preferably an integer of from 1 to 6, more preferably 1, 2, 3 or 4.
  • the alkyl compound is a raw material and is reacted in the presence of a catalyst to obtain a product;
  • the catalyst used is a basic catalyst, which may be selected from the group consisting of alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and the like; alkali metal salts of alcohols such as sodium methoxide, potassium ethoxide and sodium t-butoxide. Etc.; alkali metal carbonates, such as sodium carbonate, potassium carbonate, etc.; alkali metal hydrogencarbonates, such as sodium bicarbonate, potassium hydrogencarbonate, etc.; alkyl metal lithium compounds, such as butyl lithium, phenyl lithium, etc.; A lithium compound such as lithium diisopropylamide, lithium hexamethyldisilazide or 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 10%, based on the mole of the compound of the formula (II).
  • a solvent may optionally be contained 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 and has no adverse effect on the reaction, and may be, for example, a nitrile solvent such as acetonitrile, propionitrile or benzonitrile; N,N-dimethylformamide, N An amide solvent such as N-dimethylacetamide or N-methylpyrrolidone; an ether solvent such as tetrahydrofuran or dioxane; an aromatic solvent such as benzene, toluene or xylene; and the like. These solvents may be used singly or in combination of two or more. The total amount may be adjusted depending on the homogeneity 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 25 to 200 ° C, preferably 50 to 150 ° C.
  • the reagents used in the above preparation methods are all known compounds in the prior art and are commercially available or conveniently prepared by known synthetic procedures.
  • a wide variety of monofunctional or polyfunctional monomeric compounds can be prepared as desired by selecting the starting materials for the reaction.
  • the oxetane monomer compound of the present invention may also be an esterified product of the compound of the formula (I), particularly by reacting a hydroxyl group in the structural formula with an acid halide, a carboxylic acid, an ester compound or an isocyanate compound. Those. By such a reaction, a new reactive group can be introduced or further macromated based on the structure of the compound of the general formula (I).
  • esterified compound of the compound of the formula (I) is obtained by reacting a compound of the formula (I) with a compound having the structure represented by the formula (IV) or (V):
  • R 6 represents a single bond or an n 1 -valent linking group selected from a single bond, a C 1 -C 20 linear or branched n 1 valent alkyl group, and a C 2 -C 20 n 1 valent alkenyl group; , C 3 -C n 1 price 20 cycloalkyl, C 4 -C n 1 price 20 cycloalkylalkyl, C 4 -C n 1 price 20 alkylcycloalkyl, C 6 -C 40 of n 1 monovalent aromatic group; optionally, these groups are -CH 2 - may be substituted with -O- or 1,4-phenylene, with the proviso that two not directly connected -O-; optionally, One or more hydrogen atoms of these groups may be independently substituted with a group selected from an alkyl group, a halogen, and a nitro group;
  • R 7 represents an n 2 -valent linking group, a linear or branched n 2 -valent alkyl group selected from C 1 -C 20 , a C 2 -C 20 n 2 -valent alkenyl group, and a C 3 -C 20 n a divalent cycloalkyl group, a C 4 -C 20 n 2 valent cycloalkylalkyl group, a C 4 -C 20 n 2 valent alkylcycloalkyl group, a C 6 -C 40 n 2 valent aryl group; optionally , -CH 2 - in these groups may be substituted by -O- or 1,4-phenylene, provided that two -O- are not directly attached; optionally, one or more of these groups One hydrogen atom may be independently substituted with a group selected from an alkyl group, a halogen, and a nitro group;
  • X represents a hydroxyl group, a halogen atom, or -OR 8 , wherein R 8 represents a C 1 -C 10 linear or branched alkyl group;
  • n 1 and n 2 each independently represent an integer of 1-8.
  • R 6 represents a single bond, a C 1 -C 14 linear or branched n 1 valent alkyl group, a C 2 -C 10 n 1 valent alkenyl group, a C 3 -C 10 n 1 valent cycloalkyl group, a C 1 -C 10 n 1 valent cycloalkylalkyl group, a C 4 -C 10 n 1 valent alkylcycloalkyl group, a C 6 -C 20 n 1 valent aryl group; optionally, these groups -CH 2 - may be substituted by -O- or 1,4-phenylene, provided that the two -O- are not directly attached;
  • R 7 represents a C 1 -C 14 linear or branched n 2 valent alkyl group, a C 2 -C 10 n 2 valent alkenyl group, a C 3 -C 10 n 2 valent cycloalkyl group, C 4 - An n 2 valent cycloalkylalkyl group of C 10 , a C 2 -C 10 n 2 valent alkylcycloalkyl group, a C 6 -C 20 n 2 valent aryl group; optionally, -CH of these groups 2 - may be substituted by -O- or 1,4-phenylene, provided that two -O- are not directly attached;
  • X represents hydroxy, chloro, bromo, -OCH 3 , or -OCH 2 CH 3 ;
  • n 1 and n 2 each independently represent 1, 2, 3 or 4.
  • R 6 represents a single bond, a C 1 -C 12 linear or branched n 1 valent alkyl group, a C 2 -C 6 n 1 valent alkenyl group, and a C 6 -C 12 n 1 valence.
  • Aryl; R 7 represents a C 1 -C 8 linear or branched n 2 valent alkyl group, a C 2 -C 6 n 2 valent alkenyl group, and a C 6 -C 12 n 2 valent aryl group.
  • the compounds of formula (IV) and (V) may be selected from the following compounds:
  • reaction of the compound of the formula (I) with the compound of the formula (IV) or (V) is a conventional reaction in the field of organic chemistry. Based on the knowledge of the above-mentioned starting materials and the synthetic idea, the specific reaction conditions are known to those skilled in the art. It is easy to determine.
  • the oxetane type monomer compound of the invention has excellent reactivity and is suitable for use in a cationic photocuring system, in particular for producing a surface coating composition, a powder coating composition, a printing ink, a printing plate, a dental composition. , stereolithography resin, adhesive, release coating, color filter, resist material or image recording material.
  • the present invention also relates to a photocurable composition
  • a photocurable composition comprising:
  • the component (a1) may be one or a combination of two or more of the oxetane-based monomer compounds of the present invention.
  • Examples of the component (a2) may be selected from a cyclic ether or a vinyl ether compound, and the cyclic ether is preferably an epoxide and other oxetane compounds.
  • Suitable epoxides may be glycidyl ether type epoxy compounds, alicyclic epoxy compounds, and the like.
  • the glycidyl ether type epoxy compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, and a hydrogenated bisphenol A type ring.
  • a diglycidyl ether of an oxygenated compound an alkylene oxide adduct of bisphenol F, a diglycidyl ether of an alkylene oxide adduct of hydrogenated bisphenol A, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether , trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hepta glycid
  • Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 2-(3,4-epoxycyclohexyl)- 5,5-spiro(3,4-epoxycyclohexane)-1,3 dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, vinyl dicyclohexyl Alkene, 4-vinyl epoxy cyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 , 4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadienyl diepoxide, ethylene glycol-di (3,4-epoxycyclohexanyl)ether, bis(3,4-ep
  • composition of the present invention may also contain other oxetane compounds, which may, but are not limited to, 3,3-bis(vinyloxymethyl)oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-[(benzene Oxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, 3,3-bis(chloromethyl)oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, bis ⁇ [1-ethyl( 3-oxetanyl)]methyl ⁇ ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene
  • a vinyl ether compound which can be used as the component (a2) may include: triethylene glycol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, 4-hydroxybutyl vinyl ether , propylene ether of propylene carbonate, tert-butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, ethylene glycol monoethyl ether, 1, 4 -cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, ethylene glycol butyl vinyl ether, butane-1,4-diol divinyl ether , hexanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, triethylene glycol methyl vinyl ether, tetraethylene glycol divinyl ether,
  • Component (b) in the above composition may be those of the cationic photoinitiator conventionally used in cationic polymerization.
  • it may be a phosphonium salt having a low nucleophilic anion such as a halosulfonium salt, an iodonium salt, a phosphonium salt, a cerium oxide salt or a diazonium salt, or a combination of two or more thereof.
  • Suitable anions include, for example, hexafluoroantimonate, hexafluorophosphate or tetrakis(pentafluoroaryl)borate, and the like.
  • phosphonium salts and iodonium salts in particular triarylsulfonium salts and di(alkylphenyl)iodonium salts.
  • a sulfur salt such as triallyl sulfodihexaphosphate or triarylsulfuric acid hexafluorophosphate; diaryliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and didodecane Iodine salt such as phenyl)iodotetrakis(pentafluorophenyl)borate or [4-(4-methylphenyl-2-methylpropyl)phenyl]iodohexafluorophosphate; tetrafluorophosphorus Phosphate such as fluorophosphate; pyridinium salt and the like.
  • compositions of the present invention may optionally incorporate organic or/and inorganic additives, including but not limited to sensitizers, colorants, depending on the application and performance requirements.
  • organic or/and inorganic additives including but not limited to sensitizers, colorants, depending on the application and performance requirements.
  • Fillers, plasticizers, leveling agents, silane coupling agents, curing agents, antioxidants, stabilizers, and the like, are readily known and ascertainable to those skilled in the art.
  • the photocurable composition of the present invention can be applied to glass, semiconductor, metal by a known means such as a spinner, a roll coater, a bar coater, a die coater, a curtain coater, various printing, dipping, and the like. , paper, plastic, film and other substrates.
  • 140 g (0.5 mol) of product 1, 107 g (0.5 mol) of raw material 3 and 150 g of toluene were successively added to a 500 ml four-necked flask equipped with a stirring device, a thermometer, a rectifying column and a water separator, and the water in the system was removed by heating under reflux.
  • the main performance indicators of the oxetane monomer compounds of the present invention are evaluated by formulating exemplary photocurable compositions, including curing speed, hardness, flexibility, adhesion, etc., and are commercially available.
  • the oxetane compound OXT-101 was compared to OXE-10.
  • the raw materials were uniformly mixed in a dark room to obtain a photocurable composition. Parts indicated are by mass unless otherwise indicated.
  • TTA21, OXT-101, OXE-10, and PAG-202 are as follows:
  • composition sample was weighed into an aluminum crucible, and the sample was scanned and cured using a Perkin Elmer Differential Scanning Calorimeter (DSC8000) equipped with a mercury arc lamp ultraviolet light source (OmniCure-S2000). The time from the initiation of UV to the maximum cure exotherm was recorded, and the shorter the time to reach the peak apex, the better the cure performance.
  • DSC8000 Perkin Elmer Differential Scanning Calorimeter
  • OmniCure-S2000 mercury arc lamp ultraviolet light source
  • the composition was applied to a PET film at a thickness of 25 ⁇ m, and received radiant energy of 200 mj/cm 2 to fully cure completely.
  • the composition was applied to a tinplate at a thickness of 25 ⁇ m and subjected to a radiant energy of 200 mj/cm 2 to fully cure completely.
  • a radiant energy 200 mj/cm 2
  • the outer side of the tinplate coated with the cured coating is wound in the longitudinal direction on the rod shaft of 10, 5, 4, 3, 2, 1 mm, and bent. 2-3 s, observed with a magnifying glass, indicating the flexibility of the UV-curable coating with the diameter of the smallest rod axis destroyed by the coating layer.
  • the composition was applied to a PET film at a thickness of 25 ⁇ m, and received radiant energy of 200 mj/cm 2 to fully cure completely.
  • 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 oxetane monomer compound of the present invention exhibits high reactivity when applied to a cationic photocuring system, and has a fast curing speed, which is significantly superior to commercially available oxygen.
  • the cyclobutane compound OXT-101 is equivalent to OXE-10; its cured coating has significantly higher hardness, more excellent flexibility and adhesion.
  • the oxetane monomer compounds of the present invention exhibit superior overall application properties compared to existing products of the same class.

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  • Health & Medical Sciences (AREA)
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Abstract

Disclosed is a new oxetane monomer compound, which has a structure as shown in general formula (I) or is an ester of a compound of general formula (I). The monomer compound has a high reaction activity. After being applied to a cationic photocurable system, the cured product has excellent hardness, flexibility and adhesion performance. Thus, the monomer compound has better overall application performance compared to existing similar products.

Description

一种氧杂环丁烷类单体化合物及其制备方法Oxycyclobutane monomer compound and preparation method thereof 技术领域Technical field
本发明属于有机化学领域，具体涉及一种氧杂环丁烷类单体化合物及其制备方法。The invention belongs to the field of organic chemistry, and particularly relates to an oxetane monomer compound and a preparation method thereof.
背景技术Background technique
氧杂环丁烷类化合物是高端阳离子光固化产品的重要原料，其应用研究始于2008年，日本东亚合成公司在WO2008110512中公开了一系列氧杂环丁烷类单体和齐聚物，其主要产品有3-乙基-3-羟甲基氧杂环丁烷、3-乙基-3-[(2-乙基己氧基)甲基氧杂环丁烷]、3,3-(氧基双亚甲)-双-(3-乙基)氧杂环丁烷、1,4-双-[(3-乙基-3-氧亚甲基氧杂环丁)甲基]苯等，它们具有粘度低、固化收缩小，固化速度快等优点。近年来，针对氧杂环丁烷类单体的研究逐渐引起业内关注，如Igarashi等在US5674992中公开了可固化阳离子涂料组合物，该组合物中含有环氧(如环氧乙烷)化合物和氧杂环丁烷化合物，组合物中不含溶剂，可通过调节组份的比例来调节粘度；Takami等在US5721020中公开了一种用于罐头包装的紫外固化涂料组合物，其含有可阳离子聚合的化合物、至少一个氧杂环丁烷基团的化合物、阳离子引发剂和助剂，可用于多种基材。这些氧杂环丁烷类化合物普遍具有粘度低、毒性小、聚合速度快、热稳定性和机械性能优异等特点，应用于阳离子固化体系可加速聚合速度，提高固化后产品的性能，但 是此类单体的实际应用仍然存在明显不足，突出地表现在，市场上化合物种类有限，可选择面小，价格昂贵，固化速度仍难以达到市场需求，固化后的产物在硬度、柔韧性及附着性等性能方面的表现难以均衡。Oxetane compounds are important raw materials for high-end cationic photocuring products, and their application research began in 2008. The Japanese East Asian Synthetic Company disclosed a series of oxetane monomers and oligomers in WO2008110512. The main products are 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-[(2-ethylhexyloxy)methyloxetane], 3,3-( Oxydimethylene)-bis-(3-ethyl)oxetane, 1,4-bis-[(3-ethyl-3-oxymethylenecyclohexyl)methyl]benzene, etc. They have the advantages of low viscosity, small curing shrinkage, and fast curing speed. In recent years, research on oxetane-based monomers has drawn attention in the industry, such as Igarashi et al., US Pat. No. 5,674,992, which discloses a curable cationic coating composition containing an epoxy (e.g., ethylene oxide) compound and An oxetane compound having no solvent in the composition, the viscosity can be adjusted by adjusting the proportion of the components; Takami et al., US Pat. No. 5,721,020 discloses an ultraviolet curable coating composition for can packaging which can be cationically polymerized. The compounds, at least one oxetane group compound, cationic initiators and auxiliaries can be used in a variety of substrates. These oxetane compounds generally have the characteristics of low viscosity, low toxicity, fast polymerization speed, excellent thermal stability and mechanical properties, and are applied to a cationic curing system to accelerate the polymerization speed and improve the performance of the cured product, but such The practical application of the monomer still has obvious deficiencies. The outstanding performance is that the types of compounds on the market are limited, the surface can be selected to be small, the price is expensive, the curing speed is still difficult to meet the market demand, and the cured product has properties such as hardness, flexibility and adhesion. The performance of the aspect is difficult to balance.
发明内容Summary of the invention
针对现有技术的不足，本发明的目的主要在于提供一种氧杂环丁烷类单体化合物，其反应活性高，应用于阳离子光固化体系后固化产物的硬度、柔韧性和附着性能优异，相较于现有的同类产品具有更好的整体应用性能。In view of the deficiencies of the prior art, the object of the present invention is to provide an oxetane monomer compound which has high reactivity and is excellent in hardness, flexibility and adhesion property after being applied to a cationic photocuring system. Compared with existing similar products, it has better overall application performance.
具体来说，一种氧杂环丁烷类单体化合物，具有通式(I)所示结构、或者是通式(I)化合物的酯化物，通式(I)的结构如下：Specifically, an oxetane monomer compound has a structure represented by the formula (I) or an ester compound of the compound of the formula (I), and the structure of the formula (I) is as follows:
Figure PCTCN2018095454-appb-000001
Figure PCTCN2018095454-appb-000001
其中，among them,
R 1表示从
Figure PCTCN2018095454-appb-000002
中除去n个环氧乙烷基团结构后得到的n价有机残基，选自C 1-C 40的直链或支链的n价烷基、C 2-C 40的n价链烯基、C 3-C 40的n价环烷基、C 4-C 40的n价环烷基烷基、C 4-C 40的n价烷基环烷基、C 6-C 40的n价芳基、C 7-C 40的n价芳基烷基、
Figure PCTCN2018095454-appb-000003
Figure PCTCN2018095454-appb-000004
Figure PCTCN2018095454-appb-000005
其中的-CH 2-可任选地被-O-或-OCH 2CH 2-所取代，条件是两个-O-不直接相连； R 1 means from
Figure PCTCN2018095454-appb-000002
An n-valent organic residue obtained by removing n oxirane group structures, a linear or branched n-valent alkyl group selected from C 1 -C 40 , and a C 2 -C 40 n-valent alkenyl group , an n-valent cycloalkyl group of C 3 -C 40 , an n-valent cycloalkylalkyl group of C 4 -C 40 , an n-valent alkylcycloalkyl group of C 4 -C 40 , and an n-valent aromatic group of C 6 -C 40 a C 7 -C 40 n-valent arylalkyl group,
Figure PCTCN2018095454-appb-000003
Figure PCTCN2018095454-appb-000004
Figure PCTCN2018095454-appb-000005
Wherein -CH 2 - may be optionally substituted by -O- or -OCH 2 CH 2 - provided that the two -O- are not directly attached;
R 4和R 5相同或不同，各自独立地表示C 1-C 10的直链或支链的亚烷基； R 4 and R 5 are the same or different and each independently represents a C 1 -C 10 linear or branched alkylene group;
A 1和A 2相同或不同，各自独立地表示空、C 1-C 10的亚烷基或亚苯基； A 1 and A 2 are the same or different and each independently represents an empty, C 1 -C 10 alkylene group or a phenylene group;
m 1和m 2表示0或大于0的整数； m 1 and m 2 represent 0 or an integer greater than 0;
R 2表示-CH 2-、-(CH 2-CH 2-O) m-CH 2-、-[CH 2-CH(CH 3)-O) m-CH 2-，其中m表示0或大于0的整数； R 2 represents -CH 2 -, -(CH 2 -CH 2 -O) m -CH 2 -, -[CH 2 -CH(CH 3 )-O) m -CH 2 -, wherein m represents 0 or greater than 0 Integer
R 3表示氢、卤素、硝基、C 1-C 20的直链或支链烷基、C 2-C 20的链烯基、C 3-C 20的环烷基、C 4-C 20的环烷基烷基、C 4-C 20的烷基环烷基、C 6-C 20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； R 3 represents hydrogen, halogen, nitro, C 1 -C 20 linear or branched alkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkyl, C 4 -C 20 a cycloalkylalkyl group, a C 4 -C 20 alkylcycloalkyl group, 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 alkane Substituted by a group of a halogen, a nitro group;
n表示1-8的整数。n represents an integer of 1-8.
作为优选技术方案，上述通式(I)结构中，R 1选自C 1-C 20的直链或支链的n价烷基、C 2-C 20的n价链烯基、C 3-C 20的n价环烷基、C 4-C 20的n价环烷基烷基、C 4-C 20的n价烷基环烷基、C 6-C 20的n价芳基、C 7-C 20的n价芳基烷基、
Figure PCTCN2018095454-appb-000006
Figure PCTCN2018095454-appb-000007
其中的-CH 2-可任选地被-O-或-OCH 2CH 2-所取代，条件是两个-O-不直接相连；R 4和R 5各自独立地表示C 1-C 4的直链或支链的亚烷基，A 1和A 2各自独立地表示空、C 1-C 4的亚烷基或1,4-亚苯基，m 1和m 2表示0-6的整数。 As a preferred aspect, (I) the structure of the above formula, R 1 n is selected from C monovalent straight or branched chain alkyl of 1 -C 20, C n monovalent alkenyl of 2 -C 20, C 3 - An n-valent cycloalkyl group of C 20 , an n-valent cycloalkylalkyl group of C 4 -C 20 , an n-valent alkylcycloalkyl group of C 4 -C 20 , an n-valent aryl group of C 6 -C 20 , C 7 -C 20 n-valent arylalkyl,
Figure PCTCN2018095454-appb-000006
Figure PCTCN2018095454-appb-000007
Wherein -CH 2 - may be optionally substituted by -O- or -OCH 2 CH 2 - provided that two -O- are not directly bonded; R 4 and R 5 each independently represent C 1 -C 4 a linear or branched alkylene group, A 1 and A 2 each independently represent an empty, C 1 -C 4 alkylene group or 1,4-phenylene group, and m 1 and m 2 represent an integer of 0-6. .
进一步优选地，上述通式(I)结构中，R 1选自C 2-C 12的直链或支链的n价烷基、C 2-C 8的n价链烯基、C 3-C 10的n价环烷基、C 4-C 14的n价环烷基烷基、C 4-C 14的n价烷基环烷基、C 6-C 10的n价芳基、C 7-C 12的n价芳基烷基、
Figure PCTCN2018095454-appb-000008
Figure PCTCN2018095454-appb-000009
其中的-CH 2-可任选地被-O-所取代，条件是两个-O-不直接相连；R 4和R 5各自独立地表示C 1-C 4的直链或支链的亚烷基，A 1和A 2各自独立地表示空、C 1-C 4的亚烷基或1,4-亚苯基，m 1和m 2表示0-4的整数。 Further preferably, in the above formula (I), R 1 is selected from a linear or branched n-valent alkyl group of C 2 - C 12 , a C 2 - C 8 n-valent alkenyl group, C 3 - C 10 n-valent cycloalkyl, C 4 -C 14 n-valent cycloalkylalkyl, C 4 -C 14 n-valent alkylcycloalkyl, C 6 -C 10 n-valent aryl, C 7 - An n-valent arylalkyl group of C 12 ,
Figure PCTCN2018095454-appb-000008
Figure PCTCN2018095454-appb-000009
Wherein -CH 2 - may be optionally substituted by -O-, provided that two -O- are not directly bonded; and R 4 and R 5 each independently represent a straight or branched chain of C 1 -C 4 The alkyl group, A 1 and A 2 each independently represents an empty, C 1 -C 4 alkylene group or 1,4-phenylene group, and m 1 and m 2 represent an integer of 0-4.
示例性地，
Figure PCTCN2018095454-appb-000010
选自具有以下结构的化合物： Illustratively,
Figure PCTCN2018095454-appb-000010
Selected from compounds having the following structure:
Figure PCTCN2018095454-appb-000011
Figure PCTCN2018095454-appb-000011
优选地，R 2表示-CH 2-、-(CH 2-CH 2-O) m-CH 2-、-[CH 2-CH(CH 3)-O] m-CH 2-，其中m表示0-10的整数。 Preferably, R 2 represents -CH 2 -, -(CH 2 -CH 2 -O) m -CH 2 -, -[CH 2 -CH(CH 3 )-O] m -CH 2 -, wherein m represents 0 An integer of -10.
更为优选地，R 2中m表示0、1、2、3或4。 More preferably, m in R 2 represents 0, 1, 2 , 3 or 4.
优选地，R 3表示氢、C 1-C 10的直链或支链烷基、C 2-C 8的链烯基、C 3-C 10的环烷基、C 4-C 10的环烷基烷基、C 4-C 10的烷基环烷基、苯基。 Preferably, R 3 represents hydrogen, a C 1 -C 10 linear or branched alkyl group, a C 2 -C 8 alkenyl group, a C 3 -C 10 cycloalkyl group, a C 4 -C 10 cycloalkane Alkylalkyl, C 4 -C 10 alkylcycloalkyl, phenyl.
更为优选地，R 3表示C 1-C 4的直链或支链烷基、C 3-C 8的环烷基、C 4-C 8的环烷基烷基、或苯基。 More preferably, R 3 represents a C 1 -C 4 linear or branched alkyl group, a C 3 -C 8 cycloalkyl group, a C 4 -C 8 cycloalkylalkyl group, or a phenyl group.
n优选是1-6的整数，更优选1、2、3或4。n is preferably an integer of from 1 to 6, more preferably 1, 2, 3 or 4.
具有上述通式(I)所示结构的氧杂环丁烷类单体化合物的制备方法，包括：以通式(II)所示环氧化合物与通式(III)所示含氧杂环丁烷基的化合物为原料，在催化剂存在条件下反应得到产物；A method for producing an oxetane monomer compound having the structure represented by the above formula (I), comprising: an epoxy compound represented by the formula (II) and an oxetane group represented by the formula (III) The alkyl compound is a raw material and is reacted in the presence of a catalyst to obtain a product;
反应式如下所示：The reaction formula is as follows:
Figure PCTCN2018095454-appb-000012
Figure PCTCN2018095454-appb-000012
上述制备方法中，使用的催化剂是碱性催化剂，可选自：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1-10％。In the above preparation method, the catalyst used is a basic catalyst, which may be selected from the group consisting of alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and the like; alkali metal salts of alcohols such as sodium methoxide, potassium ethoxide and sodium t-butoxide. Etc.; alkali metal carbonates, such as sodium carbonate, potassium carbonate, etc.; alkali metal hydrogencarbonates, such as sodium bicarbonate, potassium hydrogencarbonate, etc.; alkyl metal lithium compounds, such as butyl lithium, phenyl lithium, etc.; A lithium compound such as lithium diisopropylamide, lithium hexamethyldisilazide or 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 10%, based on the mole of the compound of the formula (II).
以形成均一体系为目的，根据原料种类，反应体系中可任选地包含溶剂。对适用的溶剂种类没有特殊限定，只要能够溶解反应原料且对反应无不良影响即可，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；等等。这些溶剂可以单独使用，也可以两种以上混合使用， 总用量可根据反应体系的均一性和搅拌性进行调节，这对本领域技术人员而言是容易确定的。For the purpose of forming a uniform system, a solvent may optionally be contained 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 and has no adverse effect on the reaction, and may be, for example, a nitrile solvent such as acetonitrile, propionitrile or benzonitrile; N,N-dimethylformamide, N An amide solvent such as N-dimethylacetamide or N-methylpyrrolidone; an ether solvent such as tetrahydrofuran or dioxane; an aromatic solvent such as benzene, toluene or xylene; and the like. These solvents may be used singly or in combination of two or more. The total amount may be adjusted depending on the homogeneity and agitation of the reaction system, which is easily determined by those skilled in the art.
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。The reaction temperature varies depending on the kind of the raw material, and is usually 25 to 200 ° C, preferably 50 to 150 ° C. There is no particular limitation on the reaction pressure, and it is usually normal pressure.
反应结束后，调节体系pH值至中性，过滤，水洗，萃取，减压蒸馏，即可得到通式(I)所示的氧杂环丁烷类单体化合物。After completion of the reaction, the pH of the system is adjusted to neutrality, filtered, washed with water, extracted, and distilled under reduced pressure to obtain an oxetane monomer compound of the formula (I).
上述制备方法中使用到的反应试剂均为现有技术中的已知化合物，可通过商购获得或经已知合成工艺方便地制得。通过选择反应原料，可根据需求制得种类多样的单官能或多官能单体化合物。The reagents used in the above preparation methods are all known compounds in the prior art and are commercially available or conveniently prepared by known synthetic procedures. A wide variety of monofunctional or polyfunctional monomeric compounds can be prepared as desired by selecting the starting materials for the reaction.
如上所述，本发明的氧杂环丁烷类单体化合物还可以是通式(I)化合物的酯化物，特别是经由结构式中羟基与酰卤化物、羧酸、酯化合物或异氰酸酯化合物反应生成的那些。通过此类反应，可在通式(I)化合物的结构基础上引入新的活性基团或将其进一步大分子化。As described above, the oxetane monomer compound of the present invention may also be an esterified product of the compound of the formula (I), particularly by reacting a hydroxyl group in the structural formula with an acid halide, a carboxylic acid, an ester compound or an isocyanate compound. Those. By such a reaction, a new reactive group can be introduced or further macromated based on the structure of the compound of the general formula (I).
具体地，所述的通式(I)化合物的酯化物，由通式(I)化合物与具有通式(IV)或通式(V)所示结构的化合物反应而成：Specifically, the esterified compound of the compound of the formula (I) is obtained by reacting a compound of the formula (I) with a compound having the structure represented by the formula (IV) or (V):
Figure PCTCN2018095454-appb-000013
Figure PCTCN2018095454-appb-000013
其中，R 6表示单键或n 1价连接基团，选自单键、C 1-C 20的直链或支链的n 1价烷基、C 2-C 20的n 1价链烯基、C 3-C 20的n 1价环烷基、C 4-C 20的n 1价环烷基烷基、C 4-C 20的n 1价烷基环烷基、C 6-C 40的n 1价芳基；任选地，这些基团中的-CH 2-可被-O-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； Wherein R 6 represents a single bond or an n 1 -valent linking group selected from a single bond, a C 1 -C 20 linear or branched n 1 valent alkyl group, and a C 2 -C 20 n 1 valent alkenyl group; , C 3 -C n 1 price 20 cycloalkyl, C 4 -C n 1 price 20 cycloalkylalkyl, C 4 -C n 1 price 20 alkylcycloalkyl, C 6 -C 40 of n 1 monovalent aromatic group; optionally, these groups are -CH 2 - may be substituted with -O- or 1,4-phenylene, with the proviso that two not directly connected -O-; optionally, One or more hydrogen atoms of these groups may be independently substituted with a group selected from an alkyl group, a halogen, and a nitro group;
R 7表示n 2价连接基团，选自C 1-C 20的直链或支链的n 2价烷基、C 2-C 20的n 2价链烯基、C 3-C 20的n 2价环烷基、C 4-C 20的n 2价环烷基烷基、C 4-C 20的n 2价烷基环烷基、C 6-C 40的n 2价芳基；任选地，这些基团中的-CH 2-可被-O-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； R 7 represents an n 2 -valent linking group, a linear or branched n 2 -valent alkyl group selected from C 1 -C 20 , a C 2 -C 20 n 2 -valent alkenyl group, and a C 3 -C 20 n a divalent cycloalkyl group, a C 4 -C 20 n 2 valent cycloalkylalkyl group, a C 4 -C 20 n 2 valent alkylcycloalkyl group, a C 6 -C 40 n 2 valent aryl group; optionally , -CH 2 - in these groups may be substituted by -O- or 1,4-phenylene, provided that two -O- are not directly attached; optionally, one or more of these groups One hydrogen atom may be independently substituted with a group selected from an alkyl group, a halogen, and a nitro group;
X表示羟基、卤原子、或-OR 8，其中R 8表示C 1-C 10的直链或支链烷基； X represents a hydroxyl group, a halogen atom, or -OR 8 , wherein R 8 represents a C 1 -C 10 linear or branched alkyl group;
n 1与n 2各自独立地表示1-8的整数。 n 1 and n 2 each independently represent an integer of 1-8.
基于对原料成本和反应难易程度考虑，优选地，上述通式(IV)和(V)的结构中：Based on the consideration of the raw material cost and the ease of reaction, preferably, in the structures of the above general formulae (IV) and (V):
R 6表示单键、C 1-C 14的直链或支链的n 1价烷基、C 2-C 10的n 1价链烯基、C 3-C 10的n 1价环烷基、C 4-C 10的n 1价环烷基烷基、C 4-C 10的n 1价烷基环烷基、C 6-C 20的n 1价芳基；任选地，这些基团中的-CH 2-可被-O-或者1,4-亚苯基所取代，条件是两个-O-不直接相连； R 6 represents a single bond, a C 1 -C 14 linear or branched n 1 valent alkyl group, a C 2 -C 10 n 1 valent alkenyl group, a C 3 -C 10 n 1 valent cycloalkyl group, a C 1 -C 10 n 1 valent cycloalkylalkyl group, a C 4 -C 10 n 1 valent alkylcycloalkyl group, a C 6 -C 20 n 1 valent aryl group; optionally, these groups -CH 2 - may be substituted by -O- or 1,4-phenylene, provided that the two -O- are not directly attached;
R 7表示C 1-C 14的直链或支链的n 2价烷基、C 2-C 10的n 2价链烯基、C 3-C 10的n 2价环烷基、C 4-C 10的n 2价环烷基烷基、C 4-C 10的n 2价烷基环烷基、C 6-C 20的n 2价芳基；任选地，这些基团中的-CH 2-可被-O-或者1,4-亚苯基所取代，条件是两个-O-不直接相连； R 7 represents a C 1 -C 14 linear or branched n 2 valent alkyl group, a C 2 -C 10 n 2 valent alkenyl group, a C 3 -C 10 n 2 valent cycloalkyl group, C 4 - An n 2 valent cycloalkylalkyl group of C 10 , a C 2 -C 10 n 2 valent alkylcycloalkyl group, a C 6 -C 20 n 2 valent aryl group; optionally, -CH of these groups 2 - may be substituted by -O- or 1,4-phenylene, provided that two -O- are not directly attached;
X表示羟基、氯、溴、-OCH 3、或-OCH 2CH 3； X represents hydroxy, chloro, bromo, -OCH 3 , or -OCH 2 CH 3 ;
n 1与n 2各自独立地表示1、2、3或4。 n 1 and n 2 each independently represent 1, 2, 3 or 4.
更优选地，R 6表示单键、C 1-C 12的直链或支链的n 1价烷基、C 2-C 6的n 1价链烯基、C 6-C 12的n 1价芳基；R 7表示C 1-C 8的直链或支链的n 2价烷基、C 2-C 6的n 2价链烯基、C 6-C 12的n 2价芳基。 More preferably, R 6 represents a single bond, a C 1 -C 12 linear or branched n 1 valent alkyl group, a C 2 -C 6 n 1 valent alkenyl group, and a C 6 -C 12 n 1 valence. Aryl; R 7 represents a C 1 -C 8 linear or branched n 2 valent alkyl group, a C 2 -C 6 n 2 valent alkenyl group, and a C 6 -C 12 n 2 valent aryl group.
示例性地，通式(IV)和(V)所示化合物可选自下列化合物：Illustratively, the compounds of formula (IV) and (V) may be selected from the following compounds:
Figure PCTCN2018095454-appb-000014
Figure PCTCN2018095454-appb-000014
通式(I)化合物与通式(IV)或通式(V)所示化合物的反应是有机化学领域的常规反应，在知晓上述原料种类及合成思路的基础上，具体反应条件对本领域技术人员而言是容易确定的。The reaction of the compound of the formula (I) with the compound of the formula (IV) or (V) is a conventional reaction in the field of organic chemistry. Based on the knowledge of the above-mentioned starting materials and the synthetic idea, the specific reaction conditions are known to those skilled in the art. It is easy to determine.
本发明的氧杂环丁烷类单体化合物具有优异的反应活性，适用于阳离子光固化体系，特别是用于制造表面涂料组合物、粉末涂料组合物、印刷油墨、印刷版、牙科用组合物、立体平版印刷树脂、粘合剂、防粘涂料、滤色器、抗蚀剂材料或图像记录材料等。The oxetane type monomer compound of the invention has excellent reactivity and is suitable for use in a cationic photocuring system, in particular for producing a surface coating composition, a powder coating composition, a printing ink, a printing plate, a dental composition. , stereolithography resin, adhesive, release coating, color filter, resist material or image recording material.
相应地，本发明还涉及一种光固化组合物，包含：Accordingly, the present invention also relates to a photocurable composition comprising:
(a1)至少一种本发明的上述氧杂环丁烷类单体化合物；(a1) at least one of the above oxetane-based monomer compounds of the present invention;
(a2)阳离子或酸催化下可聚合的化合物；和(a2) a cation or acid catalyzed polymerizable compound;
(b)阳离子引发剂。(b) a cationic initiator.
组分(a1)可以是本发明所述的氧杂环丁烷类单体化合物中的一种或两种以上的组合。The component (a1) may be one or a combination of two or more of the oxetane-based monomer compounds of the present invention.
组分(a2)的实例可选自环醚或乙烯基醚化合物，所述环醚优选环氧化物和其它氧杂环丁烷类化合物。Examples of the component (a2) may be selected from a cyclic ether or a vinyl ether compound, and the cyclic ether is preferably an epoxide and other oxetane compounds.
适用的环氧化物可以是缩水甘油醚型环氧化合物、脂环族环氧化合物等。作为缩水甘油醚型环氧化合物的例子，可以举出双酚A型环氧化合物、双酚F型环氧化合物、苯酚酚醛型环氧化合物、甲酚醛型环氧化合物、氢化双酚A型环氧化合物、双酚F的环氧烷加成物的二缩水甘油醚，氢化双酚A的环氧烷加成物的二缩水甘油醚、乙二醇二缩水甘油醚、丙二醇二缩水甘油醚、新戊二醇二缩水甘油醚、丁二醇二缩水甘油醚、己二醇二缩水甘油醚、环己烷二甲醇二缩水甘油醚、 聚乙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、三羟甲基丙烷二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、季戊四醇三缩水甘油醚、季戊四醇四缩水甘油醚、山梨糖醇七缩水甘油醚、山梨糖醇六缩水甘油醚、间苯二酚缩水甘油醚、二环戊二稀苯酚加成型缩水甘油醚、1,6-二羟基萘二缩水甘油醚等。作为脂环式环氧化合物的例子，可以举出3,4-环氧环己基甲基-3,4-环氧环己烷羧酸酯、2-(3,4-环氧环己基)-5,5-螺(3,4-环氧环己烷基)-1,3二氧六环、双(3,4-环氧环己基甲基)己二酸酯、二氧化乙烯基环己烯、4-乙烯基环氧环己烷、双(3,4-环氧-6-甲基环己基甲基)己二酸酯、3,4-环氧-6-甲基环己基-3,4-环氧基-6-甲基环己烷羧酸酯、亚甲基二(3,4-环氧基环己烷)、二环戊二稀二环氧化物、乙二醇-二(3,4-环氧环己玩甲基)醚、双(3,4-环氧基环己烷羧酸)乙二酯、双(3,4-环氧基环己烷羧酸)丙二酯、环氧六氢苯二酸二辛酯、环氧六氢苯二酸二-2-乙基己酯、1,4-环己烷二甲醇-二(3,4-环氧环己烷羧酸酯)、四氢茚二环氧化物、3,4,3',4'-二环氧二环已烷等。Suitable epoxides may be glycidyl ether type epoxy compounds, alicyclic epoxy compounds, and the like. Examples of the glycidyl ether type epoxy compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, and a hydrogenated bisphenol A type ring. a diglycidyl ether of an oxygenated compound, an alkylene oxide adduct of bisphenol F, a diglycidyl ether of an alkylene oxide adduct of hydrogenated bisphenol A, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether , trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hepta glycidyl ether, sorbitol hexahydroglycidyl ether, Hydroquinone glycidyl ether, dicyclopentane phenol plus glycidyl ether, 1,6-dihydroxynaphthalene diglycidyl ether, and the like. Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 2-(3,4-epoxycyclohexyl)- 5,5-spiro(3,4-epoxycyclohexane)-1,3 dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, vinyl dicyclohexyl Alkene, 4-vinyl epoxy cyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 , 4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadienyl diepoxide, ethylene glycol-di (3,4-epoxycyclohexanyl)ether, bis(3,4-epoxycyclohexanecarboxylic acid)ethylenediester, bis(3,4-epoxycyclohexanecarboxylic acid)propane Diester, epoxy dioctyl hexahydrophthalate, di-2-ethylhexyl hexahydrophthalate, 1,4-cyclohexane dimethanol-bis(3,4-epoxycyclohexane An alkanecarboxylic acid ester), a tetrahydroindole diepoxide, a 3,4,3',4'-diepoxybicyclohexane or the like.
如果需要，本发明的上述组合物也可包含其它氧杂环丁烷类化合物，可以例举出(但不限于此)：3,3-双(乙烯氧基甲基)氧杂环丁烷、3-乙基-3-羟基甲基氧杂环丁烷、3-乙基-3-(2-乙基己氧基甲基)氧杂环丁烷、3-乙基-3-[(苯氧基)甲基]氧杂环丁烷、3-乙基-3-(己氧基甲基)氧杂环丁烷、3-乙基-3-(氯甲基)氧杂环丁烷、3,3-双(氯甲基)氧杂环丁烷、1,4-双[(3-乙基-3-氧杂环丁基甲氧基)甲基]苯、双{[1-乙基(3-氧杂环丁基)]甲基}醚、4,4’-双[(3-乙基-3-氧杂环丁基)甲氧基甲基] 双环己烷、1,4-双[(3-乙基-3-氧杂环丁基)甲氧基甲基]环己烷、3-乙基-3[[(3-乙基氧杂环丁烷-3-基)甲氧基]甲基]氧杂环丁烷等。除此以外，专利申请号为201610548580.7和201610550205.6的中国专利申请中公开的那些氧杂环丁烷类化合物也可以用于该组合物配方中，在此将其全文引入以作为参考。If desired, the above composition of the present invention may also contain other oxetane compounds, which may, but are not limited to, 3,3-bis(vinyloxymethyl)oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-[(benzene Oxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, 3,3-bis(chloromethyl)oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, bis{[1-ethyl( 3-oxetanyl)]methyl}ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]bicyclohexane, 1,4-double [(3-Ethyl-3-oxetanyl)methoxymethyl]cyclohexane, 3-ethyl-3[[(3-ethyloxetan-3-yl)methoxy Methyl]oxetane and the like. In addition, those oxetane compounds disclosed in Chinese Patent Application No. 201610548580.7 and No. 201610550205.6 can also be used in the formulation of the composition, which is hereby incorporated by reference in its entirety.
可作为组分(a2)使用的乙烯基醚化合物，其实例可包括：三乙二醇二乙烯基醚、1,4-环己烷二甲醇二乙烯基醚、4-羟基丁基乙烯基醚、碳酸丙烯酯的丙烯基醚、叔丁基乙烯基醚、叔戊基乙烯基醚、环己基乙烯基醚、2-乙基己基乙烯基醚、乙二醇单乙稀基醚、1,4-环己烷二甲醇单乙烯基醚、二乙二醇单乙烯基醚、乙二醇二乙烯基醚、乙二醇丁基乙烯基醚、丁烷-1,4-二醇二乙烯基醚、己二醇二乙烯基醚、二乙二醇二乙烯基醚、三乙二醇二乙烯基醚、三乙二醇甲基乙烯基醚、四乙二醇二乙烯基醚、聚四氢呋喃二乙烯基醚-290、三羟甲基丙烷三乙烯基醚、二丙二醇二乙烯基醚、十八烷基乙烯基醚等。A vinyl ether compound which can be used as the component (a2), and examples thereof may include: triethylene glycol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, 4-hydroxybutyl vinyl ether , propylene ether of propylene carbonate, tert-butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, ethylene glycol monoethyl ether, 1, 4 -cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, ethylene glycol butyl vinyl ether, butane-1,4-diol divinyl ether , hexanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, triethylene glycol methyl vinyl ether, tetraethylene glycol divinyl ether, polytetrahydrofuran divinyl Ethyl ether-290, trimethylolpropane trivinyl ether, dipropylene glycol divinyl ether, octadecyl vinyl ether, and the like.
上述组合物中的组分(b)可以是阳离子聚合反应中常规使用的那些阳离子光引发剂种类。示例性地，可以是具有低亲核性阴离子的鎓盐，如卤鎓盐、碘鎓盐、锍盐、氧化锍盐或重氮盐，中的一种或两种以上的组合。合适的阴离子包括，例如，六氟锑酸根、六氟磷酸根或四(五氟芳基)硼酸根等。优选锍盐和碘鎓盐，特别是三芳基锍盐和二(烷基苯基)碘鎓盐。可列举例如：三烯丙基硫六氟磷酸盐、三芳基硫六氟锑酸盐等硫盐；二芳基碘六氟磷酸盐、二苯基碘六氟锑酸盐、二(十二烷基苯基)碘四(五氟苯基)硼酸盐、[4-(4-甲基苯基-2-甲 基丙基)苯基]碘六氟磷酸盐等碘盐；四氟磷六氟磷酸盐等磷盐；吡啶盐等。Component (b) in the above composition may be those of the cationic photoinitiator conventionally used in cationic polymerization. Illustratively, it may be a phosphonium salt having a low nucleophilic anion such as a halosulfonium salt, an iodonium salt, a phosphonium salt, a cerium oxide salt or a diazonium salt, or a combination of two or more thereof. Suitable anions include, for example, hexafluoroantimonate, hexafluorophosphate or tetrakis(pentafluoroaryl)borate, and the like. Preference is given to phosphonium salts and iodonium salts, in particular triarylsulfonium salts and di(alkylphenyl)iodonium salts. For example, a sulfur salt such as triallyl sulfodihexaphosphate or triarylsulfuric acid hexafluorophosphate; diaryliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and didodecane Iodine salt such as phenyl)iodotetrakis(pentafluorophenyl)borate or [4-(4-methylphenyl-2-methylpropyl)phenyl]iodohexafluorophosphate; tetrafluorophosphorus Phosphate such as fluorophosphate; pyridinium salt and the like.
除了组分(a1)、(a2)和(b)之外，本发明组合物还可根据应用和性能需要选择性地添加有机或/和无机添加剂，包括但不限于增感剂、着色剂、填料、增塑剂、流平剂、硅烷偶联剂、固化剂、抗氧化剂、稳定剂等，这对本领域技术人员而言是容易获知和确定的。In addition to components (a1), (a2), and (b), the compositions of the present invention may optionally incorporate organic or/and inorganic additives, including but not limited to sensitizers, colorants, depending on the application and performance requirements. Fillers, plasticizers, leveling agents, silane coupling agents, curing agents, antioxidants, stabilizers, and the like, are readily known and ascertainable to those skilled in the art.
实际应用中，本发明的光固化组合物可通过旋涂器、辊涂器、棒涂器、模涂器、帘式涂布器、各种印刷、浸渍等公知手段应用于玻璃、半导体、金属、纸、塑料、薄膜等各类基材上。In practical applications, the photocurable composition of the present invention can be applied to glass, semiconductor, metal by a known means such as a spinner, a roll coater, a bar coater, a die coater, a curtain coater, various printing, dipping, and the like. , paper, plastic, film and other substrates.
具体实施方式Detailed ways
以下将通过实施例对本发明进行进一步的具体说明，但是本发明的范围不局限于这些实施例。The invention will be further specifically described by the following examples, but the scope of the invention is not limited to the examples.
制备实施例Preparation example
实施例1Example 1
产物1的制备Preparation of product 1
Figure PCTCN2018095454-appb-000015
Figure PCTCN2018095454-appb-000015
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58g(0.5mol)原料1、2g(0.05mol)氢氧化钠及100g甲苯，搅拌升温至80℃，滴加82g(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，用5％的盐酸溶液调节pH值至中性，滤去沉淀物，再水洗萃取3次、减压蒸馏除去有机溶剂，得到136g淡黄色液体。Into a 250 ml four-necked flask equipped with a stirring device, a thermometer, and a reflux condenser, 58 g (0.5 mol) of a raw material, 1, 2 g (0.05 mol) of sodium hydroxide and 100 g of toluene were successively added, and the mixture was stirred and heated to 80 ° C, and 82 g (0.5 g) was added dropwise. Mol) raw material 2, 1.5h drop addition, continue to stir the reaction, gas phase tracking until the content of raw material 1 no longer changes, stop heating, adjust the pH to neutral with 5% hydrochloric acid solution, filter the precipitate, then wash and extract 3 The organic solvent was distilled off under reduced pressure to give 136 g of pale yellow liquid.
产物1的结构通过LC-MS和 1H-NMR得到确认。 The structure of the product 1 was confirmed by LC-MS and 1 H-NMR.
MS(m/e)：281(M+1)；MS (m/e): 281 (M + 1);
1H-NMR(CDCl 3，500MHz)：δ0.96(3H，m)，δ1.25(2H，m)，δ2.01(1H，d)，δ3.29(2H，s)，δ3.52-3.87(5H，m)，δ4.63-4.65(6H，s)，δ7.19(5H，d)。 1 H-NMR (CDCl 3 , 500 MHz): δ 0.96 (3H, m), δ 1.25 (2H, m), δ 2.01 (1H, d), δ 3.29 (2H, s), δ 3.52 -3.87 (5H, m), δ 4.63-4.65 (6H, s), δ 7.19 (5H, d).
实施例2Example 2
产物2的制备Preparation of product 2
Figure PCTCN2018095454-appb-000016
Figure PCTCN2018095454-appb-000016
向装有搅拌装置、温度计、精馏柱和分水器的500ml四口烧瓶中依次加入140g(0.5mol)产物1、107g(0.5mol)原料3及150g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221g。140 g (0.5 mol) of product 1, 107 g (0.5 mol) of raw material 3 and 150 g of toluene were successively added to a 500 ml four-necked flask equipped with a stirring device, a thermometer, a rectifying column and a water separator, and the water in the system was removed by heating under reflux. After cooling to about 60 °C, add 2.5g of tetraethyl titanate, heat reflux reaction, adjust the reflux ratio to take out the methanol formed by the reaction, when the temperature of the top of the distillation column rises to 110 ° C to stop the reaction, cool down to 70 ° C, add 10 g of water was stirred for 1 h, filtered while hot, and the filtrate was evaporated under reduced pressure to give 221 g of pale yellow viscous liquid.
产物2的结构通过LC-MS和 1H-NMR得到确认。 The structure of the product 2 was confirmed by LC-MS and 1 H-NMR.
MS(m/e)：463(M+1)；MS (m / e): 463 (M + 1);
1H-NMR(CDCl 3，500MHz)：δ0.96(6H，m)，δ1.25-2.25(22H，m)，δ3.29(2H，s)，δ3.61(4H，d)，δ4.61-4.63(3H，m)，δ4.65(4H，s)，δ7.19(5H，d)。 1 H-NMR (CDCl 3 , 500 MHz): δ 0.96 (6H, m), δ 1.25-2.25 (22H, m), δ 3.29 (2H, s), δ 3.61 (4H, d), δ 4 .61-4.63 (3H, m), δ 4.65 (4H, s), δ 7.19 (5H, d).
实施例3Example 3
产物3的制备Preparation of product 3
Figure PCTCN2018095454-appb-000017
Figure PCTCN2018095454-appb-000017
向装有搅拌装置、温度计的500ml四口烧瓶中加入140g(0.5mol)产物1、51g(0.5mol)三乙胺及100g二氯乙烷，温度控制在10℃左右，再称取31.5g(0.25mol)原料4即草酰氯于50ml恒压滴液漏斗中，缓慢滴加，滴完继续反应，液相跟踪原料1反应完全，停止反应。 反应结束后，水洗至中性，过滤，滤液减压蒸馏得淡黄色粘稠液体147g。Into a 500 ml four-necked flask equipped with a stirring device and a thermometer, 140 g (0.5 mol) of product 1, 51 g (0.5 mol) of triethylamine and 100 g of dichloroethane were added, and the temperature was controlled at about 10 ° C, and then 31.5 g (... 0.25 mol) of the starting material 4, namely oxalyl chloride, was slowly added dropwise in a 50 ml constant pressure dropping funnel, and the reaction was continued after the dropwise addition, and the liquid phase was traced to the completion of the reaction of the starting material 1 to stop the reaction. After completion of the reaction, the mixture was washed with water until neutral, filtered, and the filtrate was evaporated under reduced pressure to yield 147 g of pale yellow viscous liquid.
产物3的结构通过LC-MS和 1H-NMR得到确认。 The structure of the product 3 was confirmed by LC-MS and 1 H-NMR.
MS(m/e)：615(M+1)；MS (m/e): 615 (M + 1);
1H-NMR(CDCl 3，500MHz)：δ0.96-1.25(10H，m)，δ3.29(4H，s)，δ3.61(8H，d)，δ4.61-4.65(14H，m)，δ7.19(10H，m)。 1 H-NMR (CDCl 3 , 500 MHz): δ 0.96-1.25 (10H, m), δ 3.29 (4H, s), δ 3.61 (8H, d), δ 4.61-4.65 (14H, m) , δ 7.19 (10H, m).
实施例4Example 4
产物4的制备Preparation of product 4
Figure PCTCN2018095454-appb-000018
Figure PCTCN2018095454-appb-000018
向装有搅拌装置、温度计的250ml四口烧瓶中加入140g(0.5mol)产物1及0.1g月桂酸二丁基锡，温度控制在40℃左右，滴加42g(0.25mol)原料5即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。Into a 250 ml four-necked flask equipped with a stirring device and a thermometer, 140 g (0.5 mol) of product 1 and 0.1 g of dibutyltin laurate were added, and the temperature was controlled at about 40 ° C, and 42 g (0.25 mol) of the starting material 5, hexamethylene group, was added dropwise. The diisocyanate is added to the incubation reaction until the NCO value falls below 0.05%, and the reaction is terminated.
产物4的结构通过LC-MS和 1H-NMR得到确认。 The structure of the product 4 was confirmed by LC-MS and 1 H-NMR.
MS(m/e)：729(M+1)；MS (m / e): 729 (M + 1);
1H-NMR(CDCl 3，500MHz)：δ0.96-1.25(10H，m)，δ1.29-2.96(12H，m)，δ3.29(4H，s)，δ3.61(8H，d)，δ4.61-4.65(14H，m)，δ7.19(10H，m)，δ8.0(2H，m)。 1 H-NMR (CDCl 3 , 500 MHz): δ 0.96-1.25 (10H, m), δ 1.29-2.96 (12H, m), δ 3.29 (4H, s), δ 3.61 (8H, d) , δ 4.61-4.65 (14H, m), δ 7.19 (10H, m), δ 8.0 (2H, m).
实施例5Example 5
产物5的制备Preparation of product 5
Figure PCTCN2018095454-appb-000019
Figure PCTCN2018095454-appb-000019
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6、2g(0.05mol)氢氧化钠及100g甲苯，搅拌升温至80℃，滴加78g(0.25mol)原料7，1.5h滴加完，继续搅拌反应，气相跟踪至原料6含量不再变化，停止加热，调节pH值至中性，过滤，水洗、萃取，减压蒸馏，得到136g淡黄色液体。102 g (0.5 mol) of raw materials 6, 2 g (0.05 mol) of sodium hydroxide and 100 g of toluene were sequentially added to a 250 ml four-necked flask equipped with a stirring device, a thermometer, and a reflux condenser, and the mixture was stirred and heated to 80 ° C, and 78 g (0.25 g) was added dropwise. Mol) raw material 7, 1.5h drop addition, continue to stir the reaction, gas phase tracking until the content of raw material 6 no longer changes, stop heating, adjust the pH to neutral, filter, water wash, extraction, distillation under reduced pressure, to obtain 136g light yellow liquid .
产物5的结构通过LC-MS和 1H-NMR得到确认。 The structure of the product 5 was confirmed by LC-MS and 1 H-NMR.
MS(m/e)：721(M+1)；MS (m / e): 721 (M + 1);
1H-NMR(CDCl 3，500MHz)：δ0.96-1.25(10H，m)，δ2.01(2H，d)，δ3.29(4H，s)，δ3.52-3.81(22H，m)，δ4.05-4.09(6H，m)，δ4.65(8H，s)，δ6.95(8H，d)。 1 H-NMR (CDCl 3 , 500 MHz): δ 0.96-1.25 (10H, m), δ 2.01 (2H, d), δ 3.29 (4H, s), δ 3.52-3.81 (22H, m) , δ 4.05-4.09 (6H, m), δ 4.65 (8H, s), δ 6.95 (8H, d).
实施例6Example 6
产物6的制备Preparation of product 6
Figure PCTCN2018095454-appb-000020
Figure PCTCN2018095454-appb-000020
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87g(0.75mol)原料1、2g(0.05mol)氢氧化钠及100g甲苯，搅拌升温至80℃，滴加65g(0.25mol)原料8，1.5h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值至中性，过滤，水洗、萃取，减压蒸馏，得到144g淡黄色液体。87 g (0.75 mol) of raw materials 1, 2 g (0.05 mol) of sodium hydroxide and 100 g of toluene were sequentially added to a 250 ml four-necked flask equipped with a stirring device, a thermometer, and a reflux condenser, and the mixture was stirred and heated to 80 ° C, and 65 g (0.25 g) was added dropwise. Mol) raw material 8, 1.5h drop addition, continue to stir the reaction, gas phase tracking until the content of raw material 1 no longer changes, stop heating, adjust the pH to neutral, filter, wash, extract, vacuum distillation, get 144g light yellow liquid .
产物6的结构通过LC-MS和 1H-NMR得到确认。 The structure of the product 6 was confirmed by LC-MS and 1 H-NMR.
MS(m/e)：609(M+1)；MS (m/e): 609 (M+1);
1H-NMR(CDCl 3，500MHz)：δ0.96-1.25(15H，m)，δ2.01(3H，d)，δ3.29(6H，s)，δ3.52-3.87(20H，m)，δ4.65(12H，s)。 1 H-NMR (CDCl 3 , 500 MHz): δ 0.96-1.25 (15H, m), δ 2.01 (3H, d), δ 3.29 (6H, s), δ 3.52-3.87 (20H, m) , δ 4.65 (12H, s).
实施例7-20Example 7-20
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7-20.Referring to the method of Examples 1-6, the products having the structures shown in Table 1 were synthesized from the corresponding reagents 7-20.
表1Table 1
Figure PCTCN2018095454-appb-000021
Figure PCTCN2018095454-appb-000021
Figure PCTCN2018095454-appb-000022
Figure PCTCN2018095454-appb-000022
Figure PCTCN2018095454-appb-000023
Figure PCTCN2018095454-appb-000023
Figure PCTCN2018095454-appb-000024
Figure PCTCN2018095454-appb-000024
Figure PCTCN2018095454-appb-000025
Figure PCTCN2018095454-appb-000025
性能表征Performance characterization
通过配制示例性光固化组合物，对本发明的氧杂环丁烷类单体化合物的主要性能指标进行评价，包括固化速度、硬度、柔韧性、附着性等方面，并将其与已商品化的氧杂环丁烷类化合物OXT-101和OXE-10进行对比。The main performance indicators of the oxetane monomer compounds of the present invention are evaluated by formulating exemplary photocurable compositions, including curing speed, hardness, flexibility, adhesion, etc., and are commercially available. The oxetane compound OXT-101 was compared to OXE-10.
按照表2中所示配方，于暗室中将原料混合均匀，得到光固化组合物。除非另有说明，所示份数均为质量份。According to the formulation shown in Table 2, the raw materials were uniformly mixed in a dark room to obtain a photocurable composition. Parts indicated are by mass unless otherwise indicated.
表2Table 2
Figure PCTCN2018095454-appb-000026
Figure PCTCN2018095454-appb-000026
Figure PCTCN2018095454-appb-000027
Figure PCTCN2018095454-appb-000027
表2中，TTA21、OXT-101、OXE-10以及PAG-202的结构式分别如下所示：In Table 2, the structural formulas of TTA21, OXT-101, OXE-10, and PAG-202 are as follows:
Figure PCTCN2018095454-appb-000028
Figure PCTCN2018095454-appb-000028
Figure PCTCN2018095454-appb-000029
Figure PCTCN2018095454-appb-000029
1、固化速度1, curing speed
称取约1mg组合物样品平铺于铝坩埚，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，达到峰顶点的时间越短，表示固化性能越好。About 1 mg of the composition sample was weighed into an aluminum crucible, and the sample was scanned and cured using a Perkin Elmer Differential Scanning Calorimeter (DSC8000) equipped with a mercury arc lamp ultraviolet light source (OmniCure-S2000). The time from the initiation of UV to the maximum cure exotherm was recorded, and the shorter the time to reach the peak apex, the better the cure performance.
2、硬度测试2, hardness test
将组合物以25μm的厚度涂于PET膜上，接受200mj/cm 2的辐射能量，使其充分固化完全。参照GB/T 6739-2006中规定的铅笔硬度评价标准，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。 The composition was applied to a PET film at a thickness of 25 μm, and received radiant energy of 200 mj/cm 2 to fully cure completely. Refer to the pencil hardness evaluation standard specified in GB/T 6739-2006, insert the pencil into the test instrument and fix it with the clip, keep it horizontal, put the tip of the pencil on the surface of the paint film, and leave it at a speed of 1mm/s. Push the direction at least 7mm. If there are no scratches, repeat the experiment in the untested area and replace the pencil with higher hardness until there is at least 3mm long scratches. The hardness of the hardest pencil without scratches the coating. Indicates the hardness of the coating.
3、柔韧性3, flexibility
将组合物以25μm的厚度涂于马口铁片上，接受200mj/cm 2的辐射能量，使其充分固化完全。参照GB/T 1731-93漆膜柔韧性测试标 准，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。 The composition was applied to a tinplate at a thickness of 25 μm and subjected to a radiant energy of 200 mj/cm 2 to fully cure completely. Referring to the GB/T 1731-93 paint film flexibility test standard, the outer side of the tinplate coated with the cured coating is wound in the longitudinal direction on the rod shaft of 10, 5, 4, 3, 2, 1 mm, and bent. 2-3 s, observed with a magnifying glass, indicating the flexibility of the UV-curable coating with the diameter of the smallest rod axis destroyed by the coating layer.
4、附着性4, adhesion
将组合物以25μm的厚度涂于PET膜上，接受200mj/cm 2的辐射能量，使其充分固化完全。参照GB/T 9286-1998中规定的漆膜划格评价标准，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。 The composition was applied to a PET film at a thickness of 25 μm, and received radiant energy of 200 mj/cm 2 to fully cure completely. Refer to the evaluation criteria of the paint film according to GB/T 9286-1998, cut the film into a hundred grid, the blade tip should be drawn with the substrate when cutting, and the tip should be sharp, and the tip and the coating film are 45 degrees. 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.
0级：切割边缘完全平滑无一脱落；Level 0: The cutting edge is completely smooth and has no shedding;
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％；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%;
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％；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%;
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％；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%;
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％；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%;
5级：剥落的程度超过4级。Level 5: The degree of peeling exceeds level 4.
性能测试结果汇总在表3中。The performance test results are summarized in Table 3.
表3table 3
Figure PCTCN2018095454-appb-000030
Figure PCTCN2018095454-appb-000030
从表3中可以看到，本发明的氧杂环丁烷类单体化合物在应用于阳离子光固化体系中时，表现出了很高的反应活性，固化速度快，显著优于商购氧杂环丁烷类化合物OXT-101，与OXE-10相当；其固化涂层具有明显更高的硬度、更优异的柔韧性和附着性。相较于现有同 类产品，本发明的氧杂环丁烷类单体化合物表现出了更优异的整体应用性能。It can be seen from Table 3 that the oxetane monomer compound of the present invention exhibits high reactivity when applied to a cationic photocuring system, and has a fast curing speed, which is significantly superior to commercially available oxygen. The cyclobutane compound OXT-101 is equivalent to OXE-10; its cured coating has significantly higher hardness, more excellent flexibility and adhesion. The oxetane monomer compounds of the present invention exhibit superior overall application properties compared to existing products of the same class.

Claims (15)

  1. 一种氧杂环丁烷类单体化合物，具有通式(I)所示结构、或者是通式(I)化合物的酯化物，通式(I)的结构如下：An oxetane-based monomer compound having a structure represented by the formula (I) or an ester compound of the compound of the formula (I), and the structure of the formula (I) is as follows:
    Figure PCTCN2018095454-appb-100001
    Figure PCTCN2018095454-appb-100001
    其中，among them,
    R 1表示从
    Figure PCTCN2018095454-appb-100002
    中除去n个环氧乙烷基团结构后得到的n价有机残基，选自C 1-C 40的直链或支链的n价烷基、C 2-C 40的n价链烯基、C 3-C 40的n价环烷基、C 4-C 40的n价环烷基烷基、C 4-C 40的n价烷基环烷基、C 6-C 40的n价芳基、C 7-C 40的n价芳基烷基、
    Figure PCTCN2018095454-appb-100003
    Figure PCTCN2018095454-appb-100004
    其中的-CH 2-可任选地被-O-或-OCH 2CH 2-所取代，条件是两个-O-不直接相连；     R 1 means from
    Figure PCTCN2018095454-appb-100002
    An n-valent organic residue obtained by removing n oxirane group structures, a linear or branched n-valent alkyl group selected from C 1 -C 40 , and a C 2 -C 40 n-valent alkenyl group , an n-valent cycloalkyl group of C 3 -C 40 , an n-valent cycloalkylalkyl group of C 4 -C 40 , an n-valent alkylcycloalkyl group of C 4 -C 40 , and an n-valent aromatic group of C 6 -C 40 a C 7 -C 40 n-valent arylalkyl group,
    Figure PCTCN2018095454-appb-100003
    Figure PCTCN2018095454-appb-100004
    Wherein -CH 2 - may be optionally substituted by -O- or -OCH 2 CH 2 - provided that the two -O- are not directly attached;
    R 4和R 5相同或不同，各自独立地表示C 1-C 10的直链或支链的亚烷基； R 4 and R 5 are the same or different and each independently represents a C 1 -C 10 linear or branched alkylene group;
    A 1和A 2相同或不同，各自独立地表示空、C 1-C 10的亚烷基或亚苯基； A 1 and A 2 are the same or different and each independently represents an empty, C 1 -C 10 alkylene group or a phenylene group;
    m 1和m 2表示0或大于0的整数； m 1 and m 2 represent 0 or an integer greater than 0;
    R 2表示-CH 2-、-(CH 2-CH 2-O) m-CH 2-、-[CH 2-CH(CH 3)-O) m-CH 2-，其中m表示0或大于0的整数； R 2 represents -CH 2 -, -(CH 2 -CH 2 -O) m -CH 2 -, -[CH 2 -CH(CH 3 )-O) m -CH 2 -, wherein m represents 0 or greater than 0 Integer
    R 3表示氢、卤素、硝基、C 1-C 20的直链或支链烷基、C 2-C 20的链烯基、C 3-C 20的环烷基、C 4-C 20的环烷基烷基、C 4-C 20的烷基环烷基、C 6-C 20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； R 3 represents hydrogen, halogen, nitro, C 1 -C 20 linear or branched alkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkyl, C 4 -C 20 a cycloalkylalkyl group, a C 4 -C 20 alkylcycloalkyl group, 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 alkane Substituted by a group of a halogen, a nitro group;
    n表示1-8的整数。n represents an integer of 1-8.
  2. 根据权利要求1所述的氧杂环丁烷类单体化合物，其特征在于：R 1选自C 1-C 20的直链或支链的n价烷基、C 2-C 20的n价链烯基、C 3-C 20的n价环烷基、C 4-C 20的n价环烷基烷基、C 4-C 20的n价烷基环烷基、C 6-C 20的n价芳基、C 7-C 20的n价芳基烷基、
    Figure PCTCN2018095454-appb-100005
    Figure PCTCN2018095454-appb-100006
    其中的-CH 2-可任选地被-O-或-OCH 2CH 2-所取代，条件是两个-O-不直接相连；R 4和R 5各自独立地表示C 1-C 4的直链或支链的亚烷基，A 1和A 2各自独立地表示C 1-C 4的亚烷基或1,4-亚苯基，m 1和m 2表示0-6的整数。     The oxetane monomer compound according to claim 1, wherein: R 1 is selected from C 1 -C n monovalent straight or branched chain alkyl of 20, C 2 -C n price 20 Alkenyl, C 3 -C 20 n-valent cycloalkyl, C 4 -C 20 n-valent cycloalkylalkyl, C 4 -C 20 n-valent alkylcycloalkyl, C 6 -C 20 An n-valent aryl group, a C 7 -C 20 n-valent arylalkyl group,
    Figure PCTCN2018095454-appb-100005
    Figure PCTCN2018095454-appb-100006
    Wherein -CH 2 - may be optionally substituted by -O- or -OCH 2 CH 2 - provided that two -O- are not directly bonded; R 4 and R 5 each independently represent C 1 -C 4 A linear or branched alkylene group, A 1 and A 2 each independently represent a C 1 -C 4 alkylene group or a 1,4-phenylene group, and m 1 and m 2 represent an integer of 0-6.
  3. 根据权利要求1或2所述的氧杂环丁烷类单体化合物，其特征在于：R 1选自C 2-C 12的直链或支链的n价烷基、C 2-C 8的n价链烯 基、C 3-C 10的n价环烷基、C 4-C 14的n价环烷基烷基、C 4-C 14的n价烷基环烷基、C 6-C 10的n价芳基、C 7-C 12的n价芳基烷基、
    Figure PCTCN2018095454-appb-100007
    Figure PCTCN2018095454-appb-100008
    其中的-CH 2-可任选地被-O-所取代，条件是两个-O-不直接相连；R 4和R 5各自独立地表示C 1-C 4的直链或支链的亚烷基，A 1和A 2各自独立地表示空、C 1-C 4的亚烷基或1,4-亚苯基，m 1和m 2表示0-4的整数。     The oxetane monomer compound according to claim 1 or 2, wherein R 1 is selected from a C 2 - C 12 linear or branched n-valent alkyl group, C 2 - C 8 N-valent alkenyl group, C 3 -C 10 n-valent cycloalkyl group, C 4 -C 14 n-valent cycloalkylalkyl group, C 4 -C 14 n-valent alkylcycloalkyl group, C 6 -C 10 n-valent aryl, C 7 -C 12 n-valent arylalkyl,
    Figure PCTCN2018095454-appb-100007
    Figure PCTCN2018095454-appb-100008
    Wherein -CH 2 - may be optionally substituted by -O-, provided that two -O- are not directly bonded; and R 4 and R 5 each independently represent a straight or branched chain of C 1 -C 4 The alkyl group, A 1 and A 2 each independently represents an empty, C 1 -C 4 alkylene group or 1,4-phenylene group, and m 1 and m 2 represent an integer of 0-4.
  4. 根据权利要求1所述的氧杂环丁烷类单体化合物，其特征在于：R 2中m表示0-10的整数，优选地，m表示0、1、2、3或4。 The oxetane monomer compound according to claim 1, wherein m in R 2 represents an integer of 0 to 10, and preferably m represents 0, 1, 2, 3 or 4.
  5. 根据权利要求1所述的氧杂环丁烷类单体化合物，其特征在于：R 3表示氢、C 1-C 10的直链或支链烷基、C 2-C 8的链烯基、C 3-C 10的环烷基、C 4-C 10的环烷基烷基、C 4-C 10的烷基环烷基、苯基。 The oxetane-based monomer compound according to claim 1, wherein R 3 represents hydrogen, a C 1 - C 10 linear or branched alkyl group, or a C 2 - C 8 alkenyl group; C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, phenyl.
  6. 根据权利要求1或5所述的氧杂环丁烷类单体化合物，其特征在于：R 3表示C 1-C 4的直链或支链烷基、C 3-C 8的环烷基、C 4-C 8的环烷基烷基、或苯基。 The oxetane-based monomer compound according to claim 1 or 5, wherein R 3 represents a C 1 -C 4 linear or branched alkyl group, a C 3 -C 8 cycloalkyl group, a C 4 -C 8 cycloalkylalkyl group, or a phenyl group.
  7. 根据权利要求1所述的氧杂环丁烷类单体化合物，其特征在于：n是1-6的整数，优选1、2、3或4。The oxetane monomer compound according to claim 1, wherein n is an integer of from 1 to 6, preferably 1, 2, 3 or 4.
  8. 根据权利要求1所述的氧杂环丁烷类单体化合物，其特征在 于：所述的通式(I)化合物的酯化物，是由通式(I)化合物与具有通式(IV)或通式(V)所示结构的化合物反应而成：The oxetane monomer compound according to claim 1, wherein the ester compound of the compound of the formula (I) is a compound of the formula (I) and has the formula (IV) or The compound of the structure represented by the formula (V) is reacted:
    Figure PCTCN2018095454-appb-100009
    Figure PCTCN2018095454-appb-100009
    其中，R 6表示单键或n 1价连接基团，选自单键、C 1-C 20的直链或支链的n 1价烷基、C 2-C 20的n 1价链烯基、C 3-C 20的n 1价环烷基、C 4-C 20的n 1价环烷基烷基、C 4-C 20的n 1价烷基环烷基、C 6-C 40的n 1价芳基；任选地，这些基团中的-CH 2-可被-O-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； Wherein R 6 represents a single bond or an n 1 -valent linking group selected from a single bond, a C 1 -C 20 linear or branched n 1 valent alkyl group, and a C 2 -C 20 n 1 valent alkenyl group; , C 3 -C n 1 price 20 cycloalkyl, C 4 -C n 1 price 20 cycloalkylalkyl, C 4 -C n 1 price 20 alkylcycloalkyl, C 6 -C 40 of n 1 monovalent aromatic group; optionally, these groups are -CH 2 - may be substituted with -O- or 1,4-phenylene, with the proviso that two not directly connected -O-; optionally, One or more hydrogen atoms of these groups may be independently substituted with a group selected from an alkyl group, a halogen, and a nitro group;
    R 7表示n 2价连接基团，选自C 1-C 20的直链或支链的n 2价烷基、C 2-C 20的n 2价链烯基、C 3-C 20的n 2价环烷基、C 4-C 20的n 2价环烷基烷基、C 4-C 20的n 2价烷基环烷基、C 6-C 40的n 2价芳基；任选地，这些基团中的-CH 2-可被-O-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； R 7 represents an n 2 -valent linking group, a linear or branched n 2 -valent alkyl group selected from C 1 -C 20 , a C 2 -C 20 n 2 -valent alkenyl group, and a C 3 -C 20 n a divalent cycloalkyl group, a C 4 -C 20 n 2 valent cycloalkylalkyl group, a C 4 -C 20 n 2 valent alkylcycloalkyl group, a C 6 -C 40 n 2 valent aryl group; optionally , -CH 2 - in these groups may be substituted by -O- or 1,4-phenylene, provided that two -O- are not directly attached; optionally, one or more of these groups One hydrogen atom may be independently substituted with a group selected from an alkyl group, a halogen, and a nitro group;
    X表示羟基、卤原子、或-OR 8，其中R 8表示C 1-C 10的直链或支链烷基； X represents a hydroxyl group, a halogen atom, or -OR 8 , wherein R 8 represents a C 1 -C 10 linear or branched alkyl group;
    n 1与n 2各自独立地表示1-8的整数。 n 1 and n 2 each independently represent an integer of 1-8.
  9. 根据权利要求8所述的氧杂环丁烷类单体化合物，其特征在于：The oxetane monomer compound according to claim 8, wherein:
    R 6表示单键、C 1-C 14的直链或支链的n 1价烷基、C 2-C 10的n 1价链烯基、C 3-C 10的n 1价环烷基、C 4-C 10的n 1价环烷基烷基、C 4-C 10的n 1价烷基环烷基、C 6-C 20的n 1价芳基；任选地，这些基团中的-CH 2-可被-O-或者1,4-亚苯基所取代，条件是两个-O-不直接相连； R 6 represents a single bond, a C 1 -C 14 linear or branched n 1 valent alkyl group, a C 2 -C 10 n 1 valent alkenyl group, a C 3 -C 10 n 1 valent cycloalkyl group, a C 1 -C 10 n 1 valent cycloalkylalkyl group, a C 4 -C 10 n 1 valent alkylcycloalkyl group, a C 6 -C 20 n 1 valent aryl group; optionally, these groups -CH 2 - may be substituted by -O- or 1,4-phenylene, provided that the two -O- are not directly attached;
    R 7表示C 1-C 14的直链或支链的n 2价烷基、C 2-C 10的n 2价链烯基、C 3-C 10的n 2价环烷基、C 4-C 10的n 2价环烷基烷基、C 4-C 10的n 2价烷基环烷基、C 6-C 20的n 2价芳基；任选地，这些基团中的-CH 2-可被-O-或者1,4-亚苯基所取代，条件是两个-O-不直接相连； R 7 represents a C 1 -C 14 linear or branched n 2 valent alkyl group, a C 2 -C 10 n 2 valent alkenyl group, a C 3 -C 10 n 2 valent cycloalkyl group, C 4 - An n 2 valent cycloalkylalkyl group of C 10 , a C 2 -C 10 n 2 valent alkylcycloalkyl group, a C 6 -C 20 n 2 valent aryl group; optionally, -CH of these groups 2 - may be substituted by -O- or 1,4-phenylene, provided that two -O- are not directly attached;
    X表示羟基、氯、溴、-OCH 3、或-OCH 2CH 3； X represents hydroxy, chloro, bromo, -OCH 3 , or -OCH 2 CH 3 ;
    n 1与n 2各自独立地表示1、2、3或4。 n 1 and n 2 each independently represent 1, 2, 3 or 4.
  10. 根据权利要求8或9所述的氧杂环丁烷类单体化合物，其特征在于：R 6表示单键、C 1-C 12的直链或支链的n 1价烷基、C 2-C 6的n 1价链烯基、C 6-C 12的n 1价芳基；R 7表示C 1-C 8的直链或支链的n 2价烷基、C 2-C 6的n 2价链烯基、C 6-C 12的n 2价芳基。 The oxetane monomer compound according to claim 8 or 9, wherein R 6 represents a single bond, a C 1 - C 12 linear or branched n 1 valent alkyl group, C 2 - n-valent C 6 alkenyl group, C n 6 -C 12 monovalent aromatic group; R 7 represents n 2 linear or branched divalent C 1 -C 8 chain alkyl group, n C 2 -C 6 of A divalent alkenyl group, a C 6 -C 12 n 2 valent aryl group.
  11. 权利要求1-7中任一项所述的具有通式(I)所示结构的氧杂环丁烷类单体化合物的制备方法，包括：以通式(II)所示环氧化合物与通式(III)所示含氧杂环丁烷基的化合物为原料，在催化剂存在条件下反应得到产物；A process for producing an oxetane monomer compound having a structure represented by the formula (I) according to any one of claims 1 to 7, which comprises: an epoxy compound represented by the formula (II) The oxetane group-containing compound represented by the formula (III) is used as a raw material, and is reacted in the presence of a catalyst to obtain a product;
    反应式如下所示：The reaction formula is as follows:
    Figure PCTCN2018095454-appb-100010
    Figure PCTCN2018095454-appb-100010
    Figure PCTCN2018095454-appb-100011
    Figure PCTCN2018095454-appb-100011
  12. 权利要求1-10中任一项所述的氧杂环丁烷类单体化合物在阳离子光固化体系中的应用。Use of the oxetane monomer compound according to any one of claims 1 to 10 in a cationic photocuring system.
  13. 根据权利要求12所述的应用，其特征在于：所述的氧杂环丁烷类单体化合物被用于表面涂料组合物、粉末涂料组合物、印刷油墨、印刷版、牙科用组合物、立体平版印刷树脂、粘合剂、防粘涂料、滤色器、抗蚀剂材料或图像记录材料的制造。The use according to claim 12, wherein said oxetane monomer compound is used in a surface coating composition, a powder coating composition, a printing ink, a printing plate, a dental composition, and a three-dimensional Manufacture of lithographic resins, adhesives, release coatings, color filters, resist materials or image recording materials.
  14. 一种光固化组合物，包含：A photocurable composition comprising:
    (a1)权利要求1-10中任一项所述的氧杂环丁烷类单体化合物的至少一种；(a1) at least one of the oxetane-based monomer compounds according to any one of claims 1 to 10;
    (a2)阳离子或酸催化下可聚合的化合物；和(a2) a cation or acid catalyzed polymerizable compound;
    (b)阳离子引发剂。(b) a cationic initiator.
  15. 根据权利要求14所述的光固化组合物，其特征在于：组分(a2)选自环醚或乙烯基醚化合物，所述环醚优选环氧化物和其它氧杂环丁烷类化合物。The photocurable composition according to claim 14, wherein component (a2) is selected from a cyclic ether or a vinyl ether compound, and the cyclic ether is preferably an epoxide and other oxetane compounds.
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