WO2024109808A1 - 含有氧杂环丁烷官能团的丙烯酸系预聚物及其制备和应用 - Google Patents

含有氧杂环丁烷官能团的丙烯酸系预聚物及其制备和应用 Download PDF

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WO2024109808A1
WO2024109808A1 PCT/CN2023/133271 CN2023133271W WO2024109808A1 WO 2024109808 A1 WO2024109808 A1 WO 2024109808A1 CN 2023133271 W CN2023133271 W CN 2023133271W WO 2024109808 A1 WO2024109808 A1 WO 2024109808A1
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prepolymer
group
glycol dimethacrylate
present
monomer
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PCT/CN2023/133271
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English (en)
French (fr)
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张强
邹应全
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湖北固润科技股份有限公司
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Publication of WO2024109808A1 publication Critical patent/WO2024109808A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F120/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • 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

Definitions

  • the present invention belongs to the field of polymer chemistry and photocuring technology, and specifically relates to an acrylic prepolymer containing an oxetane functional group, which can be used as a macromolecular monomer and/or a crosslinking agent and is suitable for free radical curing and/or cationic curing.
  • the present invention also relates to the preparation and application of the acrylic prepolymer containing an oxetane functional group.
  • photocuring technology can be divided into free radical curing, cationic curing and free radical/cationic mixed curing.
  • Free radical curing is the process in which a photoinitiator generates free radicals under light irradiation, which triggers the addition polymerization reaction of unsaturated groups in prepolymers and monomers.
  • Cationic curing is the process in which a cationic initiator generates proton acid or Lewis acid under light irradiation, forms a positive ion active center, and triggers cationic ring-opening polymerization.
  • Free radical/cationic mixed curing refers to the simultaneous occurrence of free radical photopolymerization and cationic photopolymerization in the same system.
  • the above-mentioned free radical and/or cationic curing systems have the advantages of fast curing speed, a wide variety of initiators, and stable storage. Therefore, there is a strong industrial demand and they have been widely used in photocurable coatings, printing inks, photosensitive resist dry films, and insulating coatings.
  • problems and shortcomings especially the few types of prepolymers or macromolecular monomers for the curing system, high prices, and the inability to adjust the performance of the cured products, which limits their practical application in certain specific fields.
  • CN104447635A prepared difunctional and trifunctional oxetane monomers by transesterification
  • EP3486238A1 prepared a series of prepolymers containing oxetane by ring-opening polymerization of epoxy compounds, and introduced epoxy groups at the end groups through subsequent polymerization modification to obtain prepolymers with multiple epoxy and oxetane groups
  • US2001002423A1 obtained copolymers with oxetane groups and fluorine atoms by free radical polymerization of vinyl monomers containing oxetane groups.
  • the multifunctional oxacycloalkane prepolymers known in the prior art are still There are shortcomings such as poor control of molecular weight and molecular weight distribution, high viscosity and poor fluidity.
  • the prior art requires multi-step organic synthesis reactions for the preparation of multifunctional oxetane monomers and prepolymers thereof, which has defects such as cumbersome post-reaction treatment and the generation of by-products.
  • the preparation of existing oxetane prepolymers mainly utilizes conventional free radical polymerization or post-polymerization modification strategies, which have problems such as incomplete reaction and uneven product properties.
  • the inventors of the present invention have conducted extensive and in-depth research on prepolymers suitable for cationic curing and/or free radical curing systems, in order to find a new multifunctional oxetane prepolymer that can be used in cationic curing and/or free radical curing systems and has a controllable molecular weight and low viscosity.
  • the inventors surprisingly found that by using an acrylic monomer containing an oxetane functional group and using an organic cobalt complex as a catalytic chain transfer agent to carry out catalytic chain transfer polymerization (CCTP), a novel acrylic prepolymer containing an oxetane functional group having an oxetane group on the side chain and an acrylate group on the end group can be obtained through a one-step reaction.
  • CCTP catalytic chain transfer polymerization
  • the novel acrylic prepolymer containing an oxetane functional group provided by the present invention has an oxetane group on the side chain and an acrylate group on the end group, and can be used as a macromonomer and/or a crosslinking agent, and can be free radical cured and cationic cured separately or simultaneously, so that it can be used for free radical curing, cationic light curing or free radical/cationic dual curing systems.
  • the object of the present invention is achieved based on the above-mentioned discovery.
  • an object of the present invention is to provide an acrylic prepolymer containing an oxetane functional group, wherein the prepolymer has an oxetane group in the side chain and an acrylate group in the terminal group, and can be used as a macromolecular monomer and/or crosslinking agent for free radical curing and/or cationic curing.
  • the present invention can regulate the molecular weight and viscosity of the obtained acrylic prepolymer containing oxetane functional groups, thereby obtaining a prepolymer having a low molecular weight and a narrow molecular weight distribution as well as a low viscosity and excellent fluidity.
  • the present invention can regulate the content and density of oxetane groups in the obtained acrylic prepolymer containing oxetane functional groups, and can also regulate the physical properties of the prepolymer such as glass transition temperature and thermal stability. Therefore, compared with conventional di-, tri- or multi-functional oxetane small molecule monomers, the acrylic prepolymer containing oxetane functional groups provided by the present invention can have a similar or greater number of oxetane groups, and can provide a higher crosslinking density during the polymerization process.
  • the present invention adopts a one-step reaction to avoid complex multi-step organic synthesis reactions, thereby avoiding the difficulties in synthesizing multifunctional oxetane monomers and the high cost, and overcomes the defects of multi-step reactions such as cumbersome post-processing and the generation of by-products.
  • Another object of the present invention is to provide a method for preparing the acrylic prepolymer containing oxetane functional groups of the present invention.
  • Another object of the present invention is to provide the use of the acrylic prepolymer containing oxetane functional groups in free radical curing and/or cationic curing.
  • An acrylic prepolymer containing an oxetane functional group characterized in that the side chain of the prepolymer has an oxetane group and the end group has an acrylate group.
  • the weight average molecular weight Mw of the prepolymer is 200-10000Da, preferably 500-8000Da, more preferably 600-5000Da; and/or,
  • the polydispersity index (PDI) of the prepolymer is 1.0-5.0, preferably 1.0-4.0, more preferably 1.0-3.0.
  • prepolymer is a homopolymer or a copolymer, wherein the copolymer is a random, gradient or block copolymer.
  • prepolymer is a hyperbranched copolymer, wherein the side chains of the hyperbranched copolymer also have acrylate groups.
  • x is an integer from 1 to 3, preferably x is 1;
  • R 1 is H or CH 3 , preferably R 1 is CH 3 ;
  • R2 is H, halogen, C1 - C6 alkyl, C1- C6 haloalkyl, C1 - C6 hydroxyalkyl, C1 - C6 alkoxy or C1 - C6 haloalkoxy; preferably R2 is H, halogen, C1 - C4 alkyl, C1 - C4 haloalkyl, C1 - C4 hydroxyalkyl, C1 - C4 alkoxy or C1 - C4 haloalkoxy; more preferably R2 is H or C1 - C4 alkyl , especially ethyl; and
  • the mass ratio of monomer (B) to the sum of other monomers is 1:1-1:5, preferably 1:1-1:3, more preferably 1:1.
  • the mass ratio of monomer (C) to the sum of other monomers is 1:3-1:20, preferably 1:4-1:10, more preferably 1:5.
  • CCTP catalytic chain transfer polymerization
  • the chain transfer agent is one or more selected from the group consisting of bis[(difluoroboryl)dimethyl glyoximato]cobalt(II) (CoBF), bis[(difluoroboryl)dimethyl phenyl-glyoximato]cobalt(II) (Co(MePh)BF), bis[(difluoroboryl)diphenyl glyoximato]cobalt(II) (CoPhBF), bis[dimethyl glyoximato]cobalt(II) (Co(dmg) 2 ), cobalt(meso-Ph4-porphyrin, CoP), tetramethyl ether of cobalt hematoporphyrin IX, CoTMHP, cobalt tetrafluorophenyl porphyrin, CoTFPP, bis[(difluoroboryl)dimethyl glyoximate]isopropyl pyr
  • the amount of the chain transfer agent used is 0.1 to 100 ppm, preferably 1 to 80 ppm, more preferably 5 to 50 ppm, based on the total weight of the monomers.
  • the free radical initiator is one or more selected from the group consisting of ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, azoisobutylcyanamide, dibenzoyl peroxide, tert-butyl hydroperoxide and cumene hydroperoxide, preferably azobisisobutyronitrile; and/or
  • the amount of the free radical initiator used is 0.1-8% by weight, preferably 0.1-4% by weight, more preferably 0.3-2% by weight, based on the total weight of the monomers.
  • reaction temperature is 50-120°C, preferably 55-100°C, more preferably 60-80°C.
  • the method according to any one of embodiments 9 to 12 is characterized in that the one-step catalytic chain transfer polymerization (CCTP) reaction is carried out by bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization or precipitation polymerization.
  • CCTP catalytic chain transfer polymerization
  • a photocurable composition comprising a prepolymer according to any one of embodiments 1 to 8 or obtained according to the method of any one of embodiments 9 to 13.
  • a method for preparing a photocurable material comprising irradiating the photocurable composition of embodiment 15 with ultraviolet light, visible light or laser.
  • FIG. 1 is a GPC spectrum of the prepolymer of the present invention (homopolymer A1) prepared according to Example 1.
  • FIG. 2 is a GPC spectrum of the prepolymer of the present invention (homopolymer A2) prepared according to Example 2.
  • FIG. 3 is a GPC spectrum of the prepolymer of the present invention (hyperbranched copolymer A5) prepared according to Example 5.
  • FIG. 4 is an NMR spectrum of the prepolymer of the present invention (homopolymer A1) prepared according to Example 1.
  • FIG5 is a NMR of the prepolymer of the present invention (hyperbranched copolymer A5) prepared according to Example 5 Atlas.
  • Figure 6 is the MALDI-ToF MS spectrum of the prepolymer of the present invention (homopolymer A2) prepared according to Example 2.
  • FIG. 7 is a schematic diagram showing the comparison of the surface morphology and columnar water flux of the prepolymers of the present invention (homopolymer A1, copolymer A3) prepared according to Examples 1 and 3 in the PVDF-based ultrafiltration membrane photocuring experimental test.
  • FIG8 is a visual effect diagram of a culture dish photocuring experimental test of the prepolymer of the present invention (hyperbranched copolymer A5) prepared according to Example 5.
  • FIG. 9 is an infrared spectrum of the culture dish light curing experimental test of the prepolymer of the present invention (hyperbranched copolymer A5) prepared according to Example 5.
  • an acrylic prepolymer containing an oxetane functional group wherein the side chain of the prepolymer has an oxetane group and the terminal group has an acrylate group.
  • the prepolymer of the present invention has both an oxetane group in the side chain and an acrylate group in the terminal group, and can therefore be used as a macromonomer and/or a crosslinking agent to perform free radical curing and cationic curing separately or simultaneously, thereby being used in free radical curing, cationic light curing or free radical/cationic dual curing systems.
  • the prepolymer of the present invention is derived from the following monomers:
  • x is an integer from 1 to 3;
  • R 1 is H or CH 3 ;
  • R2 is H, halogen, C1 - C6 alkyl, C1 - C6 haloalkyl, C1 - C6 hydroxyalkyl, C1 - C6 alkoxy or C1 - C6 haloalkoxy;
  • acrylic means acrylates or methacrylates or their derivatives and combinations containing acrylic acid groups.
  • Acrylate groups appearing alone should be understood to include both acrylate groups and methacrylate groups.
  • C n -C m denotes in each case that the number of carbon atoms contained in the group is nm.
  • Halogen refers to fluorine, chlorine, bromine and iodine. In the present invention, preferably, the halogen includes fluorine, chlorine or a combination thereof.
  • Cn - Cm- alkyl refers to a branched or unbranched saturated hydrocarbon radical having n-m, e.g. 1 to 6, preferably 1 to 4 carbon atoms.
  • C1 - C6 -alkyl may be methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers thereof, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl.
  • C1 - C4- alkyl may be methyl, ethyl, propyl, butyl and isomers thereof, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.
  • Cn - Cm- haloalkyl refers to a Cn - Cm- alkyl group substituted by one or more identical or different halogen atoms, for example a C1 - C6- haloalkyl group, preferably a C1 - C4- haloalkyl group.
  • Cn - Cm- haloalkyl groups mention may be made of monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, dichloromethylethyl, monochlorobutyl, dichloromethylpropyl, trichloromethylpropyl, monochloropentyl, dichloromethylbutyl, monochlorohexyl and isomers thereof, in particular 1-chloromethylethyl, 1,1-dichloromethylethyl, 1-chloromethylpropyl, 2-chloromethylpropyl, 1,1-dichloromethylpropyl, 1,2-dichloromethylpropyl, 2,2-dichloromethylpropyl, 1,1,2-trichloromethylpropyl and 1,2,2-trichloromethylpropyl.
  • Cn - Cm- hydroxyalkyl refers to a Cn - Cm- alkyl group having a hydroxyl group bonded to any carbon atom of the open-chain Cn - Cm - alkane corresponding to the Cn-Cm-alkyl group, for example a C1 - C6- hydroxyalkyl group, particularly preferably a C1 - C4- hydroxyalkyl group, such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group and isomers thereof, in particular a hydroxymethyl group, a hydroxyethyl group, a hydroxy-n-propyl group, a hydroxy-isopropyl group, a hydroxy-n-butyl group, a hydroxy-sec-butyl group, a hydroxy-tert-
  • C n -C m alkoxy refers to a C n -C m alkyl group having an oxygen atom as a linking group bonded to any carbon atom of an open-chain C n -C m alkane corresponding to the C n -C m alkyl group, for example, a C 1 -C 6 alkoxy group, more preferably a C 1 -C 4 alkoxy group.
  • the C 1 -C 6 alkoxy group may be a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group and isomers thereof, in particular, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a 2-butoxy group, a tert-butoxy group, a n-pentoxy group, an isopentoxy group and a n-hexoxy group.
  • the C 1 -C 4 alkoxy group may be a methoxy group, an ethoxy group, a propoxy group, a butoxy group and isomers thereof, in particular, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, an isobutoxy group and a tert-butoxy group.
  • Cn - Cm- haloalkoxy refers to a Cn - Cm- alkoxy group substituted by one or more identical or different halogen atoms, for example a C1 - C6 -haloalkoxy group, preferably a C1 - C4- haloalkoxy group.
  • Cn - Cm -haloalkoxy groups mention may be made of monochloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 4-chlorobutoxy, 5-chloropentyloxy, 6-chlorohexyloxy and isomers thereof, in particular monochloromethoxy, 2-chloroethoxy, 3-chloro-n-propoxy, 2-chloro-isopropoxy, 4-chloro-n-butoxy, 3-chloro-sec-butoxy, 2-chloro-tert-butoxy, 5-chloro-n-pentyloxy, 4-chloro-isopentyloxy and 6-chloro-n-hexyloxy.
  • R2 is typically H, halogen, C1 - C6 alkyl, C1 - C6 haloalkyl, C1 - C6 hydroxyalkyl, C1- C6 alkoxy or C1 - C6 haloalkoxy.
  • R2 is H, halogen, C1 - C4 alkyl, C1 - C4 haloalkyl, C1 - C4 hydroxyalkyl, C1 - C4 alkoxy or C1 -C4 haloalkoxy.
  • R2 is H or C1 - C4 alkyl.
  • R2 can be H, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n -butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-isopropyl, hydroxy-n-butyl, hydroxy-sec-butyl or hydroxy-tert-butyl.
  • R2 is ethyl
  • x is 1.
  • R 1 is CH 3 .
  • monomer (A) is (3-ethyloxetan-3-yl)methyl methacrylate.
  • the prepolymer of the present invention may further comprise monomer (B) Other (meth)acrylic or styrenic monomers. Therefore, the prepolymer of the present invention may be a homopolymer or a copolymer, wherein the copolymer may be a random, gradient or block copolymer.
  • monomer (B) is one or more selected from the following group: acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, benzyl acrylate and its derivatives, benzyl methacrylate and its derivatives, styrene and its derivatives.
  • monomer (B), if present, is one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and benzyl methacrylate.
  • monomer (B), if present, is methyl methacrylate and/or butyl methacrylate.
  • the mass ratio of monomer (B) to the sum of other monomers is 1:1-1:5, preferably 1:1-1:3, more preferably 1:1.
  • the prepolymer of the present invention may further comprise monomer (C) di(meth)acrylate monomers of other diols. Therefore, the prepolymer of the present invention may also be a hyperbranched copolymer, wherein the side chains of the hyperbranched copolymer also have acrylate groups.
  • monomer (C), if present, is one or more selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, 1,4-butylene glycol diacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol diacrylate and tripropylene glycol dimethacrylate.
  • monomer (C), if present, is one or more selected from the group consisting of ethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate and tripropylene glycol dimethacrylate.
  • monomer (C), if present, is ethylene glycol dimethacrylate.
  • the mass ratio of monomer (C), if present, to the sum of other monomers is 1:3-1:20, preferably 1:4-1:10, more preferably 1:5.
  • the prepolymer provided by the present invention has a low molecular weight and a narrow molecular weight distribution.
  • the degree of polymerization of the prepolymer is 1-50, preferably 2-18, and more preferably 3-15.
  • the weight average molecular weight Mw of the prepolymer is 200-10000Da, preferably 500-8000Da, and more preferably 600-5000Da.
  • the polydispersity index (PDI) of the prepolymer is 1.0-5.0, preferably 1.0-4.0, and more preferably 1.0-3.0.
  • a method for preparing the prepolymer of the present invention which comprises subjecting monomer (A) and optional monomer (B) and optional monomer (C) to a one-step catalytic chain transfer polymerization (CCTP) reaction in the presence of a chain transfer agent and a free radical initiator.
  • CCTP catalytic chain transfer polymerization
  • Catalytic chain transfer polymerization is a recently discovered free radical polymerization method that uses organic cobalt complexes as catalytic chain transfer agents.
  • the chain transfer constant of the chain transfer agent organic cobalt complex is very high, which can transfer the hydrogen on the formed free radical chain to another olefin, thereby forming a macromolecule with an unsaturated bond at the end. This terminal double bond is sufficiently active to undergo fragmentation-addition or free radical polymerization reactions with special monomers.
  • CCTP catalytic chain transfer polymerization
  • the chain transfer agent is one or more selected from the following group: bis[(difluoroboryl)dimethyl glyoximato]cobalt(II) (CoBF), bis[(difluoroboryl)dimethyl phenyl-glyoximato]cobalt(II) (Co(MePh)BF), bis[(difluoroboryl)diphenyl glyoximato]cobalt(II) (CoPhBF), bis[dimethyl glyoximato]cobalt(II) (CoBF), bis[(difluoroboryl)dimethyl phenyl-glyoximato]cobalt(II) (CoBF), bis[(difluoroboryl)dimethyl phenyl-glyoximato]cobalt(II) (CoBF), bis[(difluoroboryl)dimethyl phenyl-glyoximato]cobalt(II) (CoBF), bis[(diflu
  • the chain transfer agent is bis[(difluoroboryl)dimethylglyoxime]cobalt(II) (CoBF).
  • the amount of chain transfer agent used is 0.1-100 ppm, preferably 1-80 ppm, more preferably 5-50 ppm, for example 1 ppm, 3 ppm, 5 ppm, 10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 80 ppm based on the total weight of the monomers.
  • the free radical initiator is one or more selected from the following group: ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, azoisobutylcyanamide, dibenzoyl peroxide, tert-butyl hydroperoxide and cumene hydroperoxide.
  • the free radical initiator is azobisisobutyronitrile.
  • the amount of free radical initiator used is 0.1-8 weight%, preferably 0.1-4 weight%, more preferably 0.3-2 weight%, for example 0.1 weight%, 0.5 weight%, 1.0 weight%, 1.5 weight%, 2.0 weight%, 3.0 weight% and 4.0 weight%, based on the total weight of the monomers.
  • the above-mentioned one-step catalytic chain transfer polymerization (CCTP) reaction is usually carried out in a solvent, preferably in an organic solvent.
  • a solvent preferably in an organic solvent.
  • solvent type There is no particular restriction on the choice of solvent type, as long as it can be applied to the one-step catalytic chain transfer polymerization (CCTP) reaction and is chemically inert to the reaction participants, that is, it does not participate in the catalytic chain transfer polymerization (CCTP) reaction.
  • Suitable solvents can be, for example, one or more selected from the following group: methanol, ethanol, propanol, isopropanol, acetonitrile, butanone, toluene, propylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol ethyl ether and ethylene glycol methyl ether.
  • acetonitrile is generally used as an example of a solvent.
  • the amount of solvent used can be as follows: Technical personnel in the field can select the appropriate dosage according to the practical scale of the reaction.
  • the temperature range of the one-step catalytic chain transfer polymerization (CCTP) reaction is generally 50-120° C., preferably 55-100° C., more preferably 60-80° C., such as 50° C., 55° C., 60° C., 65° C., 70° C., 75° C., 80° C., 85° C., 90° C., 95° C. and 100° C.
  • reaction time which is generally 1-20 hours, preferably 1-12 hours.
  • the method is usually carried out under an inert atmosphere.
  • inert gas there is no particular restriction on the type of inert gas, as long as it is chemically inert to the entire reaction system.
  • nitrogen is usually used as an example of an inert gas.
  • the one-step catalytic chain transfer polymerization (CCTP) reaction can be carried out by bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization or precipitation polymerization.
  • CCTP catalytic chain transfer polymerization
  • the feeding method There is no particular restriction on the feeding method, and according to the practical scale of the reaction, the one-time feeding method, semi-continuous feeding method and continuous feeding method known to those skilled in the art can be used.
  • the acrylic prepolymer product containing oxetane functional groups of the present invention is obtained.
  • the reaction product can also be further purified, and the reaction product can be post-processed as needed, such as removing residual organic solvent.
  • the organic solvent can usually be removed by reduced pressure distillation.
  • the product can also be precipitated in a solvent to remove small molecules such as residual monomers, so as to obtain a product with higher purity.
  • the choice of solvent is conventional and is not particularly limited. According to the present invention, it is advantageous that the reaction product is treated with a mixture of methanol and water.
  • the acrylic prepolymer containing oxetane functional groups provided by the present invention has an oxetane group in the side chain and an acrylate group in the terminal group, and can be used as a macromonomer and/or a crosslinking agent to perform free radical curing and cationic curing separately or simultaneously. Therefore, the present invention also provides the use of the acrylic prepolymer containing oxetane functional groups of the present invention in free radical curing and/or cationic curing. In addition, the prepolymer of the present invention has the advantages of low molecular weight, narrow molecular weight distribution, low viscosity, good fluidity, etc.
  • the acrylic prepolymer containing oxetane functional groups provided by the present invention
  • the acrylic prepolymer can have a similar number or more oxetane groups, which can provide a higher crosslinking density during the polymerization process, thereby effectively performing the curing reaction.
  • such prepolymers have good compatibility with wide-band light sources such as ultraviolet light, visible light or laser, so they can be better applied to specific coatings, inks, microelectronics, 3D printing, and printing fields with higher requirements.
  • the preparation of the prepolymer of the present invention avoids complex multi-step organic synthesis reactions, thereby overcoming the defects of cumbersome post-processing of multi-step reactions and the generation of by-products, and is very suitable for industrial production.
  • a photocurable composition which comprises an acrylic prepolymer containing an oxetane functional group of the present invention as a polymerizable macromonomer or prepolymer.
  • the photocurable composition of the present invention can be a photocurable coating composition, a photocurable ink composition or a photoresist composition, etc.
  • the photocurable composition may also comprise a free radical photoinitiator and/or a cationic photoinitiator and optionally other monomers or oligomers containing vinyl ether double bonds, alicyclic epoxy groups or oxetane groups that can participate in free radical and/or cationic photocuring, such as 3-methyl-3-hydroxymethyloxetane (MOXE), 3,4-epoxycyclohexylcarboxylic acid 3,4-epoxycyclohexylmethyl ester (AOO) or 4-vinyl epoxycyclohexane (VOH).
  • MOXE 3-methyl-3-hydroxymethyloxetane
  • AOO 3,4-epoxycyclohexylcarboxylic acid 3,4-epoxycyclohexylmethyl ester
  • VH 4-vinyl epoxycyclohexane
  • iodine is commonly used.
  • Salt and sulfur For example, one or more selected from the group consisting of 4-(phenylthio)phenyl diphenylsulfide can be used: Hexafluorophosphate, 4-(phenylthio)phenyl diphenylsulfide Hexafluoroantimonate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfur Hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfur Hexafluoroantimonate, diphenyl iodide hexafluorophosphate Salt, 4-octyloxydiphenyl iodide Hexafluorophosphate, 4-octyloxydiphenyl iodide Hexafluoroantimonate, 4-isobutylphen
  • mono- or diacylphosphine oxides benzophenones, benzoin and benzil are commonly used.
  • one or more selected from the following group can be used: phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoylphosphonic acid ethyl ester, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenylacetone, methyl benzoylformate, benzophenone, benzil, benzoin, ⁇ , ⁇ -diethoxyacetophenone, 4-methylbenzophenone, 4 ,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone and 2,4,6-trimethylbenzophenone; preferably 2-hydroxy-2-methyl-1-pheny
  • the photocurable composition of the present invention may further comprise a sensitizer.
  • a sensitizer for example, benzophenone and its derivatives such as 4-(4-methylphenylthio)benzophenone or 4,4'-di(diethylamino)benzophenone, thioxanthone and its derivatives such as 2-isopropylthioxanthone, anthraquinone and its derivatives such as 2-ethylanthraquinone, coumarin derivatives such as 5,7-dimethoxy-3-(4-dodecylbenzoyl)coumarin, camphorquinone, phenothiazine and its derivatives, 3-(aroylmethylene)thiazoline, rhodanine and its derivatives, eosin, rhodamine, acridine, anthocyanin, merocyanine dyes may be mentioned; benzophenone and its derivatives, thioxanthone and its derivatives
  • the photocurable composition of the present invention may also optionally contain an organic solvent.
  • the selection of the organic solvent is conventional.
  • the organic solvent mention may be made of aromatic hydrocarbons such as benzene, toluene, halogenated alkanes such as chloroform, methylene chloride, ethyl chloride, ketones such as acetone, butanone, amyl ketone, etc., alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol, and glycol ethers, glycol ether acetates, propylene glycol ethers, propylene glycol ether acetates, etc.
  • the photocurable composition of the present invention may optionally further comprise other additives, such as a leveling agent, an antioxidant, an anti-settling agent, a colorant, a microbicide, and a heat preservation material additive.
  • additives such as a leveling agent, an antioxidant, an anti-settling agent, a colorant, a microbicide, and a heat preservation material additive.
  • each component of the photocurable composition of the present invention is uniformly mixed together according to the commonly used dosage.
  • another aspect of the present invention also provides a cured material obtainable from the photocurable composition of the present invention.
  • the cured material obtained may be a photocurable coating, which includes a functional material. coatings of materials, coatings of ultraviolet light, visible light or laser filters; sealants; photolithography materials; holographic recording materials; 3D printing materials; lithographic materials; materials for preparing optical devices and materials for improving mechanical properties, such as carbon fiber composites and/or inorganic nanoparticles and/or organic nanoparticles, etc.
  • the present invention also relates to a method for preparing a photocurable material, which comprises irradiating the photocurable composition of the present invention with ultraviolet light, visible light or laser.
  • the photocuring conditions are not particularly limited, as long as the photocurable composition of the present invention can be photocured.
  • the photocurable material has the advantages of good curing density, fast curing speed, anti-fouling, good heat resistance, etc. because it contains the prepolymer of the present invention as a photocurable prepolymer or macromonomer and/or crosslinking agent.
  • methyl methacrylate (3-ethyloxetane-3-yl), 5g of ethylene glycol dimethacrylate, 100ml of acetonitrile, 1g of azobisisobutyronitrile, a free radical initiator, and 5ppm of chain transfer agent CoBF to a reactor equipped with a mechanical stirrer, stir to mix thoroughly, heat to 60°C, and polymerize at 60°C for 12 hours. After that, remove acetonitrile by vacuum distillation to obtain liquid hyperbranched copolymer A5.
  • the product can be precipitated in a mixed solvent of methanol and water (volume ratio 1:1) to remove residual monomers and other small molecular substances.
  • the weight average molecular weight (M w ) and number average molecular weight (M n ) in terms of polystyrene were measured by gel permeation chromatography (Waters: Waters 707). The measurement results are shown in Table 1 and FIGS. 1-3 .
  • the product prepared in the above embodiment was dissolved in N,N-dimethylformamide (DMF) at a concentration of 4000ppm, and then 100 ⁇ l was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC, flowing in at a flow rate of 1.0ml/min, and the analysis was performed at 35°C.
  • Waters HR-05, 1, 2, and 4E were connected in series as a chromatography column. The measurement was performed at 35°C using an RI detector and a PAD detector. At the same time, the measured weight average molecular weight was divided by the number average molecular weight to calculate the polydispersity index (PDI).
  • PDI polydispersity index
  • Example 1 shows that by comparing Example 1 with Example 2, it can be seen that by controlling the amount of chain transfer agent added, the molecular weight of the prepolymer tends to decrease with the increase in the amount of catalyst CoBF.
  • the prepolymer of the present invention (homopolymer A1) prepared in Example 1 was subjected to nuclear magnetic resonance detection, and the result is shown in Figure 4.
  • the prepolymer of the present invention (hyperbranched copolymer A5) prepared in Example 5 was also subjected to nuclear magnetic resonance detection, and the result is shown in Figure 5. It can also be seen that the characteristic peak of the acrylate double bond (chemical shift is about 5.5-6.5ppm) and the characteristic peak of the methylene group (chemical shift is about 4.5ppm).
  • the prepolymer (homopolymer A2) of the present invention prepared in Example 2 was subjected to MALDI-ToF MS detection, and the results are shown in Figure 6.
  • the prepolymer has a typical peak of methyl methacrylate (3-ethyloxetane-3-yl) methyl ester prepolymer, the molecular weight is mainly concentrated between 600-3000Da, and the peak spacing is the mass of methyl methacrylate (3-ethyloxetane-3-yl) methyl ester monomer.
  • a cationic photocuring reaction was carried out on the surface of a PVDF-based ultrafiltration membrane.
  • the photocuring reaction used an oxetane-based small molecule 3-methyl-3-hydroxymethyloxetane (MOXE) and the prepolymer of the present invention (homopolymer A1, copolymer A3) and an alicyclic epoxy compound 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (AOO).
  • MOXE oxetane-based small molecule 3-methyl-3-hydroxymethyloxetane
  • AOO alicyclic epoxy compound 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate
  • Hexafluorophosphate was dissolved in methanol, and then the PVDF membrane was immersed in the methanol solution for 10 minutes, and then irradiated under a 365nm UV lamp for 10 minutes.
  • the ratio of the photocuring reactants and the structure of some raw materials are shown in Table 2.
  • the surface morphology of the original PVDF membrane and the photocured modified membranes M1-M4 was characterized by scanning electron microscopy, and it can be found that in the photocuring experiment with the addition of the prepolymer of the present invention (homopolymer A1, copolymer A3), the surface pore structure of the membranes M2, M3, and M4 was significantly reduced compared to the original membrane.
  • the surface pore structure of membrane M1 did not change significantly compared with the original PVDF membrane, and the change in water flux was also small, indicating that the cross-linking structure was not obvious.
  • 0.2 g of A5 and 3 wt% (relative to the weight of A5 added) of a cationic photoinitiator 4-(phenylthio)phenyl diphenylsulfide were added.
  • 0.2 g of A5 and 3 wt% (relative to the weight of A5 added) of a cationic photoinitiator 4-(phenylthio)phenyl diphenylsulfide were added.
  • Hexafluorophosphate and 5 wt% of free radical photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone were dissolved in 2 ml of acetone. The solution was poured into a culture dish, and after the solvent evaporated, it was illuminated under a 240 nm ultraviolet lamp for 5 minutes to observe the morphology of the culture dish surface.
  • the test results are shown in Figure 8.
  • the left side of Figure 8 shows the picture of the prepolymer solution before light curing.
  • the solutions of the three tests were all clear and transparent before light irradiation. After light irradiation, white solids were produced on the surface of the culture dish.
  • the light-cured layer produced by free radical light curing (3.2.1) and cationic light curing (3.2.2) was thinner, while the cured layer produced by dual light curing (3.2.3) combining the two curing methods was obviously denser and thicker.
  • the hyperbranched copolymer A5 prepared in Example 5 of the present invention and three photocured products (3.2.1, 3.2.2 and 3.2.3) were characterized by infrared. 1630 cm -1 is the characteristic peak of the carbon-carbon double bond of the hyperbranched copolymer A5, and the double bond characteristic peak intensity of 3.2.1 and 3.2.3 is significantly smaller than that of the characteristic peak intensity before curing; around 980 cm -1 is the characteristic peak of oxetane of the hyperbranched copolymer A5, The characteristic peak intensities of 3.2.2 and 3.2.3 are also significantly reduced here.
  • hyperbranched prepolymer containing oxetane groups and unsaturated acrylate double bonds can participate in free radical photocuring with double bonds and cationic photocuring with oxetane groups, and the two will synergistically promote the effect of photocuring, making the generated cured layer more dense.

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Abstract

本发明涉及一种含有氧杂环丁烷官能团的丙烯酸系预聚物，该类预聚物侧链具有氧杂环丁烷基团且端基具有丙烯酸酯基团，可以同时作为自由基固化和/或阳离子固化的大分子单体和/或交联剂。本发明还涉及制备本发明含有氧杂环丁烷官能团的丙烯酸系预聚物的方法及其在自由基固化和/或阳离子固化中的用途。

Description

含有氧杂环丁烷官能团的丙烯酸系预聚物及其制备和应用 技术领域
本发明属于高分子化学和光固化技术领域，具体涉及含有氧杂环丁烷官能团的丙烯酸系预聚物，该类预聚物可作为大分子单体和/或交联剂，适用于自由基固化和/或阳离子固化。本发明还涉及含有氧杂环丁烷官能团的丙烯酸系预聚物的制备及其应用。
背景技术
光固化技术按照机理可分为自由基固化、阳离子固化以及自由基/阳离子混杂固化。自由基固化是光引发剂在光辐照下产生自由基，引发预聚物和单体中的不饱和基团发生加成聚合反应。阳离子固化是阳离子引发剂在光辐照下产生质子酸或路易斯酸，形成正离子活性中心，引发阳离子开环聚合。自由基/阳离子混杂固化则是指在同一体系中同时发生自由基光聚合和阳离子光聚合。上述自由基和/或阳离子固化的体系，尤其是阳离子固化体系，具有固化速度快、引发剂种类多、储存稳定等优点，因此工业需求强烈，在光固化涂料、印刷油墨、光敏抗蚀干膜、绝缘涂层中得到了广泛应用。然而，也同时存在一些问题和不足，尤其是针对固化体系的预聚物或大分子单体种类少、价格高，固化产品性能不能调节等缺点，从而限制了其在某些特定领域的实际应用。
因此，近年来，本领域技术人员针对适用于光固化体系的各种单体及其预聚物，尤其是多官能度氧杂环烷类单体以及预聚物的合成与应用的研究不断深入。例如，CN104447635A通过酯交换反应制备了二、三官能度氧杂环丁烷单体；EP3486238A1借助环氧化合物的开环聚合制备了一系列含有氧杂环丁烷的预聚物，并通过聚合后续修饰在端基引入了环氧基团，获得了具有多环氧和氧杂环丁烷基团的预聚物；US2001002423A1利用含有氧杂环丁烷基团的乙烯基单体的自由基聚合获得了具有氧杂环丁烷基团和氟原子的共聚物。
然而，总体而言，现有技术已知的多官能度氧杂环烷类预聚物仍然 存在分子量和分子量分布的控制不佳以及粘度高和流动性不够好的不足。另外，现有技术对多官能度氧杂环丁烷单体及其预聚物的制备需要用到多步有机合成反应，存在反应后处理繁琐和产生副产物等缺陷。再者，现有氧杂环丁烷类预聚物的制备主要利用了常规自由基聚合或聚合后修饰的策略，存在反应不完全、产物性质不均一等问题。
有鉴于此，研究和开发具有更高性能的多官能度氧杂环丁烷类预聚物，尤其是开发适用于目前迅速发展的阳离子固化和/或自由基固化体系并具有可控分子量和低粘度的新型多官能度氧杂环丁烷类预聚物，逐渐成为目前该领域的核心研究方向。
发明内容
鉴于现有技术存在的问题，本发明的发明人在适用于阳离子固化和/或自由基固化体系的预聚物方面进行了广泛而又深入的研究，以期找到一种能够适用于阳离子固化和/或自由基固化体系并具有可控分子量和低粘度的新型多官能度氧杂环丁烷类预聚物。
本发明人惊讶地发现，通过采用含有氧杂环丁烷官能团的丙烯酸系单体，利用有机钴配合物作为催化链转移剂进行催化链转移聚合(CCTP)，经过一步反应即可获得侧链具有氧杂环丁烷基团且端基具有丙烯酸酯基团的含有氧杂环丁烷官能团的新型丙烯酸系预聚物。与通过常规自由基聚合或聚合后修饰策略获得的氧杂环丁烷类预聚物相比，本发明提供的含有氧杂环丁烷官能团的新型丙烯酸系预聚物的侧链具有氧杂环丁烷基团且端基具有丙烯酸酯基团，可作为大分子单体和/或交联剂，分别或同时进行自由基固化和阳离子固化，从而可以用于自由基固化、阳离子光固化或自由基/阳离子双重固化体系。
本发明目的正是基于前述发现得以实现。
因此，本发明的一个目的是提供一种含有氧杂环丁烷官能团的丙烯酸系预聚物，该类预聚物侧链具有氧杂环丁烷基团且端基具有丙烯酸酯基团，可以作为自由基固化和/或阳离子固化的大分子单体和/或交联剂。
此外，本发明提供的含有氧杂环丁烷官能团的丙烯酸系预聚物的有益效果还表现为：
(1)本发明可以调控所得含有氧杂环丁烷官能团的丙烯酸系预聚物的分子量和粘度，从而获得具有低分子量和窄分子量分布以及低粘度和优良流动性的预聚物。
(2)本发明可以调控所得含有氧杂环丁烷官能团的丙烯酸系预聚物中氧杂环丁烷基团的含量和密度，亦可以调控预聚物的玻璃化转变温度、热稳定性等物理性质。因此，与常规的二、三或多官能度氧杂环丁烷小分子单体相比，本发明提供的含有氧杂环丁烷官能团的丙烯酸系预聚物可以具有数量相似或更多的氧杂环丁烷基团数量，在聚合过程中可以提供更高的交联密度。
(3)本发明采用一步反应避免了复杂的多步有机合成反应，由此避免了多官能度氧杂环丁烷单体的合成困难以及成本过高等问题，并克服了多步反应后处理繁琐和产生副产物等缺陷。
本发明的另一目的是提供一种制备本发明含有氧杂环丁烷官能团的丙烯酸系预聚物的方法。
本发明的再一目的是提供本发明含有氧杂环丁烷官能团的丙烯酸系预聚物在自由基固化和/或阳离子固化中的用途。
实现本发明目的的技术方案可以概括如下：
1.一种含有氧杂环丁烷官能团的丙烯酸系预聚物，其特征在于所述预聚物的侧链具有氧杂环丁烷基团，端基具有丙烯酸酯基团。
2.根据实施方案1的预聚物，其特征在于所述预聚物的聚合度为1-50，优选2-18，更优选3-15；和/或，
所述预聚物的重均分子量Mw为200-10000Da，优选500-8000Da，更优选600-5000Da；和/或，
所述预聚物的多分散性指数(PDI)为1.0-5.0，优选1.0-4.0，更优选1.0-3.0。
3.根据实施方案1或2的预聚物，其特征在于所述预聚物为均聚物或共聚物，其中共聚物为无规、梯度或嵌段共聚物。
4.根据实施方案1-3中任一项的预聚物，其特征在于所述预聚物为超支化共聚物，其中超支化共聚物的侧链也具有丙烯酸酯基团。
5.根据实施方案1-4中任一项的预聚物，其特征在于所述预聚物衍生自如下单体：
(A)式1的单体：
其中
x为1-3的整数，优选x为1；
R1为H或者CH3，优选R1为CH3；以及
R2为H、卤素、C1-C6烷基、C1-C6卤代烷基、C1-C6羟烷基、C1-C6烷氧基或C1-C6卤代烷氧基；优选R2为H、卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4羟烷基、C1-C4烷氧基或C1-C4卤代烷氧基；更优选R2为H或C1-C4烷基，尤其是乙基；和
(B)任选的其他(甲基)丙烯酸类或苯乙烯类单体；和
(C)任选的二元醇的二(甲基)丙烯酸酯单体。
6.根据实施方案5的预聚物，其特征在于单体(A)为甲基丙烯酸(3-乙基氧杂环丁烷-3-基)甲酯。
7.根据实施方案5或6的预聚物，其特征在于如果存在的话，单体(B)为选自下组中的一种或多种：丙烯酸、甲基丙烯酸、富马酸、肉桂酸、巴豆酸、衣康酸、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸苄酯及其衍生物、甲基丙烯酸苄酯及其衍生物、苯乙烯及其衍生物；优选甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯及甲基丙烯酸苄酯；更优选甲基丙烯酸甲酯和/或甲基丙烯酸丁酯；和/或，
如果存在的话，单体(B)与其他单体总和的质量比为1:1-1:5，优选1:1-1:3，更优选1:1。
8.根据实施方案5-7中任一项的预聚物，其特征在于如果存在的话，单体(C)为选自下组中的一种或多种：二丙烯酸乙二醇酯、二甲基丙烯酸乙二醇酯、二丙烯酸1,2-丙二醇酯、二甲基丙烯酸1,2-丙二醇酯、二丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,4-丁二醇酯、二丙烯酸1,6-己二醇酯、二甲基丙烯酸1,6-己二醇酯、二丙烯酸二甘醇酯、二甲基丙烯酸二甘醇酯、二丙烯酸三甘醇酯、二甲基丙烯酸三甘醇酯、二丙烯酸四甘醇酯、二甲基丙烯酸四甘醇酯、二丙烯酸二丙二醇酯、二甲基丙烯酸二丙二醇酯、二丙烯酸三丙二醇酯及二甲基丙烯酸三丙二醇酯；优选二甲基丙烯酸乙二醇酯、二甲基丙烯酸1,2-丙二醇酯、二甲基丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,6-己二醇酯、二甲基丙烯酸二甘醇酯、二甲基丙烯酸三甘醇酯、二甲基丙烯酸四甘醇酯、二甲基丙烯酸二丙二醇酯及二甲基丙烯酸三丙二醇酯；更优选二甲基丙烯酸乙二醇酯；和/或
如果存在的话，单体(C)与其他单体总和的质量比为1:3-1:20，优选1:4-1:10，更优选1:5。
9.一种制备根据实施方案1-8中任一项的预聚物的方法，其特征在于在链转移剂和自由基引发剂存在下，使单体(A)及任选的单体(B)和任选的单体(C)进行一步法催化链转移聚合(CCTP)反应。
10.根据实施方案9的方法，其特征在于链转移剂为选自下组中的一种或多种：双[(二氟硼基)二甲基乙二肟根合]钴(II)(bis[(difluoroboryl)dimethyl glyoximato]cobalt(II)，CoBF)、双[(二氟硼基)二甲基苯基乙二肟根合]钴(II)(bis[(difluoroboryl)dimethyl phenyl-glyoximato]cobalt(II)，Co(MePh)BF)、双[(二氟硼基)二苯基乙二肟根合]钴(II)(bis[(difluoroboryl)diphenyl glyoximato]cobalt(II)，CoPhBF)、双[二甲基乙二肟根合]钴(II)(bis[dimethyl glyoximato]cobalt(II)，Co(dmg)2)、[内消旋-四苯基卟啉]钴(cobalt(meso-Ph4-porphyrin)，CoP)、四甲基醚型血卟啉钴(tetramethyl ether of cobalt hematoporphyrin IX，CoTMHP)、四氟苯基卟啉钴(cobalt tetrafluorophenyl porphyrin，CoTFPP)、双[(二氟硼基)二甲基乙二肟根合]异丙基吡啶钴(II)(bis[(difluoroboryl)dimethyl glyoximate]isopropyl pyridine cobalt(II)，Co(ipp)BF)及2,16-双(4-丁酰胺基)酞菁钴(II)(cobalt(II) 2,16-bis(4-butanamidoyl)phthalocyanine，CoPc)，优选双[(二氟硼基)二甲基乙二肟根合]钴(II)(CoBF)；和/或，
链转移剂的用量基于单体的总重量为0.1-100ppm，优选1-80ppm，更优选5-50ppm。
11.根据实施方案9或10的方法，其特征在于自由基引发剂为选自下组中的一种或多种：过硫酸铵、过硫酸钾、过硫酸钠、偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、偶氮异丁氰基甲酰胺、过氧化二苯甲酰、叔丁基过氧化氢及过氧化氢异丙苯，优选偶氮二异丁腈；和/或
自由基引发剂的用量基于单体的总重量为0.1-8重量％，优选0.1-4重量％，更优选0.3-2重量％。
12.根据实施方案9-11中任一项的方法，其特征在于反应温度为50-120℃，优选55-100℃，更优选60-80℃。
13.根据实施方案9-12中任一项的方法，其特征在于所述一步法催化链转移聚合(CCTP)反应采用本体聚合、溶液聚合、乳液聚合、悬浮聚合或沉淀聚合的聚合方式进行。
14.根据实施方案1-8中任一项或者根据实施方案9-13中任一项的方法获得的预聚物在自由基固化和/或阳离子固化中的用途。
15.一种包含实施方案1-8中任一项或者根据实施方案9-13中任一项的方法获得的预聚物的可光固化组合物。
16.可由实施方案15的可光固化组合物得到的固化材料。
17.一种制备光固化材料的方法，其包括用紫外光、可见光或激光对实施方案15的可光固化组合物进行辐照。
附图说明：
图1为根据实施例1制备的本发明预聚物(均聚物A1)的GPC图谱。
图2为根据实施例2制备的本发明预聚物(均聚物A2)的GPC图谱。
图3为根据实施例5制备的本发明预聚物(超支化共聚物A5)的GPC图谱。
图4为根据实施例1制备的本发明预聚物(均聚物A1)的核磁图谱。
图5为根据实施例5制备的本发明预聚物(超支化共聚物A5)的核磁 图谱。
图6为根据实施例2制备的本发明预聚物(均聚物A2)的MALDI-ToF MS图谱。
图7为根据实施例1和3制备的本发明预聚物(均聚物A1、共聚物A3)进行PVDF基超滤膜光固化实验测试的表面形貌及水通量柱状的对比示意图。
图8为根据实施例5制备的本发明预聚物(超支化共聚物A5)的培养皿光固化实验测试的直观效果图。
图9为根据实施例5制备的本发明预聚物(超支化共聚物A5)的培养皿光固化实验测试的红外谱图。
具体实施方式
根据本发明的一个方面，提供了一种含有氧杂环丁烷官能团的丙烯酸系预聚物，该预聚物的侧链具有氧杂环丁烷基团，端基具有丙烯酸酯基团。
具体而言，本发明的预聚物既在侧链具有氧杂环丁烷基团，又在端基具有丙烯酸酯基团，因此可作为大分子单体和/或交联剂，分别或同时进行自由基固化和阳离子固化，从而可以用于自由基固化、阳离子光固化或自由基/阳离子双重固化体系。
根据本发明的一个优选方面，本发明预聚物衍生自如下单体：
(A)式1的单体：
其中
x为1-3的整数；
R1为H或者CH3；以及
R2为H、卤素、C1-C6烷基、C1-C6卤代烷基、C1-C6羟烷基、C1-C6烷氧基或C1-C6卤代烷氧基；和
(B)任选的其他(甲基)丙烯酸类或苯乙烯类单体；和
(C)任选的二元醇的二(甲基)丙烯酸酯单体。
在本发明中，术语“丙烯酸系”意指包含丙烯酸基团的丙烯酸酯或甲基丙烯酸酯类或其衍生物及组合。单独出现的“丙烯酸酯基团”应理解为包括丙烯酸酯基团和甲基丙烯酸酯基团二者。
在本发明中，前缀“Cn-Cm”在每种情况下表示该基团中包含的碳原子数为n-m个。
“卤素”是指氟、氯、溴和碘。在本发明中，优选的是，卤素包括氟、氯或其组合。
本文所用的术语“Cn-Cm烷基”是指具有n-m个，例如1-6个，优选1-4个碳原子的支化或未支化饱和烃基。C1-C6烷基可以是甲基、乙基、丙基、丁基、戊基、己基及其异构体，特别是甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基。C1-C4烷基可以是甲基、乙基、丙基、丁基及其异构体，特别是甲基、乙基、正丙基、异丙基、正丁基、异丁基及叔丁基。
本文所用的术语“Cn-Cm卤代烷基”是指被一个或多个相同或不同卤素原子取代的Cn-Cm烷基，例如C1-C6卤代烷基，优选C1-C4卤代烷基。作为Cn-Cm卤代烷基的实例，可以提及一氯甲基、一氯乙基、二氯乙基、三氯乙基、一氯丙基、二氯甲基乙基、一氯丁基、二氯甲基丙基、三氯甲基丙基、一氯戊基、二氯甲基丁基、一氯己基及其异构体，特别是1-氯甲基乙基、1,1-二氯甲基乙基、1-氯甲基丙基、2-氯甲基丙基、1,1-二氯甲基丙基、1,2-二氯甲基丙基、2,2-二氯甲基丙基、1,1,2-三氯甲基丙基及1,2,2-三氯甲基丙基。
本文所用的术语“Cn-Cm羟烷基”是指在Cn-Cm烷基对应的开链Cn-Cm烷烃的任何碳原子上键合有一个羟基的Cn-Cm烷基，例如C1-C6羟烷基，尤其优选C1-C4羟烷基，例如羟甲基、羟乙基、羟丙基、羟丁基、羟戊基、羟己基及其异构体，特别是羟甲基、羟乙基、羟基正丙基、羟基异丙基、羟基正丁基、羟基仲丁基、羟基叔丁基、羟基正戊基及羟基正己基。
本文所用的术语“Cn-Cm烷氧基”是指在Cn-Cm烷基对应的开链Cn-Cm烷烃的任何碳原子上键合有一个氧原子作为连接基团的Cn-Cm烷基，例如C1-C6烷氧基，更优选C1-C4烷氧基。C1-C6烷氧基可以是甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基及其异构体，特别是甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、2-丁氧基、叔丁氧基、正戊氧基、异戊氧基及正己氧基。C1-C4烷氧基可以是甲氧基、乙氧基、丙氧基、丁氧基及其异构体，特别是甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基及叔丁氧基。
本文所用的术语“Cn-Cm卤代烷氧基”是指被一个或多个相同或不同卤素原子取代的Cn-Cm烷氧基，例如C1-C6卤代烷氧基，优选C1-C4卤代烷氧基。作为Cn-Cm卤代烷氧基的实例，可以提及一氯甲氧基、2-氯乙氧基、3-氯丙氧基、4-氯丁氧基、5-氯戊氧基、6-氯己氧基及其异构体，特别是一氯甲氧基、2-氯乙氧基、3-氯正丙氧基、2-氯异丙氧基、4-氯正丁氧基、3-氯仲丁氧基、2-氯叔丁氧基、5-氯正戊氧基、4-氯异戊氧基及6-氯正己氧基。
在本发明的一些实施方案中，R2通常为H、卤素、C1-C6烷基、C1-C6卤代烷基、C1-C6羟烷基、C1-C6烷氧基或C1-C6卤代烷氧基。优选的是，R2为H、卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4羟烷基、C1-C4烷氧基或C1-C4卤代烷氧基。特别优选的是，R2为H或C1-C4烷基。例如，R2可以为H、氯、溴、甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、叔丁氧基、羟甲基、羟乙基、羟基正丙基、羟基异丙基、羟基正丁基、羟基仲丁基或羟基叔丁基。
在本发明的一个特别优选实施方案中，R2为乙基。
在本发明的一个优选实施方案中，x为1。
在本发明的一个优选实施方案中，R1为CH3。
在本发明的一个尤其优选的实施方案中，单体(A)为甲基丙烯酸(3-乙基氧杂环丁烷-3-基)甲酯。
在本发明的一个优选实施方案中，本发明的预聚物还可以包含单体(B) 其他(甲基)丙烯酸类或苯乙烯类单体。因此，本发明的预聚物可以为均聚物或共聚物，其中共聚物可以为无规、梯度或嵌段共聚物。
在本发明的一个优选实施方案中，如果存在的话，单体(B)为选自下组中的一种或多种：丙烯酸、甲基丙烯酸、富马酸、肉桂酸、巴豆酸、衣康酸、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸苄酯及其衍生物、甲基丙烯酸苄酯及其衍生物、苯乙烯及其衍生物。
在本发明的一个更优选实施方案中，如果存在的话，单体(B)为选自下组中的一种或多种：甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯及甲基丙烯酸苄酯。
在本发明的一个特别优选实施方案中，如果存在的话，单体(B)为甲基丙烯酸甲酯和/或甲基丙烯酸丁酯。
在本发明的又一优选实施方案中，如果存在的话，单体(B)与其他单体总和的质量比为1:1-1:5，优选1:1-1:3，更优选1:1。
在本发明的一个优选实施方案中，本发明的预聚物还可以包含单体(C)其他二元醇的二(甲基)丙烯酸酯单体。因此，本发明的预聚物也可以为超支化共聚物，其中超支化共聚物的侧链也具有丙烯酸酯基团。
在本发明的一个优选实施方案中，如果存在的话，单体(C)为选自下组中的一种或多种：二丙烯酸乙二醇酯、二甲基丙烯酸乙二醇酯、二丙烯酸1,2-丙二醇酯、二甲基丙烯酸1,2-丙二醇酯、二丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,4-丁二醇酯、二丙烯酸1,6-己二醇酯、二甲基丙烯酸1,6-己二醇酯、二丙烯酸二甘醇酯、二甲基丙烯酸二甘醇酯、二丙烯酸三甘醇酯、二甲基丙烯酸三甘醇酯、二丙烯酸四甘醇酯、二甲基丙烯酸四甘醇酯、二丙烯酸二丙二醇酯、二甲基丙烯酸二丙二醇酯、二丙烯酸三丙二醇酯及二甲基丙烯酸三丙二醇酯。
在本发明的一个更优选实施方案中，如果存在的话，单体(C)为选自下组中的一种或多种：二甲基丙烯酸乙二醇酯、二甲基丙烯酸1,2-丙二醇酯、二甲基丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,6-己二醇酯、二甲基丙 烯酸二甘醇酯、二甲基丙烯酸三甘醇酯、二甲基丙烯酸四甘醇酯、二甲基丙烯酸二丙二醇酯及二甲基丙烯酸三丙二醇酯。
在本发明的一个特别优选实施方案中，如果存在的话，单体(C)为二甲基丙烯酸乙二醇酯。
在本发明的又一优选实施方案中，如果存在的话，单体(C)与其他单体总和的质量比为1:3-1:20，优选1:4-1:10，更优选1:5。
在本发明的一些具体实施方案中，本发明提供的这种预聚物具有低分子量和窄分子量分布。具体而言，该预聚物的聚合度为1-50，优选2-18，更优选3-15。该预聚物的重均分子量Mw为200-10000Da，优选500-8000Da，更优选600-5000Da。该预聚物的多分散性指数(PDI)为1.0-5.0，优选1.0-4.0，更优选1.0-3.0。
根据本发明的另一个方面，提供了一种制备本发明预聚物的方法，其包括在链转移剂和自由基引发剂存在下，使单体(A)及任选的单体(B)和任选的单体(C)进行一步法催化链转移聚合(CCTP)反应。
催化链转移聚合(CCTP)是近期发现的采用有机钴配合物作为催化链转移剂的一种自由基聚合方法。链转移剂有机钴配合物的链转移常数非常高，可使得形成的自由基链上的氢转移到另一个烯烃上，从而形成末端为不饱和键的大分子，这种端基双键具有足够的活性，可以与特殊单体发生断裂-加成或自由基聚合反应。
在本发明的方法中，通过采用一步法催化链转移聚合(CCTP)反应，即向反应体系内同时加入单体(A)及任选的单体(B)和任选的单体(C)、链转移试剂和自由基引发剂，在规定的条件下完成聚合。
在本发明的一步法催化链转移聚合(CCTP)反应中，链转移剂为选自下组中的一种或多种：双[(二氟硼基)二甲基乙二肟根合]钴(II)(bis[(difluoroboryl)dimethyl glyoximato]cobalt(II)，CoBF)、双[(二氟硼基)二甲基苯基乙二肟根合]钴(II)(bis[(difluoroboryl)dimethyl phenyl-glyoximato]cobalt(II)，Co(MePh)BF)、双[(二氟硼基)二苯基乙二肟根合]钴(II)(bis[(difluoroboryl)diphenyl glyoximato]cobalt(II)，CoPhBF)、双[二甲基乙二肟根合]钴(II)(bis[dimethyl glyoximato]cobalt(II)， Co(dmg)2)、[内消旋-四苯基卟啉]钴(cobalt(meso-Ph4-porphyrin)，CoP)、四甲基醚型血卟啉钴(tetramethyl ether of cobalt hematoporphyrin IX，CoTMHP)、四氟苯基卟啉钴(cobalt tetrafluorophenyl porphyrin，CoTFPP)、双[(二氟硼基)二甲基乙二肟根合]异丙基吡啶钴(II)(bis[(difluoroboryl)dimethyl glyoximate]isopropyl pyridine cobalt(II)，Co(ipp)BF)及2,16-双(4-丁酰胺基)酞菁钴(II)(cobalt(II)2,16-bis(4-butanamidoyl)phthalocyanine，CoPc)。
在本发明的一个优选实施方案中，链转移剂为双[(二氟硼基)二甲基乙二肟根合]钴(II)(CoBF)。
在本发明的一些具体实施方案中，链转移剂的用量基于单体的总重量为0.1-100ppm，优选1-80ppm，更优选5-50ppm，例如1ppm、3ppm、5ppm、10ppm、20ppm、30ppm、40ppm、50ppm、60ppm、80ppm。
在本发明的一步法催化链转移聚合(CCTP)反应中，自由基引发剂为选自下组中的一种或多种：过硫酸铵、过硫酸钾、过硫酸钠、偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、偶氮异丁氰基甲酰胺、过氧化二苯甲酰、叔丁基过氧化氢及过氧化氢异丙苯。
在本发明的一个优选实施方案中，自由基引发剂为偶氮二异丁腈。
在本发明的一些具体实施方案中，自由基引发剂的用量基于单体的总重量为0.1-8重量％，优选0.1-4重量％，更优选0.3-2重量％，例如0.1重量％、0.5重量％、1.0重量％、1.5重量％、2.0重量％、3.0重量％和4.0重量％。
上述一步法催化链转移聚合(CCTP)反应通常在溶剂中，优选在有机溶剂中进行。对于溶剂类型的选择，没有特别的限制，只要能够适用于一步法催化链转移聚合(CCTP)反应并且对反应参与物呈化学惰性即可，即不参与该催化链转移聚合(CCTP)反应即可。合适的溶剂例如可以为选自下组中的一种或多种：甲醇、乙醇、丙醇、异丙醇、乙腈、丁酮、甲苯、丙二醇甲醚、乙二醇乙醚、丙二醇乙醚及乙二醇甲醚。作为溶剂的实例，通常采用乙腈。此外，对于溶剂的用量，没有特别的限制，本领 域技术人员根据反应的实践规模选择合适的用量即可。
在本发明的一些具体实施方案中，该一步法催化链转移聚合(CCTP)反应的温度范围通常为50-120℃，优选55-100℃，更优选60-80℃，例如50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃和100℃。对反应时间没有特别的限制，通常进行1-20小时，优选1-12小时。
此外，该方法通常在惰性气氛下进行。对于惰性气体类型的选择，没有特别的限制，只要能够对整个反应体系呈化学惰性即可。作为惰性气体的实例，通常采用氮气即可。
就本发明而言，该一步法催化链转移聚合(CCTP)反应可以采用本体聚合、溶液聚合、乳液聚合、悬浮聚合或沉淀聚合的聚合方式进行。对投料方法也没有特别的限制，根据反应的实践规模，可以采用本领域技术人员已知的一次性投料法、半连续投料法和连续投料法进行。
在一步法催化链转移聚合(CCTP)反应完成之后，获得本发明的含有氧杂环丁烷官能团的丙烯酸系预聚物产物。通常而言，如果想要进一步提高反应产物的纯度，还可对该反应产物进行进一步提纯，根据需要可以选择对该反应产物进行后处理，例如除去残留的有机溶剂。作为这里除去有机溶剂的手段，没有特别的限制，通常可通过减压蒸馏来除去有机溶剂。除去残留有机溶剂之后，还可以选择将产物沉淀在溶剂中，由此除掉残留的单体等小分子物质，以得到更高纯度的产品。溶剂的选择是常规的，没有特别的限制。根据本发明，有利的是，采用甲醇和水的混合物对反应产物进行处理。
本发明提供的含有氧杂环丁烷官能团的丙烯酸系预聚物的侧链具有氧杂环丁烷基团且端基具有丙烯酸酯基团，可作为大分子单体和/或交联剂，分别或同时进行自由基固化和阳离子固化。因此，本发明还提供了本发明的含有氧杂环丁烷官能团的丙烯酸系预聚物在自由基固化和/或阳离子固化中的用途。此外，本发明预聚物具有分子量低、分子量分布窄，粘度低，流动性好等优点。更进一步地，与常规的二、三或多官能度氧杂环丁烷小分子单体相比，本发明提供的含有氧杂环丁烷官能团的 丙烯酸系预聚物可以具有数量相似或更多的氧杂环丁烷基团数量，在聚合过程中可以提供更高的交联密度，从而有效地进行固化反应，再加上此类预聚物与紫外光、可见光或激光的宽幅光源匹配性良好，由此可以更好地应用于具有更高要求的特定涂料、油墨、微电子、3D打印、印刷领域。另外，本发明的预聚物制备避免了复杂的多步有机合成反应，由此克服了多步反应后处理繁琐和产生副产物等缺陷，非常适合于工业生产。
因此，根据本发明的又一方面，提供了一种可光固化组合物，该组合物包含本发明的含有氧杂环丁烷官能团的丙烯酸系预聚物作为可聚合的大分子单体或预聚物。本发明可光固化组合物可以为光固化涂料组合物、光固化油墨组合物或光致抗蚀组合物等。该可光固化组合物除了包含本发明的预聚物以外，还可包含自由基光引发剂和/或阳离子光引发剂以及任选地其它含有乙烯基醚双键、脂环族环氧基或氧杂环烷烃基等可参与自由基和/或阳离子光固化的基团的单体或低聚物，例如3-甲基-3-羟甲基氧杂环丁烷(MOXE)、3,4-环氧环己基甲酸3,4-环氧环己基甲基酯(AOO)或4-乙烯基环氧环己烷(VOH)。
作为阳离子光固化的光引发剂，常用的有碘盐和硫盐。例如，可以使用选自下组中的一种或多种:4-(苯硫基)苯基·二苯基硫六氟磷酸盐、4-(苯硫基)苯基·二苯基硫六氟锑酸盐、10-(4-联苯基)-2-异丙基噻吨酮-10-硫六氟磷酸盐、10-(4-联苯基)-2-异丙基噻吨酮-10-硫六氟锑酸盐、六氟磷酸二苯基碘盐、4-辛氧基二苯碘六氟磷酸盐、4-辛氧基二苯碘六氟锑酸盐、4-异丁基苯基·4'-甲基苯基碘六氟磷酸盐、4-异丁基苯基·4'-甲基苯基碘六氟锑酸盐、双(4-十二烷基苯)碘六氟锑酸盐、双(4-十二烷基苯)碘六氟磷酸盐、双(4-叔丁基苯)碘六氟磷酸盐或双(4-叔丁基苯)碘六氟锑酸盐；优选4-(苯硫基)苯基·二苯基硫六氟磷酸盐、4-(苯硫基)苯基·二苯基硫六氟锑酸盐、10-(4-联苯基)-2-异丙基噻吨酮-10-硫六氟磷酸盐、10-(4-联苯基)-2-异丙基噻吨酮-10-硫六氟锑酸盐、六氟磷酸二苯基碘盐、4-辛氧基二苯碘六氟磷酸盐及4-辛氧基二苯碘六氟锑酸盐；尤其是4-(苯硫基)苯基·二苯基硫六氟磷酸盐。
作为自由基光固化的光引发剂，常用的有单-或双酰基膦氧化物、苯酮类、苯偶姻和苯偶酰类。例如，可以使用选自下组中的一种或多种:苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2,4,6-三甲基苯甲酰基膦酸乙酯、1-羟基-环己基-苯基甲酮、2-羟基-2-甲基-1-苯基丙酮、苯甲酰甲酸甲酯、二苯甲酮、苯偶酰、苯偶姻、α,α-二乙氧基苯乙酮、4-甲基二苯甲酮、4,4’-双(二甲氨基)二苯甲酮、4,4’-双(二乙氨基)二苯甲酮及2,4,6-三甲基二苯甲酮；优选2-羟基-2-甲基-1-苯基丙酮、α,α-二乙氧基苯乙酮、4-甲基二苯甲酮、4,4’-双(二甲氨基)二苯甲酮、4,4’-双(二乙氨基)二苯甲酮及2,4,6-三甲基二苯甲酮；尤其是2-羟基-2-甲基-1-苯基丙酮。
本发明可光固化组合物还可以包含增感剂。作为增感剂，例如可以提及二苯甲酮及其衍生物如4-(4-甲基苯硫基)二苯甲酮或4,4’-二(二乙氨基)二苯甲酮、硫杂蒽酮及其衍生物如2-异丙基硫杂蒽酮、蒽醌及其衍生物如2-乙基蒽醌、香豆素衍生物如5,7-二甲氧基-3-(4-十二烷基苯甲酰基)香豆素、樟脑醌、吩噻嗪及其衍生物、3-(芳酰基亚甲基)噻唑啉、绕丹宁及其衍生物、曙红、罗丹明、吖啶、花青素、部花青染料；优选二苯甲酮及其衍生物、硫杂蒽酮及其衍生物、蒽醌及其衍生物、香豆素及其衍生物，尤其优选2-异丙基硫杂蒽酮。
本发明的可光固化组合物还可任选地包含有机溶剂。有机溶剂的选择是常规的。作为有机溶剂，可以提及芳烃类如苯、甲苯，卤代烷烃类如三氯甲烷、二氯甲烷、氯乙烷，酮类如丙酮、丁酮、戊酮等，醇类如甲醇、乙醇、丙醇、异丙醇、乙二醇，以及乙二醇醚类，乙二醇醚醋酸酯类，丙二醇醚类，丙二醇醚醋酸酯类等。
本发明的可光固化组合物还可任选地包含其他添加剂，例如流平剂、抗氧化剂、抗沉降剂、着色剂、杀微生物剂及保温材料添加剂等。
本发明可光固化组合物的制备及各种组分的用量是常规的，通常将本发明可光固化组合物的各个组分按照常用剂量均匀混合在一起即可。
因此，本发明的另一方面还提供了可由本发明可光固化组合物得到的固化材料。得到的固化材料可以是光固化涂层，这包括包含功能性材 料的涂层，紫外光、可见光或激光的滤色器的涂层；密封剂；光刻材料；全息记录材料；3D打印材料；平版印刷材料；光学器件的制备材料及改善机械性能的材料，例如碳纤维复合材料和/或无机纳米颗粒和/或有机纳米颗粒等。
再者，本发明还涉及一种制备光固化材料的方法，其包括用紫外光、可见光或激光对本发明可光固化组合物进行辐照。光固化条件不受特别限制，只要能使本发明的可光固化组合物进行光固化即可。该光固化材料由于包含本发明的预聚物作为可光固化预聚物或大分子单体和/或交联剂的缘故，具有固化密度好，固化速度快、抗沾污，耐热性好等优点。
实施例
下面将结合实施例对本发明的方案进行解释。本领域技术人员将会理解，下面的实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体技术或条件的，按照本领域内文献所描述的技术或条件或产品说明书进行。
下述实施例中所用的材料和试剂如表A所列，其他材料和试剂均可从商业途径得到。
表A-实验材料和试剂
下述实施例中所用的仪器如表B所列。
表B-实验仪器
实施例1.本发明预聚物(均聚物A1)的制备
在惰性气体氮气保护下，向配有机械搅拌器的反应釜中加入甲基丙烯酸(3-乙基氧杂环丁烷-3-基)甲酯50g、乙腈100ml、自由基引发剂偶氮二异丁腈1g和链转移剂CoBF 50ppm，搅拌使之充分混合，加热至60℃，并于60℃聚合12小时。之后，通过减压蒸馏除掉乙腈，即可获得液体状均聚物A1。为了进一步纯化产物，可以将产物沉淀在甲醇和水(体积比1:1)的混合溶剂中，由此除掉残留的单体等小分子物质。
实施例2.本发明预聚物(均聚物A2)的制备
在惰性气体氮气保护下，向配有机械搅拌器的反应釜中加入甲基丙烯酸(3-乙基氧杂环丁烷-3-基)甲酯50g、乙腈100ml、自由基引发剂偶氮二异丁腈1g和链转移剂CoBF 5ppm，搅拌使之充分混合，加热至60℃，并于60℃聚合12小时。之后，通过减压蒸馏除掉乙腈，即可获得液体状均聚物A2。为了进一步纯化产物，可以将产物沉淀在甲醇和水(体积比1:1)的混合溶剂中，由此除掉残留的单体等小分子物质。
实施例3.本发明预聚物(共聚物A3)的制备
在惰性气体氮气保护下，向配有机械搅拌器的反应釜中加入甲基丙烯酸(3-乙基氧杂环丁烷-3-基)甲酯25g、甲基丙烯酸甲酯25g、乙腈100ml、自由基引发剂偶氮二异丁腈1g和链转移剂CoBF 50ppm，搅拌使之充分混合，加热至60℃，并于60℃聚合12小时。之后，通过减压蒸馏除掉乙腈，即可获得液体状共聚物A3。为了进一步纯化产物，可以将产物沉淀在甲醇和水(体积比1:1)的混合溶剂中，由此除掉残留的单体等小分子物质。
实施例4.本发明预聚物(共聚物A4)的制备
在惰性气体氮气保护下，向配有机械搅拌器的反应釜中加入甲基丙烯酸(3-乙基氧杂环丁烷-3-基)甲酯25g、甲基丙烯酸丁酯25g、乙腈100ml、自由基引发剂偶氮二异丁腈1g和链转移剂CoBF 5ppm，搅拌使之充分混合，加热至60℃，并于60℃聚合12小时。之后，通过减压蒸馏除掉乙腈，即可获得液体状共聚物A4。为了进一步纯化产物，可以将产物沉淀在甲醇和水(体积比1:1)的混合溶剂中，由此除掉残留的单体等小分子物质。
实施例5.本发明预聚物(超支化共聚物A5)的制备
在惰性气体氮气保护下，向配有机械搅拌器的反应釜中加入甲基丙烯酸(3-乙基氧杂环丁烷-3-基)甲酯25g、二甲基丙烯酸乙二醇酯5g、乙腈100ml、自由基引发剂偶氮二异丁腈1g和链转移剂CoBF 5ppm，搅拌使之充分混合，加热至60℃，并于60℃聚合12小时。之后，通过减压蒸馏除掉乙腈，即可获得液体状超支化共聚物A5。为了进一步纯化产物，可以将产物沉淀在甲醇和水(体积比1:1)的混合溶剂中，由此除掉残留的单体等小分子物质。
表征及性能测试结果
1.分子量及PDI测定结果
利用凝胶渗透色谱(Waters:Waters707)来测定用聚苯乙烯换算的重均分子量(Mw)及数均分子量(Mn)，测定结果如表1和图1-3所示。
具体而言，将上述实施例制备的产物溶于N,N-二甲基甲酰胺(DMF)中，浓度配置为4000ppm，然后将100μl注入到GPC中。GPC的流动相使用四氢呋喃，以1.0ml/min的流速流入，在35℃下进行分析。将Waters HR-05、1、2、4E这四个串联连接作为层析管柱。使用RI检测器和PAD检测器在35℃下进行测定。同时，将测定的重均分子量除以数均分子量来计算得到多分散指数(PDI)。
表1.预聚物的分子量及分子量分布数据
结果表明：本发明方法可以有效调控所得含有氧杂环丁烷官能团的丙烯酸系预聚物的分子量，从而获得具有低分子量和窄分子量分布以及低粘度和优良流动性的预聚物。此外，通过实施例1与实施例2的对比还可以看出，通过控制加入链转移试剂的量，预聚物的分子量随着催化剂CoBF用量的增加呈下降的趋势。
2.核磁表征及质谱分析结果
对实施例1制备的本发明预聚物(均聚物A1)进行核磁检测，结果如图4所示。通过分析对比可以看出：存在甲基丙烯酸(3-乙基氧杂环丁烷-3-基)甲酯的特征峰，其中可以明显看到氧杂环丁烷中的亚甲基的特征峰(化学位移在4.5ppm左右)；也可以明显看到端基的丙烯酸酯双键的特征峰(化学位移在5.0-6.5ppm左右)。此外，将实施例5制备的本发明预聚物(超支化共聚物A5)也进行核磁检测，结果如图5所示。同样可以看出，丙烯酸酯双键的特征峰(化学位移5.5-6.5ppm左右)，亚甲基的特征峰(化学位移在4.5ppm左右)。
对实施例2制备的本发明预聚物(均聚物A2)进行MALDI-ToF MS检测，结果如图6所示。通过分析对比可以看出，预聚物具有甲基丙烯酸(3-乙基氧杂环丁烷-3-基)甲酯预聚物的典型出峰，分子量主要集中在600-3000Da之间，峰间距为甲基丙烯酸(3-乙基氧杂环丁烷-3-基)甲酯单体的质量，对典型峰的解析可以推导出甲基丙烯酸(3-乙基氧杂环丁烷-3-基)甲酯预聚物的聚合度(DP＝5)和精确结构。
3.光固化效果分析结果
3.1.PVDF基超滤膜光固化实验测试
为了验证本发明预聚物参与光固化反应的具体效果，在PVDF基超滤膜表面进行了阳离子光固化反应。光固化反应采用氧杂环丁烷基小分子3-甲基-3-羟甲基氧杂环丁烷(MOXE)和本发明预聚物(均聚物A1、共聚物A3)以及脂环族环氧化合物3,4-环氧环己基甲基3,4-环氧环己基甲酸酯(AOO)。首先将上述化合物与阳离子光引发剂4-(苯硫基)苯基·二苯基硫六氟磷酸盐溶解在甲醇中，然后将PVDF膜浸泡在上述甲醇溶液中10min，之后在365nm紫外灯下照射10min。光固化的反应物比例及部分原料结构如表2所示。
表2.在PVDF膜表面进行阳离子光固化的反应物比例

通过在PVDF膜表面进行一系列光固化平行实验，获得了膜M1-M4，并进行了水通量及表面形貌的测试，结果如图7所示。通过分析对比可以看出，在添加了本发明预聚物(均聚物A1、共聚物A3)的光固化实验中，相对于PVDDF原始膜，光固化改性膜M2、M3、M4具有更小的水通量。这表明预聚物可以起到交联剂的作用，使光固化涂层具有更加致密的结构。通过扫描电镜对PVDF原始膜和光固化改性膜M1-M4进行表面形貌表征，可以发现在添加了本发明预聚物(均聚物A1、共聚物A3)的光固化实验中，膜M2、M3、M4的表面孔隙结构相对于原始膜显著减 少；而不添加本发明预聚物(均聚物A1、共聚物A3)的光固化实验中，膜M1的表面孔隙结构与PVDF原始膜相比没有显著的改变，水通量的变化也较小，表明交联结构不明显。
上述实验充分表面，本发明的预聚物可以作为阳离子光固化反应交联剂，赋予光固化涂层致密的交联结构。
3.2.培养皿光固化实验测试
3.2.1.本发明预聚物(超支化共聚物A5)的自由基光固化
将0.2g A5、5重量％(相对于添加的A5的重量)的自由基光引发剂2-羟基-2-甲基-1-苯基丙酮溶解在2ml丙酮中。将溶液倾倒在培养皿里，待溶剂挥发后，在240nm紫外灯下光照5分钟，观察培养皿表面的形貌。
3.2.2.本发明预聚物(超支化共聚物A5)的阳离子光固化
将0.2g A5、3重量％(相对于添加的A5的重量)的阳离子光引发剂4-(苯硫基)苯基·二苯基硫六氟磷酸盐溶解在2ml丙酮中。将溶液倾倒在培养皿里，待溶剂挥发后，在240nm紫外灯下光照5分钟，观察培养皿表面的形貌。
3.2.3.本发明预聚物(超支化共聚物A5)的自由基和阳离子双重光固化
将0.2g A5、3重量％(相对于添加的A5的重量)的阳离子光引发剂4-(苯硫基)苯基·二苯基硫六氟磷酸盐和5重量％的自由基光引发剂2-羟基-2-甲基-1-苯基丙酮溶解在2ml丙酮中。将溶液倾倒在培养皿里，待溶剂挥发后，在240nm紫外灯下光照5分钟，观察培养皿表面的形貌。
测试结果如图8所示。图8左边为光固化前预聚物溶液的图片，三项测试的溶液在光照前均为澄清透明的状态。光照后，在培养皿的表面产生了白色固体。自由基光固化(3.2.1)和阳离子光固化(3.2.2)固化产生的光固化层较薄，而两种固化手段结合的双重光固化(3.2.3)产生的固化层明显更致密、更厚一些。
对本发明实施例5制备的超支化共聚物A5以及三种光固化(3.2.1、3.2.2和3.2.3)产物进行了红外表征。其中1630cm-1为超支化共聚物A5的碳碳双键的特征峰，3.2.1和3.2.3的双键特征峰强度明显要比未固化前的特征峰强度小；980cm-1左右为超支化共聚物A5的氧杂环丁烷的特征峰， 3.2.2和3.2.3在此处的特征峰强度也明显减小。由此证明了这种含有氧杂环丁烷基团和不饱和丙烯酸酯类双键的超支化预聚物既能以双键参与自由基光固化，也能以氧杂环丁烷基团参与阳离子光固化，且两者会协同促进光固化的效果，使生成的固化层更加致密。

Claims (17)

  1. 一种含有氧杂环丁烷官能团的丙烯酸系预聚物，其特征在于所述预聚物的侧链具有氧杂环丁烷基团，端基具有丙烯酸酯基团。
  2. 根据权利要求1的预聚物，其特征在于所述预聚物的聚合度为1-50，优选2-18，更优选3-15；和/或，
    所述预聚物的重均分子量Mw为200-10000Da，优选500-8000Da，更优选600-5000Da；和/或，
    所述预聚物的多分散性指数(PDI)为1.0-5.0，优选1.0-4.0，更优选1.0-3.0。
  3. 根据权利要求1或2的预聚物，其特征在于所述预聚物为均聚物或共聚物，其中共聚物为无规、梯度或嵌段共聚物。
  4. 根据权利要求1-3中任一项的预聚物，其特征在于所述预聚物为超支化共聚物，其中超支化共聚物的侧链也具有丙烯酸酯基团。
  5. 根据权利要求1-4中任一项的预聚物，其特征在于所述预聚物衍生自如下单体：
    (A)式1的单体：
    其中
    x为1-3的整数，优选x为1；
    R1为H或者CH3，优选R1为CH3；以及
    R2为H、卤素、C1-C6烷基、C1-C6卤代烷基、C1-C6羟烷基、C1-C6烷氧基或C1-C6卤代烷氧基；优选R2为H、卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4羟烷基、C1-C4烷氧基或C1-C4卤代烷氧基；更优选R2为H或C1-C4烷基，尤其是乙基；和
    (B)任选的其他(甲基)丙烯酸类或苯乙烯类单体；和
    (C)任选的二元醇的二(甲基)丙烯酸酯单体。
  6. 根据权利要求5的预聚物，其特征在于单体(A)为甲基丙烯酸(3-乙基氧杂环丁烷-3-基)甲酯。
  7. 根据权利要求5或6的预聚物，其特征在于如果存在的话，单体(B)为选自下组中的一种或多种：丙烯酸、甲基丙烯酸、富马酸、肉桂酸、巴豆酸、衣康酸、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸苄酯及其衍生物、甲基丙烯酸苄酯及其衍生物、苯乙烯及其衍生物；优选甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯及甲基丙烯酸苄酯；更优选甲基丙烯酸甲酯和/或甲基丙烯酸丁酯；和/或，
    如果存在的话，单体(B)与其他单体总和的质量比为1:1-1:5，优选1:1-1:3，更优选1:1。
  8. 根据权利要求5-7中任一项的预聚物，其特征在于如果存在的话，单体(C)为选自下组中的一种或多种：二丙烯酸乙二醇酯、二甲基丙烯酸乙二醇酯、二丙烯酸1,2-丙二醇酯、二甲基丙烯酸1,2-丙二醇酯、二丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,4-丁二醇酯、二丙烯酸1,6-己二醇酯、二甲基丙烯酸1,6-己二醇酯、二丙烯酸二甘醇酯、二甲基丙烯酸二甘醇酯、二丙烯酸三甘醇酯、二甲基丙烯酸三甘醇酯、二丙烯酸四甘醇酯、二甲基丙烯酸四甘醇酯、二丙烯酸二丙二醇酯、二甲基丙烯酸二丙二醇酯、二丙烯酸三丙二醇酯及二甲基丙烯酸三丙二醇酯；优选二甲基丙烯酸乙二醇酯、二甲基丙烯酸1,2-丙二醇酯、二甲基丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,6-己二醇酯、二甲基丙烯酸二甘醇酯、二甲基丙烯酸三甘醇酯、二甲基丙烯酸四甘醇酯、二甲基丙烯酸二丙二醇酯及二甲基丙烯酸三丙二醇酯；更优选二甲基丙烯酸乙二醇酯；和/或
    如果存在的话，单体(C)与其他单体总和的质量比为1:3-1:20，优选1:4-1:10，更优选1:5。
  9. 一种制备根据权利要求1-8中任一项的预聚物的方法，其特征在于 在链转移剂和自由基引发剂存在下，使单体(A)及任选的单体(B)和任选的单体(C)进行一步法催化链转移聚合(CCTP)反应。
  10. 根据权利要求9的方法，其特征在于链转移剂为选自下组中的一种或多种：双[(二氟硼基)二甲基乙二肟根合]钴(II)、双[(二氟硼基)二甲基苯基乙二肟根合]钴(II)、双[(二氟硼基)二苯基乙二肟根合]钴(II)、双[二甲基乙二肟根合]钴(II)、[内消旋-四苯基卟啉]钴、四甲基醚型血卟啉钴、四氟苯基卟啉钴、双[(二氟硼基)二甲基乙二肟根合]异丙基吡啶钴(II)及2,16-双(4-丁酰胺基)酞菁钴(II)，优选双[(二氟硼基)二甲基乙二肟根合]钴(II)(CoBF)；和/或，
    链转移剂的用量基于单体的总重量为0.1-100ppm，优选1-80ppm，更优选5-50ppm。
  11. 根据权利要求9或10的方法，其特征在于自由基引发剂为选自下组中的一种或多种：过硫酸铵、过硫酸钾、过硫酸钠、偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、偶氮异丁氰基甲酰胺、过氧化二苯甲酰、叔丁基过氧化氢及过氧化氢异丙苯，优选偶氮二异丁腈；和/或
    自由基引发剂的用量基于单体的总重量为0.1-8重量％，优选0.1-4重量％，更优选0.3-2重量％。
  12. 根据权利要求9-11中任一项的方法，其特征在于反应温度为50-120℃，优选55-100℃，更优选60-80℃。
  13. 根据权利要求9-12中任一项的方法，其特征在于所述一步法催化链转移聚合(CCTP)反应采用本体聚合、溶液聚合、乳液聚合、悬浮聚合或沉淀聚合的聚合方式进行。
  14. 根据权利要求1-8中任一项或者根据权利要求9-13中任一项的方法获得的预聚物在自由基固化和/或阳离子固化中的用途。
  15. 一种包含权利要求1-8中任一项或者根据权利要求9-13中任一项的方法获得的预聚物的可光固化组合物。
  16. 可由权利要求15的可光固化组合物得到的固化材料。
  17. 一种制备光固化材料的方法，其包括用紫外光、可见光或激光对权利要求15的可光固化组合物进行辐照。
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