CN115819645A - Preparation method of polyreactive ultraviolet curing conductive adhesive resin matrix - Google Patents
Preparation method of polyreactive ultraviolet curing conductive adhesive resin matrix Download PDFInfo
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- CN115819645A CN115819645A CN202211100688.1A CN202211100688A CN115819645A CN 115819645 A CN115819645 A CN 115819645A CN 202211100688 A CN202211100688 A CN 202211100688A CN 115819645 A CN115819645 A CN 115819645A
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- 239000011159 matrix material Substances 0.000 title claims abstract description 28
- 239000004840 adhesive resin Substances 0.000 title claims abstract description 20
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
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- 230000001070 adhesive effect Effects 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 15
- 238000007265 chloromethylation reaction Methods 0.000 claims abstract description 15
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims abstract description 14
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- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
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- 239000003054 catalyst Substances 0.000 claims description 8
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- 239000005051 trimethylchlorosilane Substances 0.000 claims description 6
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- 230000035484 reaction time Effects 0.000 claims description 5
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
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- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- VMOWKUTXPNPTEN-UHFFFAOYSA-N n,n-dimethylpropan-2-amine Chemical compound CC(C)N(C)C VMOWKUTXPNPTEN-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 125000004185 ester group Chemical group 0.000 abstract description 4
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- 125000003636 chemical group Chemical group 0.000 abstract 1
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- 239000000243 solution Substances 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 7
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- 229920005989 resin Polymers 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
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- 238000007306 functionalization reaction Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
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Abstract
The invention belongs to the technical field of conductive adhesive, and discloses a preparation method of a polyreactive ultraviolet curing conductive adhesive resin matrix. The invention makes the conductive adhesive resin matrix have higher reaction activity based on the chemical structure characteristics of beta-ketoester group. The preparation method comprises the following specific steps: firstly, dissolving a styrene copolymer in a solvent, mixing and reacting with a chloromethylation reagent, and grafting a chloromethyl functional group on a benzene ring of the styrene copolymer; then, converting a chloromethyl functional group into alcoholic hydroxyl through electrophilic substitution reaction; finally, the alcoholic hydroxyl and the ester are subjected to ester exchange reaction to introduce beta-ketoester group, so as to obtain beta-ketoester group grafted styrene copolymer, namely the polyreactive ultraviolet curing conductive adhesive resin matrix. The beta-ketoester group is easy to react with various chemical groups, so the conductive adhesive resin matrix prepared by the method has higher reaction activity and wide application range.
Description
Technical Field
The invention belongs to the technical field of conductive adhesives, and particularly relates to a preparation method of a polyreactive ultraviolet curing conductive adhesive resin matrix.
Background
With the gradual miniaturization and portability development of electronic products, the conductive adhesive for electronic packaging is widely applied to the microelectronic packaging and assembly industries. The traditional Pb/Sn material has low resolution, serious pollution and overhigh curing temperature, and is easy to damage parts among electronic components, thereby influencing the connection reliability of the electronic devices and being incapable of meeting the requirements. Therefore, conductive adhesive connecting materials with low pollution and even without pollution gradually become a research hotspot. The ultraviolet light curing conductive adhesive is generally composed of components such as resin, conductive particles, a photoinitiator and the like, wherein the resin directly determines the adhesive property of the conductive adhesive, so that how to improve the reactivity of the resin and expand the application range of the resin is very important.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a polyreactive ultraviolet curing conductive adhesive resin matrix. The invention also aims to provide the polyreactive ultraviolet curing conductive adhesive resin matrix prepared by the method.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a polyreactive ultraviolet curing conductive adhesive resin matrix comprises the following steps:
(1) Dissolving a styrene copolymer resin matrix in a solvent, mixing and reacting with a chloromethylation reagent, and grafting a chloromethyl functional group on a benzene ring of the styrene copolymer;
(2) The chloromethyl functional group is converted into alcoholic hydroxyl group through electrophilic substitution reaction;
(3) And (3) carrying out ester exchange reaction on alcoholic hydroxyl and esters to introduce beta-ketoester group to obtain beta-ketoester group grafted styrene copolymer, namely the polyreactive ultraviolet curing conductive adhesive resin matrix.
Preferably, the comonomer of the styrenic copolymer in step (1) is selected from one or more of α -olefinic monomers in which butadiene, ethylene, acrylonitrile, acrylic acid, acrylates and styrene are copolymerized using an ionic or radical mechanism, more preferably a styrene-ethylene-butadiene-styrene copolymer.
Preferably, the chloromethylation reagent in step (1) is trimethylchlorosilane, and the catalyst used in the reaction is trioxane and tin tetrachloride.
Preferably, the solvent in step (1) is chloroform.
Preferably, the reaction temperature in the step (1) is 0-25 ℃, more preferably 0 ℃, and the reaction time is 1-6 h; the mass volume ratio g/mL of the styrene copolymer to the chloromethylation reagent is 1-6, the mass ratio of the catalyst trioxane to the styrene copolymer is 3-6.
Preferably, the electrophilic substitution reaction in step (2) is specifically an electrophilic substitution reaction between a chloromethyl functional group and a thiol group in β -mercaptoethanol.
Preferably, the electrophilic substitution reaction in step (2) is carried out under catalysis of a basic catalyst selected from one of sodium ethoxide, potassium tert-butoxide, diisopropylamine, piperidine, dimethylisopropylamine, 1-methylpyrrolidine, triethylamine, 1-methylpiperidine, diisopropylethylamine, imidazole, pyridine, 2-methylpyridine, 2, 6-dimethylpyridine, 4-dimethylaminopyridine, 1, 8-diazabicyclo [5,4,0] undec-7-ene, 1, 5-diazabicyclo [4,3,0] undec-7-ene.
Preferably, the electrophilic substitution reaction temperature in the step (2) is 30-90 ℃, and the reaction time is 2-8 h.
Preferably, the ester in step (3) is tert-butyl acetoacetate.
Preferably, the transesterification solvent in step (3) is one selected from xylene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, chlorobenzene, dimethyl sulfoxide and butyl acetate; the transesterification reaction temperature is 90-170 ℃, and the reaction time is 2-4 h.
A polyreactive ultraviolet curing conductive adhesive resin matrix is prepared by the method.
Preferably, the structural formula of the polyreactive ultraviolet curing conductive adhesive resin matrix is as follows:
wherein the mol percentage content of the beta-ketoester is 10 to 60 percent.
The ultraviolet light curing conductive adhesive resin matrix is applied to the preparation of conductive adhesives.
The invention carries out beta-ketoester group functionalization on the resin matrix by a continuous chemical modification method. Beta-ketoester group is a common organic synthesis intermediate, and methylene between carbonyl and ester group in the molecule is influenced by two strong electron-withdrawing groups, so that the beta-ketoester group has high reaction activity and is called as active methylene. The active methylene can be heterolytic to form free radicals under the radiation of ultraviolet light, and can also be subjected to reactions such as acylation, alkylation and the like; the carbonyl group can react with various nucleophilic reagents, and the carbonyl group and the ester group bifunctional group can also carry out various ring closing to prepare various heterocycles. Therefore, the beta-ketoester group is introduced into the resin matrix of the conductive adhesive, so that the reaction activity of the resin matrix can be improved, and the application range of the conductive adhesive is expanded.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention makes the styrene copolymer resin matrix contain beta-ketoester group through continuous chemical modification of the styrene copolymer resin matrix, endows the styrene copolymer resin matrix with higher reaction activity and enlarges the application range of the ultraviolet curing conductive adhesive.
(2) The chloromethylation reactant has low toxicity and mild reaction conditions, the chloromethylation degree can be manually regulated, and the average grafting rate of chloromethyl is 10-60%.
Drawings
FIG. 1 is a reaction scheme of a β -ketoester functionalized styrenic copolymer;
FIG. 2 is the NMR chart of chloromethyl-modified styrene-based copolymer in example 1;
FIG. 3 is the NMR chart of the hydroxyl group modified styrene-based copolymer in example 1;
FIG. 4 is the NMR spectrum of the styrenic copolymer β -ketoester group modification in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The following examples are intended to illustrate the invention but should not be construed as limiting it.
The styrene-ethylene-butadiene-styrene copolymer (SEBS) in the examples was purchased from Kentum technology, inc., of USA, trioxane, tin tetrachloride (SnCl) 4 ) 1, 8-diazacyclo [5,4,0]]Undecene-7 (DBU), xylene and t-butyl acetoacetate were purchased from Hadamard reagent (Shanghai) Co., ltd, and trimethylchlorosilane and β -mercaptoethanol were purchased from Tokyo chemical industries, ltd. Other chemical reagents were purchased from common reagent platforms and used directly without special instructions.
The chloromethylation reaction is to graft and modify the para-position of a benzene ring into chloromethyl. The invention adopts trimethylchlorosilane as chloromethylation reagent, trioxane and SnCl 4 The chloromethylated SEBS can be successfully obtained by using the method as a catalyst, and the method has the advantages of low reactant toxicity, mild reaction conditions, artificial regulation and control of chloromethylation degree and the like.
According to the integral area of the characteristic proton peak in the hydrogen spectrogram of nuclear magnetic resonance, the average grafting rate of SEBS chloromethylation can be calculated according to the formula (1).
Wherein F is the average grafting rate, and A is the integral area of the characteristic peak of the spectrogram.
The hydroxylation reaction is to further modify the chloromethylated styrenic copolymer to contain alcoholic hydroxyl groups. The method comprises the steps of carrying out substitution reaction on chloromethyl and sulfydryl in beta-mercaptoethanol under the catalysis of an alkaline catalyst, and further introducing an alcoholic hydroxyl functional group. Finally, the alcoholic hydroxyl group can be converted into beta-ketoester group through the ester exchange reaction of the alcoholic hydroxyl group and the acetoacetic acid tert-butyl ester, and the styrene copolymer resin matrix with the functionalized beta-ketoester group is prepared. The reaction mechanism of the beta-ketoester functionalized styrene copolymer is shown in figure 1.
Example 1
(1) 5g of SEBS was dissolved in chloroform, and 5.4g of trioxane and 22.8mL of trimethylchlorosilane were added thereto and stirred uniformly. The evenly mixed solution is put into an ice water bath to be cooled to 0 ℃, and 3.8mL of SnCl is added dropwise under the stirring condition 4 Then, the reaction was carried out for 2 hours under stirring at room temperature. After the reaction is finished, the solution is poured into a beaker containing absolute ethyl alcohol with about ten times of the volume of the solution for precipitation and washing, and finally the precipitated chloromethylation product (SEBS-CH) 2 -Cl) was dried in a vacuum oven at 60 ℃ to constant weight. The average grafting ratio of chloromethyl group can be calculated to be about 30% according to the NMR chart and the formula (1) shown in FIG. 2.
(2) 2g of SEBS-CH 2 dissolving-Cl in a chloroform solvent, adding 0.20g of mercaptoethanol and 0.26mL of DBU, stirring and mixing uniformly, and finally carrying out condensation reflux reaction for 4 hours under the condition of nitrogen protection at 60 ℃. After the reaction is finished, the solution is poured into a beaker filled with ethanol with about ten times of the volume of the solution for precipitation and washing, and a precipitated product (SEBS-SH-OH) is dried in a vacuum oven at 60 ℃ to constant weight. According to the NMR spectrum shown in FIG. 3, the chloromethyl group had been converted substantially completely to the alcoholic hydroxyl group.
(3) Dissolving 2g of SEBS-SH-OH in xylene, adding 6g of tert-butyl acetoacetate, stirring and reacting at 140 ℃ for 4 hours, finally pouring the solution into a beaker containing absolute ethanol with about ten times of the volume of the solution for precipitation, and washing twice. The precipitated product was dried in a vacuum oven at 60 ℃ to constant weight. From the NMR chart shown in FIG. 4, it was found that the beta-ketoester group was successfully grafted to the styrenic copolymer.
Example 2
(1) 3g of SEBS was dissolved in chloroform, and 3.2g of trioxane and 14mL of trimethylchlorosilane were added thereto and stirred uniformly. The evenly mixed solution is put into an ice water bath to be cooled to 0 ℃, and 2.4mL of SnCl is added dropwise under the stirring condition 4 Then, the reaction was carried out for 4 hours under stirring at room temperature. After the reaction is finished, the solution is poured into a beaker containing absolute ethyl alcohol with about ten times of the volume of the solution for precipitation and washing, and finally the precipitated chloromethylation product (SEBS-CH) 2 -Cl) was dried in a vacuum oven at 60 ℃ to constant weight. According to the NMR hydrogen spectrum test and the formula (1), the average grafting rate of chloromethyl can be calculated to be about 52%.
(2) 1g of SEBS-CH 2 dissolving-Cl in a chloroform solvent, adding 0.10g of mercaptoethanol and 0.15mL of DBU, stirring and mixing uniformly, and finally carrying out condensation reflux reaction for 6h under the condition of nitrogen protection at 60 ℃. After the reaction is finished, pouring the solution into a beaker filled with ethanol with about ten times of the volume of the solution for precipitation and washing, and placing a precipitation product (SEBS-SH-OH) in a vacuum oven at 60 ℃ for drying until the weight is constant.
(3) 1g of SEBS-SH-OH is dissolved in dimethylbenzene, 3g of tert-butyl acetoacetate is added, the mixture is stirred and reacted for 3 hours at the temperature of 140 ℃, and finally the solution is poured into a beaker containing absolute ethyl alcohol with about ten times of the volume of the solution for precipitation and washing twice. The precipitated product was dried in a vacuum oven at 60 ℃ to constant weight. The nuclear magnetic resonance test result shows that the beta-keto ester group is successfully grafted to the styrene copolymer.
Example 3
The beta-ketoester modified styrene copolymer prepared in the example 2 is used as a conductive adhesive resin matrix to prepare the ultraviolet light cured conductive adhesive. The formula is as follows: 40 parts of beta-ketoester modified styrene copolymer, 12 parts of n-butyl acrylate, 0.2 part of p-hydroxyanisole, 3 parts of vinyl triethoxysilane and 3 parts of hydrogenated castor oil are added into a homogenizer to be mixed for 30min, then 40 parts of silver-plated copper powder with the particle size of 10-100nm are added to be continuously mixed for 30min, and then the mixture is kept in a dark stateAdding 2 parts of 1-hydroxycyclohexyl phenyl ketone, continuously mixing for 15min, and finally vibrating and defoaming in vacuum to obtain the ultraviolet curing conductive adhesive. Cleaning the glass slide with ethanol, drying, uniformly coating the conductive adhesive on the glass slide by using a blade coating method, wherein the film thickness is about 100-120um, standing for 10min in a dark place, and then placing at 365nm 100mW/cm 2 Curing for 30min in an ultraviolet curing machine. The volume resistivity of the prepared conductive adhesive is 1.72 multiplied by 10 measured by a four-probe method -3 Ω·cm。
Claims (10)
1. A preparation method of a polyreactive ultraviolet curing conductive adhesive resin matrix is characterized by comprising the following steps:
(1) Dissolving styrene copolymer in solvent, mixing with chloromethylation reagent, reacting, and grafting chloromethyl functional group on benzene ring of styrene copolymer;
(2) The chloromethyl functional group is converted into alcoholic hydroxyl group through electrophilic substitution reaction;
(3) And (3) carrying out ester exchange reaction on alcoholic hydroxyl and esters to introduce beta-ketoester group to obtain beta-ketoester group grafted styrene copolymer, namely the polyreactive ultraviolet curing conductive adhesive resin matrix.
2. The process of claim 1, wherein the comonomer of the styrenic copolymer in step (1) is selected from one or more of alpha-olefin monomers copolymerized with styrene by an ionic or free radical mechanism, such as butadiene, ethylene, acrylonitrile, acrylic acid, acrylates.
3. The method according to claim 1, wherein the chloromethylation reagent in step (1) is trimethylchlorosilane, and the catalyst used in the reaction is trioxane and tin tetrachloride.
4. The method according to claim 3, wherein the reaction temperature in the step (1) is 0-25 ℃, and the reaction time is 1-6 h;
the mass volume ratio g/mL of the styrene copolymer to the chloromethylation reagent is 1-6, the mass ratio of the catalyst trioxane to the styrene copolymer is 3-6.
5. The method according to claim 1, wherein the electrophilic substitution in step (2) is specifically an electrophilic substitution of a chloromethyl functional group with a thiol group in β -mercaptoethanol.
6. The method according to claim 5, wherein the electrophilic substitution in step (2) is carried out under catalysis of a basic catalyst selected from the group consisting of sodium ethoxide, potassium tert-butoxide, diisopropylamine, piperidine, dimethylisopropylamine, 1-methylpyrrolidine, triethylamine, 1-methylpiperidine, diisopropylethylamine, imidazole, pyridine, 2-methylpyridine, 2, 6-dimethylpyridine, 4-dimethylaminopyridine, 1, 8-diazabicyclo [5,4,0] undec-7-ene, 1, 5-diazabicyclo [4,3,0] undec-7-ene.
7. The method of claim 5, wherein the electrophilic substitution in step (2) is performed at a temperature of 30 ℃ to 90 ℃ for a time of 2h to 8h.
8. The method according to claim 1, wherein the ester in step (3) is t-butyl acetoacetate, and the transesterification solvent is one selected from xylene, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, chlorobenzene, dimethyl sulfoxide and butyl acetate; the ester exchange reaction temperature is 90-170 ℃, and the reaction time is 2-4 h.
9. A polyreactive ultraviolet-curable conductive adhesive resin matrix prepared by the method of any one of claims 1 to 9, wherein the polyreactive ultraviolet-curable conductive adhesive resin matrix has the following structural formula:
wherein the mol percentage content of the beta-ketoester is 10 to 60 percent.
10. Use of the uv curable conductive adhesive resin matrix according to claim 9 in the preparation of conductive adhesives.
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