CN113943420A - UV (ultraviolet) light-cured resin composition and preparation method and application thereof - Google Patents
UV (ultraviolet) light-cured resin composition and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/08—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by replacement of hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/02—Monothiocarboxylic acids
- C07C327/04—Monothiocarboxylic acids having carbon atoms of thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C327/06—Monothiocarboxylic acids having carbon atoms of thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of an acyclic saturated carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
- C09J181/02—Polythioethers; Polythioether-ethers
Abstract
The invention belongs to the field of photocuring, and particularly relates to a UV (ultraviolet) photocuring resin composition as well as a preparation method and application thereof. The UV light-cured resin composition comprises unsaturated resin which has more than two carbon-carbon double bond groups and does not contain ester bonds, a thiol compound shown as a general formula (I), a photoinitiator, a polymerization inhibitor and an optional coupling agent and an auxiliary agent. The thiol compound adopted in the UV photocuring resin composition is liquid at room temperature, has no ester bond, has little smell, has no crystal precipitation in the storage of the corresponding UV photocuring resin composition, has long application life, good heat and moisture resistance, can be quickly cured, has high crosslinking degree and bonding strength after curing, and can be used for preparing adhesives and sealantsAnd the application prospect is wide.
Description
Technical Field
The invention belongs to the field of photocuring, and particularly relates to a UV (ultraviolet) photocuring resin composition as well as a preparation method and application thereof.
Background
In recent years, in the field of electronic circuits, there has been an increasing demand for the performance and process conditions of adhesive and sealing materials, and for example, in the manufacturing process of image sensor modules for electronic products such as mobile phones, the adhesive materials used up to now are usually cured by heating at high temperatures, which may cause deterioration of lenses used in the modules. In addition, in the assembly and mounting of electronic components, for the purpose of maintaining reliability and the like, an adhesive and a sealant having high adhesion strength and moisture resistance reliability are often required regardless of the material of the adherend.
The ultraviolet curing technology adopts a mode of UV light initiation rapid curing, can avoid the problem of high heating temperature in the thermosetting bonding process, and has the advantages of second-speed curing, energy conservation, environmental protection and the like. However, in the conventional acrylate radical UV photo-curing system, due to the reaction mechanism problem of radical chain self-polymerization, the polymerization inhibition effect of oxygen is easily affected in the UV photo-curing process, so that the oxygen polymerization inhibition effect brings inconvenience to the photo-curing process, and the performance of the photo-curing product is also reduced. The mercapto-alkene system is a novel UV photocuring system, and the polymerization inhibition effect of oxygen on the photocuring process is very small due to the gradually-increased reaction mechanism, so that inert gas protection is not needed during curing, the photoinitiation efficiency is greatly improved, and the dosage of a photoinitiator can be reduced.
CN105706264A discloses a sealant for display elements, which employs a mercapto-ene system of a thiol compound and a polyene compound, but the thiol compound employed contains an ester bond structure which is easily hydrolyzed, inevitably resulting in poor hydrolysis resistance of the product. CN110072564A and CN111491674A both disclose primer compositions for adhesives, also using mercapto-ene systems of compounds having at least two thiol groups and compounds containing allyl groups, but using thiol compounds which are also ester bond type polythiols not resistant to hydrolysis or 1,3, 5-tris (3-mercaptopropyl) -1,3, 5-triazacycloheptane-2, 4, 6-trione having a large sulfur odor and ethoxylated trimethylolpropane trithiol. In addition, CN112840004A discloses a resin composition containing a compound having a carbon-carbon double bond group in the molecule, a difunctional thiol compound, an initiator and a radical polymerization inhibitor, wherein although there is no ester bond in the thiol compound used, there still exists an ester bond which may be hydrolyzed in the compound having a carbon-carbon double bond group in the molecule, and since the thiol compound used has only two functional groups, the cured product has flexibility, low degree of crosslinking, poor curing effect, poor barrier property against moisture, and heat resistance, thermal bonding strength and wet-heat hydrolysis resistance are still to be improved.
In summary, it has been a problem to be solved how to use a suitable multifunctional thiol compound and a suitable polyene compound to prepare a resin composition that can be rapidly cured by UV light, has a good crosslinking curing effect, a small odor, a good moisture barrier property, a high thermal bonding strength, and a good heat and moisture resistance, and an adhesive and a sealing material using the resin composition.
Disclosure of Invention
The first purpose of the invention is to overcome the defects that the resin composition obtained by combining the existing multifunctional group mercaptan compound and polyene compound cannot be simultaneously and rapidly cured, has good crosslinking curing effect, small smell, good moisture barrier property, high thermal bonding strength and good heat and moisture resistance, and provide a novel UV light curing resin composition, a preparation method and application thereof.
The second object of the present invention is to provide a method for preparing the above UV light curable resin composition.
The third purpose of the invention is to provide an application of the UV light-cured resin composition in preparing an adhesive.
The fourth object of the present invention is to provide a use of the above-mentioned UV light curable resin composition for preparing a sealant.
Specifically, the UV light-cured resin composition provided by the invention comprises the following components:
(A) an unsaturated resin having two or more carbon-carbon double bond groups and no ester bond;
(B) a thiol compound represented by the following general formula (I);
(C) a photoinitiator; and
(D) a polymerization inhibitor;
in the general formula (I), R1、R2、R3And R4Wherein only one is a mercaptoalkoxy group having 2 to 5 carbon atoms, R5、R6、R7And R8Wherein only one is a mercaptoalkoxy group having 2 to 5 carbon atoms, R1、R2、R3、R4、R5、 R6、R7And R8The remaining six of (A) are each independently selected from one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms and a lower alkoxy group having 1 to 3 carbon atoms.
In a preferred embodiment, in the thiol compound of the formula (I), R1、R2And R4One of them is a mercaptoalkoxy group having 2 to 5 carbon atoms and the other two are both hydrogen atoms, R3And R7Each independently selected from a hydrogen atom or a methoxy group, R5、R6And R8One of them is a mercaptoalkoxy group having 2 to 5 carbon atoms and the other two are both hydrogen atoms.
In a preferred embodiment, in the thiol compound of the formula (I), R1And R5Are each a hydrogen atom, R3And R7Each independently selected from a hydrogen atom or a methoxy group, R2And R4One ofOne is a mercaptoalkoxy group having 2 to 5 carbon atoms and the other is a hydrogen atom, R6And R8One of them is a mercaptoalkoxy group having 2 to 5 carbon atoms and the other is a hydrogen atom.
In a preferred embodiment, in the thiol compound of the formula (I), R1And R5Are each a hydrogen atom, R3And R7Each independently selected from a hydrogen atom or a methoxy group, and when R is2And R6When all are mercapto alkoxy groups having 2 to 5 carbon atoms, R4And R8Are each a hydrogen atom; when R is4And R8When all are mercapto alkoxy groups having 2 to 5 carbon atoms, R2And R6Are each a hydrogen atom; when R is4And R6When all are mercapto alkoxy groups having 2 to 5 carbon atoms, R2And R8Are each a hydrogen atom; when R is2And R8When all are mercapto alkoxy groups having 2 to 5 carbon atoms, R4And R6Are all hydrogen atoms.
In a preferred embodiment, the thiol compound is prepared according to a process comprising the steps of:
the method comprises the following steps: performing substitution reaction on the biphenol compound represented by the general formula (II) and the first compound represented by the general formula (III) in the presence of a phase transfer catalyst under an alkaline condition, and purifying to obtain a liquid colorless or light yellow first intermediate product;
step two: carrying out free radical addition reaction on the first intermediate product and thioacetic acid in the presence of a free radical initiator, and purifying to obtain a liquid colorless or light yellow second intermediate product;
step three: carrying out hydrolysis reaction on the second intermediate product, and purifying to obtain a colorless or light yellow viscous liquid product, namely the mercaptan compound;
in the general formula (II), R9、R10、R11And R12In which only one is hydroxy, R13、R14、R15And R16In which only one is hydroxy, R9、R10、R11、R12、R13、R14、R15And R16The remaining six of the groups are respectively and independently selected from one of hydrogen atoms, alkyl groups with 1-3 carbon atoms and alkoxy groups with 1-3 carbon atoms;
in the general formula (III), X represents chlorine or bromine, and m is 0, 1, 2 or 3.
In a preferred embodiment, in the step one, the substitution reaction is carried out by dissolving the biphenol compound represented by the general formula (ii) in an organic solvent, adding alkali to provide alkaline conditions, adding a phase transfer catalyst, then heating to 40-100 ℃ under the protection of inert gas, stirring for 10-60 minutes, then adding the first compound represented by the general formula (iii), reacting for 4-12 hours, then filtering the reaction solution, distilling the filtrate under reduced pressure to remove the solvent, washing with water three times, extracting with chloroform, collecting the organic phase, and evaporating to dryness to obtain the first intermediate product which is liquid and colorless or light yellow.
In a preferred embodiment, in step two, the free radical addition reaction is carried out by dissolving the first intermediate product in an organic solvent, adding a free radical initiator, raising the temperature to 40-100 ℃ under the protection of inert gas, slowly adding thioacetic acid, carrying out the free radical addition reaction for 4-12 hours, and then distilling under reduced pressure to remove the solvent to obtain a liquid colorless or light yellow second intermediate product.
In a preferred embodiment, in step three, the hydrolysis reaction is performed by dissolving the second intermediate product in an organic solvent, adding hydrochloric acid or sodium hydroxide, heating to 50-100 ℃ for reaction for 3-12 hours, distilling under reduced pressure to remove the solvent, washing twice with 2-8% sodium bicarbonate solution, extracting with chloroform, collecting the organic phase, and evaporating to dryness to obtain a colorless or light yellow viscous liquid product, i.e., the thiol compound.
In a preferred embodiment, the carbon-carbon double bond group in the unsaturated resin is at least one of a vinyl group, an allyl group, a vinyl ether group and an allyl ether group.
In a preferred embodiment, the unsaturated resin is a combination of at least one trifunctional unsaturated resin and at least one difunctional unsaturated resin in a weight ratio of 1 (0.1-0.5).
In a preferred embodiment, the unsaturated resin is a combination of triallyl isocyanurate and bisphenol A diallyl ether in a weight ratio of 1 (0.1-0.5).
In a preferred embodiment, the unsaturated resin is contained in an amount of 30 to 45 parts by weight, and the thiol compound is contained in an amount of 40 to 60 parts by weight.
In a preferred embodiment, the ratio of equivalents of carbon-carbon double bond functional groups in the unsaturated resin to equivalents of thiol functional groups in the thiol compound is from 0.7 to 1.5, preferably from 0.9 to 1.2.
In a preferred embodiment, the photoinitiator is a free radical photoinitiator selected from the group consisting of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl methanone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphinate, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzylphenyl) butanone, 2-hydroxy-1- (2-hydroxyethoxy) -2-methylpropiophenone, 2-hydroxy-4- (2-hydroxy-2-methyl) phenylphosphine oxide, 2-methyl phenyl-propanone, 2-methyl-1- (4-morpholinyl) propanone, and, 4-benzoyl-4 '-methyl-diphenyl sulfide, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ], 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-1-hexanophenone, bis-2, 6-difluoro-3-pyrrolylphenyltitanocene, methyl benzoylformate, benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, methyl benzoylbenzoate, methyl N-propylbenzenesulfonate, N-2-propylbenzenesulfonate, N-propylphenoxide, N-2-propylphenoxide, N-p-phenylbenzophenone, N-2-p-propylphenoxide, N-p-propylphenoxide, N-2-p-2-p-phenylbenzophenone, p-2-p-2-phenylbenzophenone, p-2-p-2-p-phenyltole, p-methyle, p-2-p-m-2-p-2-p-m-p-m-p-m-p-, At least one of ethyl 4-dimethylaminobenzoate, isooctyl p-dimethylaminobenzoate, 4' -bis (diethylamino) benzophenone, isopropyl thioxanthone, 2, 4-diethyl thioxanthone, and 2-ethylanthraquinone.
In a preferred embodiment, the photoinitiator is present in an amount of 0.3 to 5 parts by weight.
In a preferred embodiment, the polymerization inhibitor is at least one selected from hydroquinone, p-hydroxyanisole, p-benzoquinone, methylhydroquinone, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, 4-hydroxypiperidinol oxyl, phenothiazine and anthraquinone.
In a preferred embodiment, the polymerization inhibitor is contained in an amount of 0.01 to 0.5 parts by weight.
In a preferred embodiment, the UV light curable resin composition further comprises a coupling agent and/or an auxiliary agent; the coupling agent is at least one selected from gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 8-epoxypropoxytrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane; the auxiliary agent is selected from at least one of filler, antioxidant, stabilizer, flame retardant, diluent, pigment, defoaming agent, leveling agent and ion trapping agent.
In a preferred embodiment, the coupling agent is present in an amount of 0.01 to 3 parts by weight.
In a preferred embodiment, the content of the auxiliary is 0.01 to 30 parts by weight.
The preparation method of the UV light-cured resin composition comprises the step of uniformly mixing unsaturated resin, thiol compounds shown in a general formula (I), a photoinitiator, a polymerization inhibitor and optional coupling agent and auxiliary agent in a dark environment.
The invention also provides application of the UV light-cured resin composition in preparation of an adhesive.
The invention also provides application of the UV light-cured resin composition in preparing a sealant.
The invention has the following beneficial effects:
(1) the thiol-ene resin composition is composed of thiol compounds with specific structures and unsaturated resin which has more than two carbon-carbon double bond groups in molecules and does not contain ester bonds, the thiol-ene resin composition system is slightly influenced by an oxygen inhibition effect, can be quickly cured under UV illumination, avoids a series of problems caused by high-temperature heating and curing in the bonding process, and has high crosslinking degree and thermal bonding strength after curing and good heat resistance and humidity resistance.
(2) The thiol compound adopted by the invention is liquid at normal temperature and has low odor, so that the resin composition is easy to mix and use, and the condition of overlarge odor can be avoided.
(3) The thiol compound adopted by the invention is liquid at normal temperature, can be directly used as a curing agent for curing the resin composition, does not need to be additionally coupled to form an oligomer mixture, does not need to be combined with other thiol compounds, has low cost, and can be used as a component of a sealant and a binder. In addition, the thiol compound adopted by the invention can improve the storage stability of the unsaturated resin, has long application period and has great industrial application prospect.
Drawings
FIG. 1 is a drawing showing 5,5 '-bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) biphenyl1H-NMR chart;
FIG. 2 is an IR spectrum of 5,5 '-bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) biphenyl;
FIG. 3 is a drawing showing 5,5' -bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) -3,3' -dimethoxybiphenyl1H-NMR chart;
FIG. 4 is an IR spectrum of 5,5' -bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) -3,3' -dimethoxybiphenyl.
Detailed Description
The UV light-cured resin composition provided by the invention comprises unsaturated resin, a thiol compound shown as a general formula (I), a photoinitiator and a polymerization inhibitor, and further comprises a coupling agent and/or an auxiliary agent. Wherein the content of the unsaturated resin is preferably 30 to 45 parts by weight, such as 30, 35, 40, 45 parts by weight. The content of the thiol compound is preferably 40 to 60 parts by weight, such as 40, 45, 50, 55, 60 parts by weight. The photoinitiator is preferably present in an amount of 0.3 to 5 parts by weight, such as 0.3, 0.5, 1, 2,3, 4, 5 parts by weight. The content of the polymerization inhibitor is preferably 0.01 to 0.5 parts by weight, such as 0.01, 0.1, 0.2, 0.3, 0.4, 0.5 parts by weight. The coupling agent is preferably present in an amount of 0.01 to 3 parts by weight, such as 0.01, 0.1, 0.5, 1, 1.5, 2, 2.5, 3 parts by weight. The content of the auxiliaries is preferably from 0.01 to 30 parts by weight, such as 0.01, 1, 5, 10, 15, 20, 25, 30 parts by weight.
The thiol compound has a structure represented by general formula (I):
in the general formula (I), R1、R2、R3And R4Wherein only one is a mercaptoalkoxy group having 2 to 5 carbon atoms, R5、R6、R7And R8Wherein only one is a mercaptoalkoxy group having 2 to 5 carbon atoms, R1、R2、R3、R4、R5、R6、R7And R8The remaining six of (A) are each independently selected from one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms and a lower alkoxy group having 1 to 3 carbon atoms. The mercaptoalkoxy group having 2 to 5 carbon atoms may be, for example, mercaptoethoxy, mercapto-n-propoxy, mercapto-isopropoxy, mercapto-n-butoxy, mercapto-sec-butoxy, mercapto-isobutoxy, mercapto-tert-butoxy, mercapto-n-pentoxy, mercapto-isopentoxy, mercapto-tert-pentoxy or mercapto-neopentoxy. Specific examples of the alkyl group having 1 to 3 carbon atoms include, but are not limited to: methyl, ethyl, n-propyl or isopropyl. Specific examples of the alkoxy group having 1 to 3 carbon atoms include, but are not limited to: methoxy, ethoxy, propoxy or isopropoxy.
In the thiol compound represented by the general formula (I), preferably, R1、R2And R4One of them is a mercaptoalkoxy group having 2 to 5 carbon atoms and the other two are both hydrogen atoms, R3And R7Each independently selected from a hydrogen atom or a methoxy group, R5、R6And R8One of them is a mercaptoalkoxy group having 2 to 5 carbon atoms and the other two are both hydrogen atoms. More preferably, in the thiol compound represented by the general formula (I), R is1And R5Are each a hydrogen atom, R3And R7Each independently selected from a hydrogen atom or a methoxy group, R2And R4One of them is a mercaptoalkoxy group having 2 to 5 carbon atoms and the other is a hydrogen atom, R6And R8One of them is a mercaptoalkoxy group having 2 to 5 carbon atoms and the other is a hydrogen atom. Most preferably, in the thiol compound of the formula (I), R1And R5Are each a hydrogen atom, R3And R7Each independently selected from a hydrogen atom or a methoxy group, and when R is2And R6When all are mercapto alkoxy groups having 2 to 5 carbon atoms, R4And R8Are each a hydrogen atom; when R is4And R8When all are mercapto alkoxy groups having 2 to 5 carbon atoms, R2And R6Are each a hydrogen atom; when R is4And R6When all are mercapto alkoxy groups having 2 to 5 carbon atoms, R2And R8Are each a hydrogen atom; when R is2And R8When all are mercapto alkoxy groups having 2 to 5 carbon atoms, R4And R6Are all hydrogen atoms.
In one embodiment, the thiol compound is prepared according to a method comprising the steps of:
the method comprises the following steps: performing substitution reaction on the biphenol compound represented by the general formula (II) and the first compound represented by the general formula (III) in the presence of a phase transfer catalyst under an alkaline condition, and purifying to obtain a liquid colorless or light yellow first intermediate product;
step two: carrying out free radical addition reaction on the first intermediate product and thioacetic acid in the presence of a free radical initiator, and purifying to obtain a liquid colorless or light yellow second intermediate product;
step three: carrying out hydrolysis reaction on the second intermediate product, and purifying to obtain a colorless or light yellow viscous liquid product, namely the mercaptan compound;
in the general formula (II), R9、R10、R11And R12In which only one is hydroxy, R13、R14、R15And R16In which only one is hydroxy, R9、R10、R11、R12、R13、R14、R15And R16The remaining six of them are each independently selected from one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms. Preferably, R9、 R10And R12One of them being a hydroxyl group and the other two being hydrogen atoms, R11And R15Each independently selected from a hydrogen atom or a methoxy group, R13、R14And R16One of which is a hydroxyl group and the other two are both hydrogen atoms. More preferably, R9And R13Are each a hydrogen atom, R11And R15Each independently selected from a hydrogen atom or a methoxy group, R10And R12One of which is a hydroxyl group and the other is a hydrogen atom, R14And R16One of which is a hydroxyl group and the other is a hydrogen atom. Most preferably, R9And R13Are each a hydrogen atom, R11And R15Each independently selected from a hydrogen atom or a methoxy group, and when R is10And R14When both are hydroxy, R12And R16Are each a hydrogen atom; when R is12And R16When both are hydroxy, R10And R14Are each a hydrogen atom; when R is12And R14When both are hydroxy, R10And R16Are each a hydrogen atom; when R is10And R16When both are hydroxy, R12And R14Are all hydrogen atoms.
In the general formula (III), X represents chlorine or bromine, and m is 0, 1, 2 or 3.
In the first step, the substitution reaction is preferably performed by dissolving the biphenol compound represented by the general formula (ii) in an organic solvent, adding an alkali to provide an alkaline condition, adding a phase transfer catalyst, then heating to 40-100 ℃ under the protection of an inert gas, stirring for 10-60 minutes, then adding the first compound represented by the general formula (iii), reacting for 4-12 hours, then filtering the reaction solution, distilling the filtrate under reduced pressure to remove the solvent, washing with water for three times, extracting with chloroform, collecting the organic phase, and evaporating to dryness to obtain a liquid colorless or light yellow first intermediate product.
The kind of the base is not particularly limited and may be conventionally selected in the art, and specific examples thereof include, but are not limited to: at least one of potassium carbonate, sodium hydroxide, potassium hydroxide, triethylamine and p-dimethylaminopyridine.
The phase transfer catalyst may be any of various conventional materials capable of catalyzing a substitution reaction between a phenolic hydroxyl group in the biphenol compound represented by the general formula (ii) and chlorine or bromine in the first compound represented by the general formula (iii), and is preferably at least one of cyclic crown ethers, polyethers, and ammonium compounds. Specific examples of the cyclic crown ethers include, but are not limited to: at least one of 18-crown-6, 15-crown-5 and cyclodextrin. Specific examples of such polyethers include, but are not limited to: chain polyethylene glycol and/or chain polyethylene glycol dialkyl ether. Specific examples of such ammonium species include, but are not limited to: at least one of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride.
And in the second step, the free radical addition reaction mode is that the first intermediate product is dissolved in an organic solvent, a free radical initiator is added, the temperature is raised to 40-100 ℃ under the protection of inert gas, thioacetic acid is slowly added to carry out the free radical addition reaction for 4-12 hours, and then the solvent is removed by reduced pressure distillation to obtain a liquid colorless or light yellow second intermediate product.
The free radical initiator may be any one of the existing substances capable of initiating the free radical addition reaction between the double bond in the first intermediate product and the mercapto group in the thioacetic acid, and may be an azo initiator and/or a peroxy initiator. Specific examples of the azo-based initiator include, but are not limited to: at least one of azobisisobutyronitrile, 2 '-azobis (2-methylbutyronitrile), dimethyl 2,2' -azobis (2-methylpropionate), dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisformamide, azobisisopropylimidazoline hydrochloride, azobisisobutyronitrile formamide, azobiscyclohexylcarbonitrile, azobiscyanovaleric acid, azobisisopropylimidazoline, azobisisovaleronitrile, and azobisisoheptonitrile. Specific examples of the peroxy-based initiator include, but are not limited to: at least one of t-hexyl peroxyisopropyl monocarbonate, t-hexyl peroxy-2-ethylhexanoate, 1,3, 3-tetramethylbutyl peroxy-2-ethylhexanoate, t-butyl peroxy pivalate, t-hexyl peroxy pivalate, t-butyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, 1,3, 3-tetramethylbutyl peroxy neodecanoate, 1-bis (t-hexyl peroxy) cyclohexane, benzoyl peroxide, 3,5, 5-trimethyl peroxy hexanoyl, lauroyl peroxide, and t-butyl benzoyl peroxide. From the viewpoint of availability of raw materials, the radical initiator is preferably azobisisobutyronitrile, 2 '-azobis (2-methylbutyronitrile), dimethyl 2,2' -azobis (2-methylpropionate), t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy2-ethylhexanoate, 1,3, 3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxy pivalate, at least one of tert-hexyl peroxypivalate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, 1,3, 3-tetramethylbutyl peroxyneodecanoate, 1-bis (tert-hexyl peroxy) cyclohexane, benzoyl peroxide, 3,5, 5-trimethylhexanoyl peroxide, and lauroyl peroxide.
In the third step, the hydrolysis reaction is preferably performed by dissolving the second intermediate product in an organic solvent, adding hydrochloric acid or sodium hydroxide, heating to 50-100 ℃ for reaction for 3-12 hours, distilling under reduced pressure to remove the solvent, washing twice with 2-8% sodium bicarbonate solution, extracting with chloroform, collecting the organic phase, and evaporating to dryness to obtain a colorless or light yellow viscous liquid product, namely the thiol compound.
In a preferred embodiment of the present invention, the substitution reaction of the first step is carried out in the presence of an organic solvent I, the radical addition reaction of the second step is carried out in the presence of an organic solvent II, and the hydrolysis reaction of the third step is carried out in the presence of an organic solvent III. The organic solvent I and the organic solvent II are preferably at least one selected from methanol, ethanol, propanol, butanol, isopropanol, ethyl acetate, propyl acetate, butyl acetate, tetrahydrofuran, dioxane, acetonitrile, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide and dimethylsulfoxide. The organic solvent III is preferably an alcohol, more preferably a C1-5 monoalcohol, such as at least one of methanol, ethanol, propanol and n-butanol.
The unsaturated resin has more than two carbon-carbon double bond groups and does not contain ester bonds, wherein the contained carbon-carbon double bond groups are preferably at least one of vinyl groups, allyl groups, vinyl ether groups and allyl ether groups. Specific examples of the unsaturated resin include, but are not limited to: at least one of triallyl isocyanurate, triallyl cyanurate, tetraallylglycoluril, pentaerythritol tetraallyl ether, pentaerythritol triallyl ether, tetraallylsilane, 2,4, 6-triallylphenol, cyclohexanedimethanol divinyl ether, bisphenol a diallyl ether, epoxy-modified polybutadiene, and diallyl monoglycidyl isocyanurate. The unsaturated resin is preferably a combination of at least one trifunctional unsaturated resin and at least one difunctional unsaturated resin in a weight ratio of 1 (0.1-0.5), and more preferably a combination of triallyl isocyanurate and bisphenol A diallyl ether in a weight ratio of 1 (0.1-0.5), which has the advantages of good heat resistance, high bonding strength and better wet heat resistance. The ratio of equivalents of carbon-carbon double bond functional groups in the unsaturated resin to equivalents of thiol functional groups in the thiol compound is preferably 0.7 to 1.5, such as 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5. The ratio of the equivalent of the carbon-carbon double bond functional group in the unsaturated resin to the equivalent of the thiol functional group in the thiol compound is most preferably 0.9 to 1.2, and when the ratio is outside this range, the adhesive property, the moisture and heat resistance and the moisture barrier property of the resulting UV light-curable resin composition are lowered to some extent.
The photoinitiator of the present invention is not particularly limited in kind, and may be any of various conventional radical photoinitiators capable of reacting a carbon-carbon double bond in an unsaturated resin with a mercapto group in a thiol compound to complete curing. Specific examples of the radical type photoinitiator include, but are not limited to: 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzyl) butanone, 4-benzoyl-4' -methyl-diphenylsulfide, methyl-2-phenylpropiophenone, methyl-2-propanone, methyl-2-methylbenzyl-1-propanone, methyl-4-methylbenzyl-ether, methyl-1-propanone, methyl-2-methylbenzyl-4-methylbenzyl-1-methyl-phenyl-2-methyl-1-propanone, methyl-2-methylbenzyl-methyl-1-methyl-2-methyl-phenyl-1-propanone, methyl-2-methylbenzyl-methyl-1-phenyl-methyl-1-one, methyl-phenyl-2-methyl-one, methyl-phenyl-2-methyl-one, methyl-2-phenyl-one, methyl-2-methyl-one, and methyl-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ], 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-1-phenylhexanone, bis 2, 6-difluoro-3-pyrrolophenyldicyclopentadienyl titanium, methyl benzoylformate, benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, methyl benzoylbenzoate, ethyl 4-dimethylaminobenzoate, isooctyl p-dimethylaminobenzoate, methyl tert-butyl acetate, methyl ethyl p-dimethylaminobenzoate, methyl benzoate, ethyl p-dimethylaminobenzoate, ethyl p-ethyl ester, ethyl p-methyl benzoate, ethyl p-dimethylaminobenzoate, ethyl ester, p-dimethylaminobenzoate, p-ethyl ester, p-methyl benzoate, p-ethyl ester, p-methyl benzoate, p-ethyl ester, p-methyl benzoate, p-ethyl ester, p-methyl benzoate, p-ethyl ester, p-methyl ester, p-ethyl ester, p-methyl ester, p-ethyl ester, p-ethyl ester, p-p, 4,4' -bis (diethylamino) benzophenone, isopropylthioxanthone, 2, 4-diethylthioxanthone, and 2-ethylanthraquinone.
The type of the polymerization inhibitor in the present invention is not particularly limited, and may be conventionally selected in the art, and specific examples thereof include, but are not limited to: at least one of hydroquinone, p-hydroxyanisole, p-benzoquinone, methylhydroquinone, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, 4-hydroxypiperidinol oxyl, phenothiazine and anthraquinone.
The UV light-curable resin composition preferably further comprises a coupling agent to improve the dispersion performance of inorganic substances in the system in the resin. Specific examples of the coupling agent include, but are not limited to: at least one of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 8-epoxypropoxytyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.
The UV light-curable resin composition preferably further comprises an auxiliary agent. The auxiliary agent may be at least one selected from fillers, antioxidants, stabilizers, flame retardants, diluents, pigments, defoamers, leveling agents, and ion traps, and specific selection of the above various auxiliary agents is well known to those skilled in the art and will not be described herein.
The preparation method of the UV light-cured resin composition comprises the step of uniformly mixing unsaturated resin, thiol compounds shown in a general formula (I), a photoinitiator, a polymerization inhibitor and optional coupling agent and auxiliary agent in a dark environment.
The invention also provides application of the UV light-cured resin composition in preparation of an adhesive.
The invention also provides application of the UV light-cured resin composition in preparing a sealant.
The present invention will be further described with reference to the following examples.
In the following preparation examples, the sources of the raw materials used in the preparation of the thiol compounds 5,5' -bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) biphenyl and 5,5' -bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) -3,3' -dimethoxybiphenyl were as follows: 5,5' -diallyl-2, 2' -biphenol available from Sahn's chemical technology (Shanghai) Inc. under the designation E100338; the phase transfer catalyst 18-crown-6 is from Shanghai Tantake Technology, Inc. under the designation 30243D; allyl bromide is available from Shanghai Tantake Technique, Inc. under the designation 13125C; azobisisobutyronitrile (abbreviated as "AIBN") available from shanghai mclin biochemistry technology limited under the designation a 800353; the thioacetic acid is from national pharmaceutical group chemical reagent limited, and the brand is 80128126; 5,5 '-diallyl-3, 3' -dimethoxy-2, 2 '-biphenol available from Sahn's chemical technology (Shanghai) Inc. under the designation D050881.
Preparation example 1
This preparation example is used to illustrate the preparation of a thiol compound (5,5 '-bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) biphenyl) and comprises the following specific steps and reaction schemes:
the method comprises the following steps: dissolving 80g of 5,5 '-diallyl-2, 2' -biphenol in 200mL of acetone, adding 103.6g of potassium carbonate and 18-crown-67.9 g of a phase transfer catalyst, heating to 70 ℃ under the protection of inert gas, stirring for 10 minutes, slowly adding 79.8g of allyl bromide, reacting for 8 hours, filtering the reaction solution, distilling the filtrate under reduced pressure to remove the solvent, washing with water for three times, extracting with trichloromethane, collecting the organic phase, and evaporating to dryness to obtain a liquid light yellow first intermediate product;
step two: dissolving the first intermediate product obtained in the second step in 200mL of tetrahydrofuran, adding 5.4g of azodiisobutyronitrile serving as a free radical initiator, heating to 70 ℃ under the protection of inert gas, slowly adding 96.2g of thioacetic acid, reacting for 12 hours, and then carrying out reduced pressure distillation to remove the solvent and excessive thioacetic acid to obtain a liquid light yellow second intermediate product;
step three: and (3) dissolving the second intermediate product obtained in the second step in 300mL of methanol, adding 60mL of hydrochloric acid for hydrolysis, heating to 60 ℃ for hydrolysis reaction for 12 hours, distilling under reduced pressure to remove the solvent, washing twice with a 5% sodium bicarbonate solution, extracting with chloroform, collecting the organic phase, and evaporating to dryness to obtain 124.8g of a final product which is a light yellow viscous liquid, namely 5,5 '-bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) biphenyl, wherein the total yield is 86.2%, the mercaptan equivalent weight is 120g/eq, and the molecular weight is 482.8. The 5,5 '-bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) biphenyl was substantially free of sulfur odor.
Preparation of the 5,5 '-bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) biphenyl1The H-NMR chart and the IR spectrum are shown in FIGS. 1 and 2, respectively. As can be seen from FIGS. 1 and 2, the 5,5' -bisThe (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) biphenyl has the formula (IV).
Preparation example 2
This preparation example is used to illustrate the preparation of a thiol compound (5,5' -bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) -3,3' -dimethoxybiphenyl), and the specific steps and reaction scheme are as follows:
the method comprises the following steps: dissolving 98g of 5,5' -diallyl-3, 3' -dimethoxy-2, 2' -biphenol in 250mL of acetone, adding 103.6g of potassium carbonate and 18-crown-67.9 g of a phase transfer catalyst, heating to 70 ℃ under the protection of inert gas, stirring for 10 minutes, slowly adding 79.8g of allyl bromide, reacting for 8 hours, filtering the reaction solution, distilling the filtrate under reduced pressure to remove the solvent, washing with water for three times, extracting with trichloromethane, collecting the organic phase, and evaporating to dryness to obtain a liquid pale yellow first intermediate product;
step two: dissolving the first intermediate product obtained in the step one in 200mL of tetrahydrofuran, adding 5.4g of azodiisobutyronitrile serving as a free radical initiator, heating to 70 ℃ under the protection of inert gas, slowly adding 96.2g of thioacetic acid, reacting for 12 hours, and then carrying out reduced pressure distillation to remove the solvent and excessive thioacetic acid to obtain a liquid light yellow second intermediate product;
step three: and (3) dissolving the second intermediate product obtained in the second step in 300mL of methanol, adding 60mL of hydrochloric acid for hydrolysis, heating to 70 ℃ for hydrolysis reaction for 12 hours, distilling under reduced pressure to remove the solvent, washing twice with a 5% sodium bicarbonate solution, extracting with chloroform, collecting the organic phase, and evaporating to dryness to obtain 137.7g of a final product which is a light yellow viscous liquid, namely 5,5' -bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) -3,3' -dimethoxybiphenyl, wherein the total yield is 84.5%, the mercaptan equivalent is 135g/eq, and the molecular weight is 542.8. The 5,5' -bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) -3,3' -dimethoxybiphenyl had substantially no sulfur odor.
The 5,5 '-bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) group) Of (E) -3,3' -dimethoxybiphenyl1The H-NMR chart and the IR spectrum are shown in FIGS. 3 and 4, respectively. As can be seen from fig. 3 and 4, the 5,5' -bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) -3,3' -dimethoxybiphenyl has the structure shown in formula (v).
Examples 1 to 17
S1: preparing raw materials according to the components and parts by weight in the following table 1:
s2: the raw materials prepared in S1 were added to a planetary mixer, preliminarily mixed at room temperature for 15 minutes, and then dispersed at room temperature for 30 minutes using a three-roll mill, the whole process being carried out in a dark environment, to obtain a UV light curable resin composition.
Comparative examples 1 to 6
S1: preparing raw materials according to the components and parts by weight in the following table 2:
s2: the raw materials prepared in S1 were added to a planetary mixer, preliminarily mixed at room temperature for 15 minutes, and then dispersed at room temperature for 30 minutes using a three-roll mill, the whole process being carried out in a dark environment, to obtain a UV light curable resin composition.
TABLE 1
TABLE 2
In tables 1 and 2, a1 in component (a) is triallyl isocyanurate, a2 is bisphenol a diallyl ether, A3 is dicyclopentyl acrylate; in component (B), B1 is 5,5' -bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) biphenyl, B2 is 5,5' -bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) -3,3' -dimethoxybiphenyl, B3 is pentaerythritol tetrakis (3-mercaptopropionate), B4 is the bifunctional hybrid thiol compound disclosed in CN 112840004A; b5 is 1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril, B6 is 1,1- (dithiobisethanediyl) -bis [3,4, 6-tris (2-mercaptoethyl) glycoluril ]; the component (C) is 2, 2-dimethoxy-2-phenylacetophenone; the component (D) is p-hydroxyanisole; the component (E) is gamma-mercaptopropyltrimethoxysilane; component (F) is fumed silica.
The main raw material sources used in examples 1-17 and comparative examples 1-6 are as follows:
triallyl isocyanurate is used as the winning for the debridement
The equivalent of the carbon-carbon double bond functional group is 83 g/eq;
the bisphenol A diallyl ether is B303589 of Shanghai Aladdin Biotechnology GmbH, with a carbon-carbon double bond functional group equivalent of 154 g/eq;
dicyclopentyl acrylate is DCP-A of KyoeishｃA chemical Co., Ltd, and the equivalent of the carbon-carbon double bond functional group is 152/eq;
the thiol compound 5,5 '-bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) biphenyl was prepared from preparation example 1, the thiol equivalent was 120g/eq, and the structural formula was as shown in formula (iv):
the thiol compound 5,5' -bis (3-mercaptopropyl) -2,2' -bis (3-mercaptopropoxy) -3,3' -dimethoxybiphenyl was prepared from preparation example 2, had a thiol equivalent of 135g/eq and a structural formula shown in formula (V):
pentaerythritol tetrakis (3-mercaptopropionate) was PEMP from SC organic Chemicals, Japan, the mercaptan equivalent was 122g/eq, and the structural formula was represented by the formula (VI):
the bifunctional hybrid thiol compound has a structure represented by formula (VII), is liquid at room temperature, has a molecular weight of 389, and has a thiol equivalent of 211 g/eq:
1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril, derived from the four kingdom chemical industries, as a crystalline solid at room temperature, with a thiol equivalent of 95 g/eq;
the mercaptan equivalent weight of 1,1- (dithio-bis-ethanediyl) -bis [3,4, 6-tris (2-mercaptoethyl) glycoluril ] is 127g/eq, and the preparation method comprises the following steps: adding 3.18g of 1,3,4, 6-tetra (2-hydroxyethyl) glycoluril into a reaction bottle, stirring at room temperature, dropwise adding 11.75g of thionyl chloride, and refluxing for 2 hours after dropwise adding; cooling to 10 ℃, adding 10mL of water and 3.65g of thiourea, and continuously refluxing and stirring for reaction for 12 hours; then cooling to 25 ℃, dropwise adding 4.00g of 48% sodium hydroxide aqueous solution under nitrogen atmosphere, and stirring and reacting for 9 hours at 70 ℃; after cooling to 20 ℃ again, 3.50g of concentrated hydrochloric acid and 10mL of chloroform were added thereto, and the mixture was stirred for 30 minutes, followed by 1 st suction filtration, 10mL of chloroform was added to the resulting cake, and the mixture was stirred for 30 minutes, followed by 2 nd suction filtration. The filtrates from the two suction filtrations were combined to remove the aqueous layer, the organic layer was washed 5 times with 5mL of water, and the organic layer was concentrated under reduced pressure to give 3.1g of a yellow oil (crude product); separating and purifying the crude product by column chromatography (eluent: chloroform) to obtain 2.85g of white crystal (melting point: 75.3-77.8 deg.C), i.e. 1,3,4, 6-tetra (2-mercaptoethyl) glycoluril; in addition, 0.28g of a pale yellow oily substance was obtained, i.e., 1' - (dithiobisethanediyl) -bis [3,4, 6-tris (2-mercaptoethyl) glycoluril ] as a product, and the mercaptan equivalent was 127 g/eq;
2, 2-dimethoxy-2-phenylacetophenone is Irgacure-651 from BASF, Germany;
p-hydroxyanisole is MEHQ of Solvay company;
gamma-mercaptopropyl radicalTrimethoxysilane by Meiji corporation
A-189；
The filler is fumed silica selected from H20 from Waker.
Test example
(1) Measurement of crystal precipitation time:
the resin compositions prepared in examples 1 to 17 and comparative examples 1 to 6 were each left at room temperature for a period of time from completion of the preparation of the resin compositions until crystal precipitation was confirmed. The crystal deposition was confirmed by visual observation, and the maximum time of the test was 240 hours. The results are shown in Table 3.
(2) Measurement of glass transition temperature:
the resin compositions prepared in examples 1 to 17 and comparative examples 1 to 6 were stored in a sealed and static manner at room temperature for 240 hours, respectively, and then the resin compositions were taken out, injected into a tetrafluoroethylene mold, scraped off, and irradiated with an ultraviolet light source (365nm, light intensity 1000 mW/cm)2) Irradiating and curing for 9 seconds, preparing the completely cured resin composition into 42mm multiplied by 8mm multiplied by 0.3mm slices, testing by using a Q-800 type dynamic thermo-mechanical analysis tester of a American TA instrument, and measuring the change rule of a loss factor (tan delta) along with the temperature in a liquid nitrogen atmosphere and a film stretching mode within the temperature range of-40 to 250 ℃, wherein the temperature rise rate is 10 ℃/min, the testing frequency is 10Hz, and thus the glass transition temperature (DEG C) of the cured resin composition is determined.
(3) Measurement of Hot tack Strength:
the resin compositions prepared in examples 1 to 17 and comparative examples 1 to 6 were respectively stored for 240 hours at room temperature by sealing and standing, and then the resin compositions were taken out and respectively coated on a stainless steel sheet, laminated with a tempered glass sheet, the thickness of the adhesive layer was controlled with 0.13mm copper wire, the area of the adhesive layer was 25.4mm × 5mm, and an ultraviolet light source (365nm, light intensity 1000 mW/cm)2) Irradiating and curing for 9 seconds, then pulling the completely cured sample apart in opposite directions by using a universal tester, testing at the ambient temperature of 85 ℃, and measuring the force valueI.e. the hot adhesion strength immediately after sample preparation, recorded as strength (MPa); and (3) treating the cured sample for 120 hours at 85 ℃/85% RH under heating and humidifying conditions, and testing the shear bonding strength of the sample again under the condition that the environmental temperature is 85 ℃, namely the thermal bonding strength (MPa) after heating and humidifying. The results are shown in Table 3.
(4) Water absorption: preparing a sample of 3mm multiplied by 1.5mm from the completely cured resin composition, weighing and recording the sample, immersing the sample into deionized water at the temperature of 100 ℃, and carrying out constant temperature treatment for 2 hours; taking the sample out of the water, carefully absorbing the water attached to the surface of the sample by using filter paper, weighing the sample again and recording; the weight percentage increase of the sample before and after boiling was calculated as the water absorption (%). The results are shown in Table 3.
TABLE 3
When comparative examples 1 to 17 and/or comparative examples 1 to 6 are analyzed in conjunction with table 3, it can be seen that, first, when examples 1 to 8 are analyzed, the crystal precipitation time of the UV light-curable resin composition of the present invention exceeds the maximum test time of 240 hours, since the thiol compound of the present invention is in a liquid state at room temperature, the resin composition is more stable in storage and thus has a long pot life, and meanwhile, the thiol compound of the present invention has no ester bond and a small odor, the resin composition can be rapidly cured by UV light irradiation after being stored for 240 hours on standing and has a high degree of crosslinking after curing, the glass transition temperature exceeds 120 ℃, the water absorption rate is within 2.61%, high heat resistance and good moisture barrier property are exhibited, and the thermal bonding strength of the cured product measured at a high temperature of 85 ℃ reaches 6MPa or more, and after the heating and humidifying test, the hot bonding strength of more than 88 percent can be maintained, which shows that the resin composition of the invention has excellent hot bonding strength and heat-resistant and moisture-resistant performance.
The analysis of examples 9 to 13 shows that the ratio of the carbon-carbon double bond to the equivalent weight of the thiol functional group has no significant effect on the storage stability and the moisture and heat resistance of the resin composition, the resin composition has no crystal precipitation within 240 hours, the reduction range of the thermal bonding strength of the resin composition before and after the heating and humidifying experiment after curing is still relatively small, but the ratio of the carbon-carbon double bond to the equivalent weight of the thiol functional group has a certain effect on the bonding performance of the resin composition, the ratio is optimally 0.9 to 1.2, when the ratio is too large or too small, the thermal bonding strength of the resin composition after curing is slightly reduced, but still can reach more than 5.55MPa, the glass transition temperature is also reduced to a certain extent, but the glass transition temperature is still more than 95 ℃ as a whole, the barrier performance of moisture is reduced to a certain extent, but the water absorption rate is still maintained within 3%.
By comparing and analyzing example 1 and examples 14 to 17, it can be seen that the storage stability of the resin composition is not affected but the adhesive property, the moisture barrier property and the resistance to wet heat hydrolysis are all reduced to some extent after the preferred unsaturated resin combination of the present invention is replaced by one of the unsaturated resins alone, which indicates that the preferred unsaturated resin combination of the present invention has a significant effect on the adhesive property, the moisture barrier property and the resistance to wet heat hydrolysis of the resin composition.
By comparing and analyzing example 1 and comparative example 1, it can be found that after the thiol compound prepared by the present invention is replaced by pentaerythritol tetrakis (3-mercaptopropionate) ester containing ester bond, since pentaerythritol tetrakis (3-mercaptopropionate) ester is liquid at room temperature, the resin composition does not precipitate crystals, the storage stability and pot life are not greatly affected, but the glass transition temperature of the cured product is sharply decreased to 65 ℃, the thermal bonding strength is also decreased to 4.52MPa, the heat resistance and the bonding property are both significantly decreased, meanwhile, the water absorption of the cured product is as high as 7.97%, and the thermal bonding strength after the heating and humidifying test is almost disappeared, which shows that the thiol compound without ester bond in the present invention has a very critical effect on the heat resistance, the bonding property, the moisture barrier property and the wet-heat hydrolysis resistance after the resin composition is cured.
By comparing and analyzing the example 1 and the comparative example 2, it can be found that after the thiol compound prepared by the invention is replaced by the bifunctional hybrid thiol compound shown in the structural formula (VII), because the thiol compound is liquid at room temperature, the resin composition has no crystal precipitation, and the storage stability and the pot life are not greatly influenced, but the glass transition temperature of the cured product is sharply reduced to 27 ℃, the thermal bonding strength is also reduced to 4.17MPa, the heat resistance and the thermal bonding performance are obviously reduced, meanwhile, the water absorption of the cured product is also as high as 5.25%, and the thermal bonding strength after a heating and humidifying test is also obviously reduced, thereby further explaining that the thiol compound has very key influence on the heat resistance, the bonding performance, the moisture barrier performance and the wet and hot hydrolysis resistance after the resin composition is cured.
By comparing and analyzing example 1 and comparative example 3, it can be found that after the thiol compound prepared by the present invention is replaced by 1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril, because the pure thiol compound is solid crystal at room temperature, the crystal precipitation time of the resin composition is greatly shortened to 5 hours, the glass transition temperature after curing is reduced to 89 ℃, the thermal bonding strength is reduced to 5.28MPa, and the water absorption rate also reaches 3.86%, which indicates that the solid polythiol curing agent 1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril is crystallized after being stored for a period of time, and incomplete curing is easy to occur to cause the reduction of the comprehensive performance of the resin composition.
By comparing and analyzing example 1 and comparative examples 3 to 4, it can be seen that the problems of short crystal precipitation time and performance degradation of the solid thiol compound 1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril are improved to some extent in comparative example 4 by adding a partially liquid 1,1- (dithiobis (ethanediyl) -bis [3,4, 6-tris (2-mercaptoethyl) glycoluril ], but this solution still has limited storage stability of the resin composition while significantly increasing the cost, and the glass transition temperature, thermal bond strength and water absorption after curing are inferior to those of the resin composition of example 1 of the present invention, indicating that the thiol compound of the present invention can provide storage stability, heat resistance, and water absorption of the resin composition at low cost without crystal precipitation, The adhesive properties, moisture barrier properties and resistance to wet thermal hydrolysis have a significant impact.
By comparing and analyzing example 1 and comparative examples 5 to 6, it can be found that the storage stability of the resin composition is not affected when the preferable unsaturated resin composition of the present invention is replaced with the ester bond-containing dicyclopentanyl acrylate, but the glass transition temperature and the thermal bonding strength are both greatly reduced, the thermal bonding strength after the heating and humidifying experiment is also maintained less than 50%, and the water absorption rate is increased more than twice, which shows that the unsaturated resin composition of the present invention has a significant effect on the heat resistance, the adhesive property, the moisture barrier property and the wet-heat hydrolysis resistance of the resin composition.
In conclusion, the combination of the thiol compound and the optimized unsaturated resin provided by the invention has obvious influence on the comprehensive performance of the UV light curing resin composition; the multifunctional group mercaptan compound is liquid at room temperature, has no ester bond and little smell, and the corresponding UV light-cured resin composition has no crystal precipitation in the storage process; the UV light-cured resin composition provided by the invention has the advantages of fast curing, small smell, long service life and the like, and has high crosslinking degree, good moisture barrier property, excellent heat resistance, adhesive property and humidity-heat hydrolysis resistance after curing.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (18)
1. A UV light-curable resin composition is characterized in that the following components are included in the UV light-curable resin composition:
(A) an unsaturated resin having two or more carbon-carbon double bond groups and no ester bond;
(B) a thiol compound represented by the following general formula (I);
(C) a photoinitiator; and
(D) a polymerization inhibitor;
in the general formula (I), R1、R2、R3And R4Wherein only one is a mercaptoalkoxy group having 2 to 5 carbon atoms, R5、R6、R7And R8Wherein only one is a mercaptoalkoxy group having 2 to 5 carbon atoms, R1、R2、R3、R4、R5、R6、R7And R8The remaining six of (A) are each independently selected from one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms and a lower alkoxy group having 1 to 3 carbon atoms.
2. The UV-curable resin composition according to claim 1, wherein R in the thiol compound represented by the general formula (I)1、R2And R4One of them is a mercaptoalkoxy group having 2 to 5 carbon atoms and the other two are both hydrogen atoms, R3And R7Each independently selected from a hydrogen atom or a methoxy group, R5、R6And R8One of them is a mercaptoalkoxy group having 2 to 5 carbon atoms and the other two are both hydrogen atoms.
3. The UV-curable resin composition according to claim 1, wherein R in the thiol compound represented by the general formula (I)1And R5Are each a hydrogen atom, R3And R7Each independently selected from a hydrogen atom or a methoxy group, R2And R4One of them is a mercaptoalkoxy group having 2 to 5 carbon atoms and the other is a hydrogen atom, R6And R8One of them is a mercaptoalkoxy group having 2 to 5 carbon atoms and the other is a hydrogen atom.
4. The UV-curable resin composition according to claim 1, wherein R in the thiol compound represented by the general formula (I)1And R5Are each a hydrogen atom, R3And R7Each independently selected from a hydrogen atom or a methoxy group, and when R is2And R6When all are mercapto alkoxy groups having 2 to 5 carbon atoms, R4And R8Are each a hydrogen atom; when R is4And R8When all are mercapto alkoxy groups having 2 to 5 carbon atoms, R2And R6Are each a hydrogen atom; when R is4And R6When all are mercapto alkoxy groups having 2 to 5 carbon atoms, R2And R8Are each a hydrogen atom; when R is2And R8When all are mercapto alkoxy groups having 2 to 5 carbon atoms, R4And R6Are all hydrogen atoms.
5. The UV curable resin composition according to claim 1, wherein the thiol compound is prepared according to a method comprising the steps of:
the method comprises the following steps: performing substitution reaction on the biphenol compound represented by the general formula (II) and the first compound represented by the general formula (III) in the presence of a phase transfer catalyst under an alkaline condition, and purifying to obtain a liquid colorless or light yellow first intermediate product;
step two: carrying out free radical addition reaction on the first intermediate product and thioacetic acid in the presence of a free radical initiator, and purifying to obtain a liquid colorless or light yellow second intermediate product;
step three: carrying out hydrolysis reaction on the second intermediate product, and purifying to obtain a colorless or light yellow viscous liquid product, namely the mercaptan compound;
in the general formula (II), R9、R10、R11And R12In which only one is hydroxy, R13、R14、R15And R16In which only one is hydroxy, R9、R10、R11、R12、R13、R14、R15And R16The remaining six of the groups are respectively and independently selected from one of hydrogen atoms, alkyl groups with 1-3 carbon atoms and alkoxy groups with 1-3 carbon atoms;
in the general formula (III), X represents chlorine or bromine, and m is 0, 1, 2 or 3.
6. The UV curable resin composition according to claim 5, wherein in the first step, the substitution reaction is carried out by dissolving the biphenol compound represented by the general formula (II) in an organic solvent, adding a base to provide alkaline conditions, adding a phase transfer catalyst, then heating to 40-100 ℃ under the protection of an inert gas, stirring for 10-60 minutes, then adding the first compound represented by the general formula (III), reacting for 4-12 hours, then filtering the reaction solution, distilling the filtrate under reduced pressure to remove the solvent, washing with water for three times, extracting with chloroform, collecting the organic phase, and evaporating to dryness to obtain a first intermediate product which is liquid and colorless or pale yellow.
7. The UV curable resin composition according to claim 5, wherein in the second step, the radical addition reaction is carried out by dissolving the first intermediate product in an organic solvent, adding a radical initiator, raising the temperature to 40-100 ℃ under the protection of an inert gas, slowly adding thioacetic acid, carrying out the radical addition reaction for 4-12 hours, and then distilling off the solvent under reduced pressure to obtain a second intermediate product which is liquid and colorless or pale yellow.
8. The UV curable resin composition according to claim 5, wherein in the third step, the hydrolysis reaction is performed by dissolving the second intermediate product in an organic solvent, adding hydrochloric acid or sodium hydroxide, heating to 50-100 ℃ for reaction for 3-12 hours, distilling under reduced pressure to remove the solvent, washing twice with 2-8% sodium bicarbonate solution, extracting with chloroform, collecting the organic phase, and evaporating to dryness to obtain a colorless or light yellow viscous liquid product, i.e., the thiol compound.
9. The UV-curable resin composition according to any one of claims 1 to 8, wherein the carbon-carbon double bond group in the unsaturated resin is at least one of a vinyl group, an allyl group, a vinyl ether group and an allyl ether group.
10. The UV-curable resin composition according to any one of claims 1 to 8, wherein the unsaturated resin is a combination of at least one trifunctional unsaturated resin and at least one difunctional unsaturated resin in a weight ratio of 1 (0.1) to 0.5.
11. The UV-curable resin composition according to any one of claims 1 to 8, wherein the unsaturated resin is a combination of triallyl isocyanurate and bisphenol A diallyl ether in a weight ratio of 1 (0.1) to 0.5.
12. The UV-curable resin composition according to any one of claims 1 to 8, wherein the unsaturated resin is contained in an amount of 30 to 45 parts by weight, and the thiol compound is contained in an amount of 40 to 60 parts by weight; the ratio of the equivalent of the carbon-carbon double bond functional group in the unsaturated resin to the equivalent of the thiol functional group in the thiol compound is 0.7 to 1.5, preferably 0.9 to 1.2.
13. The UV curable resin composition according to any one of claims 1 to 8, wherein the photoinitiator is a radical photoinitiator selected from the group consisting of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenylmethanone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, and mixtures thereof, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinobenzylphenyl) butanone, 4-benzoyl-4 '-methyl-diphenylsulfide, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ], 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-1-hexanophenone, bis-2, 6-difluoro-3-pyrrolylphenyltitanocene, methyl benzoylformate, benzophenone, 4-methylbenzophenone, methyl benzoylformate, methyl ester, at least one of 4-phenylbenzophenone, 4-chlorobenzophenone, methyl benzoylbenzoate, ethyl 4-dimethylaminobenzoate, isooctyl p-dimethylaminobenzoate, 4' -bis (diethylamino) benzophenone, isopropylthioxanthone, 2, 4-diethylthioxanthone, and 2-ethylanthraquinone; the content of the photoinitiator is 0.3-5 parts by weight.
14. The UV-curable resin composition according to any one of claims 1 to 8, wherein the polymerization inhibitor is at least one selected from hydroquinone, p-hydroxyanisole, p-benzoquinone, methylhydroquinone, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, 4-hydroxypiperidinoxy free radical, phenothiazine and anthraquinone; the content of the polymerization inhibitor is 0.01-0.5 weight part.
15. The UV-curable resin composition according to any one of claims 1 to 8, further comprising a coupling agent and/or an auxiliary agent; the coupling agent is at least one selected from gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 8-epoxypropoxytrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane; the auxiliary agent is selected from at least one of filler, antioxidant, stabilizer, flame retardant, diluent, pigment, defoamer, leveling agent and ion trapping agent; the content of the coupling agent is 0.01-3 parts by weight; the content of the auxiliary agent is 0.01-30 parts by weight.
16. The method for producing a UV curable resin composition according to any one of claims 1 to 15, which comprises uniformly mixing an unsaturated resin, a thiol compound represented by the general formula (i), a photoinitiator, a polymerization inhibitor and optionally a coupling agent and an auxiliary agent in a dark environment.
17. Use of the UV light-curable resin composition according to any one of claims 1 to 15 for the preparation of an adhesive.
18. Use of the UV light-curable resin composition according to any one of claims 1 to 15 for the preparation of a sealant.
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