CN118308053B - Preparation method of modified epoxy resin adhesive - Google Patents
Preparation method of modified epoxy resin adhesive Download PDFInfo
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- CN118308053B CN118308053B CN202410384860.3A CN202410384860A CN118308053B CN 118308053 B CN118308053 B CN 118308053B CN 202410384860 A CN202410384860 A CN 202410384860A CN 118308053 B CN118308053 B CN 118308053B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 60
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 60
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 39
- 239000000853 adhesive Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 103
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 40
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 14
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 claims abstract description 12
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical group ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 12
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 54
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 43
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 25
- -1 sulfhydryl silicon dioxide Chemical compound 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims description 13
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000001276 controlling effect Effects 0.000 claims description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 9
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Substances CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 7
- 238000010025 steaming Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 claims 1
- OWIQFIKOPWDOGX-UHFFFAOYSA-N (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methanamine;hydrochloride Chemical compound Cl.CC1(C)OB(CN)OC1(C)C OWIQFIKOPWDOGX-UHFFFAOYSA-N 0.000 abstract description 5
- 230000021523 carboxylation Effects 0.000 abstract description 4
- 238000006473 carboxylation reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000007142 ring opening reaction Methods 0.000 abstract description 4
- WTGIOQMHIHCSPZ-UHFFFAOYSA-N sulfanylsilicon Chemical compound S[Si] WTGIOQMHIHCSPZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 229920006332 epoxy adhesive Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000010125 resin casting Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
本发明公开了一种改性环氧树脂胶粘剂的制备方法，涉及胶粘剂技术领域。本发明一种改性环氧树脂胶粘剂的制备方法，包括如下步骤：以纳米二氧化硅为原料经过硅烷偶联剂有机化处理后，再依次通过丁二酸酐开环羧基化、氨基甲基硼酸频哪醇酯盐酸盐接枝，得到改性二氧化硅；再将改性二氧化硅、1‑硫代甘油为原料制备得到巯基化二氧化硅；将巯基化二氧化硅、1,8‑二氮杂二环十一碳‑7‑烯、环氧树脂共混、固化处理，得到胶粘剂。本申请制备的胶粘剂具有优良的力学性能和柔韧性，且耐水性能好。The invention discloses a method for preparing a modified epoxy resin adhesive, and relates to the technical field of adhesives. The invention discloses a method for preparing a modified epoxy resin adhesive, comprising the following steps: using nano silicon dioxide as a raw material, after being organically treated with a silane coupling agent, and then sequentially through succinic anhydride ring-opening carboxylation, aminomethylboronic acid pinacol ester hydrochloride grafting, to obtain modified silicon dioxide; then using modified silicon dioxide and 1-thioglycerol as raw materials to prepare mercapto silicon dioxide; mercapto silicon dioxide, 1,8-diazabicycloundecane-7-ene, epoxy resin are blended and cured to obtain an adhesive. The adhesive prepared by the present application has excellent mechanical properties and flexibility, and good water resistance.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a preparation method of a modified epoxy resin adhesive.
Background
Epoxy resin is one of the most commonly used thermosetting resins, is a polymer prepolymer, is composed of two or more groups of epoxy groups, and uses an aromatic or aliphatic main chain. Epoxy resin is widely applied to the fields of aviation, vehicles, buildings and the like because of strong adhesive property, good chemical corrosion resistance, good mechanical property, excellent insulating property and the like. The epoxy resin adhesive has the advantages of room temperature curing, curing pressure being only contact pressure, high bonding strength, wide mechanical strength, wide bonding surface and the like. However, the unmodified epoxy resin has high crosslinking density after being cured, is in a three-dimensional network structure, has the defects of large internal stress, brittle quality, poor heat resistance, poor impact resistance and the like, and severely limits the application range.
The common epoxy resin toughening methods are as follows: (1) Rubber elastomer is added into epoxy resin to form a disperse phase, for example, carboxyl-terminated nitrile rubber is used as a toughening agent, so that the mechanical property and the thermal property of the adhesive are improved; (2) thermotropic liquid crystal polymer toughening resin alloying; (3) Adding thermoplastic resin to form an interpenetrating network structure, such as polyether sulfone resin, in an epoxy resin system; (4) When the epoxy resin system is cured, a soft segment is introduced into the crosslinked network of the system. However, rubber or thermoplastic elastomers can greatly improve the impact strength of epoxy resins, but at the cost of reduced tensile strength; the reinforcing fiber can greatly improve the tensile strength of the epoxy resin, but the impact strength and the elongation at break are reduced; the in-situ composite reinforcing technology of the liquid crystal polymer can improve the tensile strength and impact strength of the epoxy resin, but reduce the elongation at break. In contrast, inorganic nanoparticle modified epoxy resins can effectively combine the rigidity, dimensional stability and thermal stability of inorganic substances with the toughness, processability and dielectric properties of polymers, so that research on inorganic nanoparticle modified epoxy resins is becoming an increasingly focused research. However, the surface area of the nano particles is large, the occupancy of surface atoms is high, and the surface has a special structure of unsaturated bonds or dangling bonds, so that the nano particles have very large surface activity, are easy to agglomerate, are difficult to achieve uniform dispersion of nano size in an epoxy resin matrix, and further cause the reduction of the bonding performance.
Disclosure of Invention
The invention aims to provide a preparation method of a modified epoxy resin adhesive, which solves the following technical problems:
The existing inorganic particles are added into the epoxy resin, and the inorganic particles are easy to agglomerate with the increase of the addition amount, so that the adhesive property of the epoxy resin is reduced.
The aim of the invention can be achieved by the following technical scheme:
A preparation method of a modified epoxy resin adhesive comprises the following steps:
A1: adding modified silicon dioxide, 1-thioglycerol, tetrahydrofuran and deionized water into a reaction kettle, dispersing uniformly, adding magnesium sulfate, reacting for 24-30 hours at normal temperature under stirring, filtering, and steaming in a rotary way to obtain sulfhydryl silicon dioxide;
A2: adding sulfhydrylation silicon dioxide, 1, 8-diazabicyclo undec-7-ene and epoxy resin into a reaction bottle, placing the reaction bottle in a vacuum drying oven for defoaming, and then performing curing treatment in the drying oven to obtain the adhesive.
As a further aspect of the invention: the addition ratio of the modified silicon dioxide, the 1-thioglycerol, the tetrahydrofuran, the deionized water and the magnesium sulfate in the A1 is 10g:2-4g:100-200mL:0.5-1mL:3-7g.
As a further aspect of the invention: the mass ratio of the mercapto silicon dioxide to the 1, 8-diazabicyclo undec-7-ene to the epoxy resin in the A2 is 1-10:0.5-2:100.
As a further aspect of the invention: the specific steps of the curing treatment in A2 are as follows: the temperature is controlled to be 70-90 ℃ for heat preservation for 1-3h, and the temperature is controlled to be 120-150 ℃ for heat preservation for 0.5-1h.
As a further aspect of the invention: the preparation method of the modified silicon dioxide comprises the following steps:
S1: adding gamma-aminopropyl triethoxysilane and deionized water component I into a reaction bottle, and regulating the pH to 3-4 to obtain a solution A; uniformly dispersing nano silicon dioxide, deionized water component II and absolute ethyl alcohol to obtain a solution B; adding the solution B into the solution A, controlling the temperature to be 50-60 ℃, preserving the temperature for 3-6 hours under the stirring condition, centrifuging, filtering, washing and drying to obtain a component I;
S2: adding the component I and N, N-dimethylformamide into a reaction kettle, dispersing uniformly, adding succinic anhydride, reacting for 6-9 hours at normal temperature under the stirring condition, washing with water, and drying to obtain a component II;
S3: in nitrogen atmosphere, amino methyl boric acid pinacol ester hydrochloride (CAS: 298689-75-5), 2- (1H-benzotrisazo L-1-group) -1, 3-tetramethyl urea tetrafluoroborate (CAS: 125700-67-6) and N, N-dimethylformamide are added into a reaction bottle, the temperature is controlled to be minus 20-0 ℃, the reaction is carried out for 1-3 hours under the heat preservation condition, N-diisopropylamine is added, the reaction is carried out for 1-3 hours under the heat preservation condition, the solvent is removed in vacuum, and the modified silicon dioxide is obtained after washing and drying.
As a further aspect of the invention: in S1, the addition ratio of gamma-aminopropyl triethoxysilane, deionized water component I, nano silicon dioxide, deionized water component II and absolute ethyl alcohol is 0.1-0.5g:2-5mL:1g:10-50mL:10-50mL.
As a further aspect of the invention: in the S2, the addition ratio of the component I to the component N, N-dimethylformamide to the succinic anhydride is 1g:30-50mL:0.1-0.3g.
As a further aspect of the invention: in S3, the addition ratio of the amino methyl boric acid pinacol ester hydrochloride to the components of the two, the 2- (1H-benzotrisazo L-1-yl) -1, 3-tetramethyl urea tetrafluoroborate to the N, N-dimethylformamide to the N, N-diisopropylamine is 0.4-1g:10g:0.5-1g:10-100mL:0.5-1g.
The invention has the beneficial effects that:
(1) Firstly, organically modifying the surface of nano silicon dioxide by utilizing gamma-aminopropyl triethoxy silane, and grafting amino groups on the surface of the silicon dioxide to obtain a component I; performing ring-opening carboxylation by utilizing the amino group of the component I and succinic anhydride, and grafting a large number of carboxyl groups on the surface of silicon dioxide to obtain a component II; and finally, reacting amino groups of the amino methyl boric acid pinacol ester hydrochloride with carboxyl groups of the component II to obtain the modified silicon dioxide. The surface of the modified silicon dioxide prepared by the application is grafted with functional groups such as boric acid groups, amino groups, carboxyl groups and the like through an organosilicon chain segment. The modified epoxy resin adhesive is prepared by carrying out chemical reaction on modified silicon dioxide and 1-thioglycerol serving as raw materials to prepare sulfhydrylated silicon dioxide, taking the sulfhydrylated silicon dioxide as a toughening agent, taking 1, 8-diazabicyclo undec-7-ene as a curing agent accelerator and taking epoxy resin as a base material, and carrying out blending defoaming and then curing treatment.
The surface of the added modified silicon dioxide has unsaturated residual bonds and organic functional bonds in different bonding states, the molecular state is in a three-dimensional network structure, the surface of the modified silicon dioxide has stronger surface energy and chemical reaction activity, the modified silicon dioxide also has elastic mechanical properties similar to a polymer chain, chemical bonding is carried out between the modified silicon dioxide and the epoxy polymer chain to form a chemical crosslinking point, the organic functional groups on the molecular chain on the surface of the silicon dioxide and the epoxy polymer chain are mutually entangled and adsorbed to form a composite three-dimensional network structure, so that a particle network and the epoxy polymer network are mutually prolonged and are staggered and mixed together, the interface energy difference of the particle network and the epoxy polymer network is effectively eliminated, and the composite of organic and inorganic particles is realized; the silica is used as an inorganic substance to introduce rigid particles into the epoxy resin, and forms physical crosslinking points with polymer chains; the modified silicon dioxide actually plays a role of a physical and chemical crosslinking point in the adhesive, the high rigidity of the inorganic structure can reduce the adverse effect on the strength, modulus or thermal property of the cured material, the organic structure can endow the epoxy cured material with good toughness and good compatibility with epoxy resin, and the groups on the surface of the modified silicon dioxide, which can react with the epoxy resin, are favorable for improving the crosslinking density and can achieve the effect of toughening and reinforcing simultaneously.
(2) According to the application, firstly, organic siloxane is utilized to carry out organic modification on silicon dioxide, then succinic anhydride is utilized to carry out ring opening carboxylation, amino methyl boric acid pinacol ester hydrochloride is grafted and 1-thioglycerol is utilized to carry out sulfhydrylation modification, and the prepared sulfhydrylation silicon dioxide is subjected to chemical copolymerization with epoxy resin, so that the compatibility of organic silicon and the epoxy resin is improved, and the problem that the organic silicon is difficult to be effectively dispersed in the epoxy resin due to the fact that the organic silicon and the epoxy resin have larger solubility parameter difference in the prior art is solved. With the addition of the sulfhydryl silicon dioxide, a flexible and stable silicon-oxygen chain is introduced into a curing system to improve the heat resistance of an epoxy resin system and the toughness of the curing system, and the surface energy of organic silicon is lower than that of the epoxy resin, so that the adhesive is endowed with water resistance and oil resistance; and the crosslinking density is increased, the movement of the polymer chain segment is limited by space, the shrinkage rate of the adhesive layer is reduced, the heat-resistant dimensional stability of the epoxy resin curing is further improved, and the thermal performance of the adhesive can be effectively improved.
(3) According to the application, modified silicon dioxide and 1-thioglycerol are used as raw materials to react to prepare the sulfhydryl silicon dioxide, mercaptan at the interface of the silicon dioxide is mixed with the epoxy resin and enters the cured epoxy resin structure, so that the crosslinked epoxy resin is endowed with good flexibility, high shear strength and peel strength. The application grafts amino on the surface of silicon dioxide by utilizing gamma-aminopropyl triethoxy silane, carries out ring opening carboxylation by utilizing the amino of the component I and succinic anhydride, and reacts with the carboxyl of the component II by utilizing the amino of the amino methyl boric acid pinacol ester hydrochloride; the reaction on the surface of silicon dioxide generates a large amount of carbamate groups, has high polarity and activity and has high cohesiveness to various materials. And the borate ester bond generated in the reaction process has the bonding property similar to self-repairing.
Detailed Description
The following description will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation method of the modified silicon dioxide in the embodiment 1 comprises the following steps:
S1: adding 5g of gamma-aminopropyl triethoxysilane and 20mL of deionized water component I into a reaction bottle, and adding glacial acetic acid to adjust the pH to 3 to obtain a solution A; uniformly dispersing 10g of nano silicon dioxide, 100mL of deionized water component II and 100mL of absolute ethyl alcohol to obtain a solution B; adding the solution B into the solution A, controlling the temperature to be 50 ℃, preserving the temperature for 3 hours under the stirring condition, centrifuging, filtering, washing and drying to obtain a component I;
s2: adding 10g of component one and 300mL of N, N-dimethylformamide into a reaction kettle, dispersing uniformly, adding 1g of succinic anhydride, reacting for 6 hours at normal temperature under stirring, washing with water, and drying to obtain a component two;
S3: under nitrogen atmosphere, 1g of amino methyl boric acid pinacol ester hydrochloride (CAS: 298689-75-5), 10g of component two, 1g of 2- (1H-benzo trisazo L-1-yl) -1, 3-tetramethyl urea tetrafluoroborate (CAS: 125700-67-6) and 100mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is controlled to be minus 20 ℃, the reaction is kept at the temperature for 3 hours, 0.5g of N, N-diisopropylamine is added, the reaction is kept at the temperature for 1 hour, the solvent is removed in vacuum, and the reaction is washed and dried, thus obtaining the modified silicon dioxide.
The preparation method of the modified silicon dioxide in the embodiment 2 comprises the following steps:
S1: adding 5g of gamma-aminopropyl triethoxysilane and 40mL of deionized water component I into a reaction bottle, and adding glacial acetic acid to adjust the pH to 3 to obtain a solution A; uniformly dispersing 10g of nano silicon dioxide, 100mL of deionized water component II and 100mL of absolute ethyl alcohol to obtain a solution B; adding the solution B into the solution A, controlling the temperature to be 55 ℃, preserving the temperature for 3 hours under the stirring condition, centrifuging, filtering, washing and drying to obtain a component I;
S2: adding 10g of component one and 300mL of N, N-dimethylformamide into a reaction kettle, dispersing uniformly, adding 2g of succinic anhydride, reacting for 6 hours at normal temperature under stirring, washing with water, and drying to obtain component two;
S3: in a nitrogen atmosphere, 1g of amino methyl boric acid pinacol ester hydrochloride (CAS: 298689-75-5), 10g of component two, 1g of 2- (1H-benzo trisazo L-1-yl) -1, 3-tetramethyl urea tetrafluoroborate (CAS: 125700-67-6) and 100mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is controlled to be minus 10 ℃, the reaction is kept at the temperature for 1H, 1g of N, N-diisopropylamine is added, the reaction is kept at the temperature for 1H, the solvent is removed in vacuum, and the reaction is washed and dried to obtain the modified silicon dioxide.
Example 3 the preparation method of the modified silica comprises the following steps:
s1: adding 5g of gamma-aminopropyl triethoxysilane and 50mL of deionized water component I into a reaction bottle, and adding glacial acetic acid to adjust the pH to 3 to obtain a solution A; uniformly dispersing 10g of nano silicon dioxide, 100mL of deionized water component II and 100mL of absolute ethyl alcohol to obtain a solution B; adding the solution B into the solution A, controlling the temperature to be 50 ℃, preserving the temperature for 3 hours under the stirring condition, centrifuging, filtering, washing and drying to obtain a component I;
S2: adding 10g of component one and 300mL of N, N-dimethylformamide into a reaction kettle, dispersing uniformly, adding 3g of succinic anhydride, reacting for 9 hours at normal temperature under the stirring condition, washing with water, and drying to obtain a component two;
s3: in a nitrogen atmosphere, 1g of amino methyl boric acid pinacol ester hydrochloride (CAS: 298689-75-5), 10g of component two, 1g of 2- (1H-benzo trisazo L-1-yl) -1, 3-tetramethyl urea tetrafluoroborate (CAS: 125700-67-6) and 100mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is controlled to be 0 ℃, the reaction is kept at the temperature for 3 hours, 1g of N, N-diisopropylamine is added, the reaction is kept at the temperature for 1-3 hours, the solvent is removed in vacuum, and the reaction is washed and dried, thus obtaining the modified silicon dioxide.
Example 4a method for preparing a modified epoxy adhesive comprising the steps of:
A1: adding 10g of modified silicon dioxide prepared in example 1, 2g of 1-thioglycerol, 100mL of tetrahydrofuran and 1mL of deionized water into a reaction kettle, uniformly dispersing, adding 3g of magnesium sulfate, reacting for 24 hours at normal temperature under stirring, filtering, and steaming to obtain sulfhydryl silicon dioxide;
a2: 5g of sulfhydryl silicon dioxide, 2g of 1, 8-diazabicyclo undec-7-ene and 100g of bisphenol A type epoxy resin (the epoxy resin with the brand CYD-127 produced by Baling petrochemical company of China petrochemical group asset management and management effective company) are added into a reaction bottle, and are placed into a vacuum drying box for defoaming, then the mixture is placed into the drying box, the temperature is controlled to be 70 ℃ for heat preservation treatment for 3 hours, and the temperature is controlled to be 150 ℃ for heat preservation treatment for 1 hour, so that the adhesive is obtained.
Example 5 a method for preparing a modified epoxy adhesive comprising the steps of:
a1: adding 10g of modified silicon dioxide prepared in example 2, 2g of 1-thioglycerol, 100mL of tetrahydrofuran and 1mL of deionized water into a reaction kettle, uniformly dispersing, adding 3g of magnesium sulfate, reacting for 24 hours at normal temperature under stirring, filtering, and steaming to obtain sulfhydryl silicon dioxide;
a2: 5g of sulfhydryl silicon dioxide, 2g of 1, 8-diazabicyclo undec-7-ene and 100g of bisphenol A type epoxy resin (the epoxy resin with the brand CYD-127 produced by Baling petrochemical company of China petrochemical group asset management and management effective company) are added into a reaction bottle, and are placed into a vacuum drying box for defoaming, then the mixture is placed into the drying box, the temperature is controlled to be 70 ℃ for heat preservation treatment for 3 hours, and the temperature is controlled to be 150 ℃ for heat preservation treatment for 1 hour, so that the adhesive is obtained.
Example 6a method of preparing a modified epoxy adhesive comprising the steps of:
a1: adding 10g of modified silicon dioxide prepared in example 3, 2g of 1-thioglycerol, 100mL of tetrahydrofuran and 1mL of deionized water into a reaction kettle, uniformly dispersing, adding 3g of magnesium sulfate, reacting for 24 hours at normal temperature under stirring, filtering, and steaming to obtain sulfhydryl silicon dioxide;
a2: 5g of sulfhydryl silicon dioxide, 2g of 1, 8-diazabicyclo undec-7-ene and 100g of bisphenol A type epoxy resin (the epoxy resin with the brand CYD-127 produced by Baling petrochemical company of China petrochemical group asset management and management effective company) are added into a reaction bottle, and are placed into a vacuum drying box for defoaming, then the mixture is placed into the drying box, the temperature is controlled to be 70 ℃ for heat preservation treatment for 3 hours, and the temperature is controlled to be 150 ℃ for heat preservation treatment for 1 hour, so that the adhesive is obtained.
The preparation method of the modified silicon dioxide of the comparative example 1 comprises the following steps:
Adding 5g of gamma-aminopropyl triethoxysilane and 20mL of deionized water component I into a reaction bottle, and adding glacial acetic acid to adjust the pH to 3 to obtain a solution A; uniformly dispersing 10g of nano silicon dioxide, 100mL of deionized water component II and 100mL of absolute ethyl alcohol to obtain a solution B; adding the solution B into the solution A, controlling the temperature to be 50 ℃, preserving the temperature for 3 hours under the stirring condition, centrifuging, filtering, washing and drying to obtain the modified silicon dioxide.
The preparation method of the modified silicon dioxide of the comparative example 2 comprises the following steps:
S1: adding 5g of gamma-aminopropyl triethoxysilane and 20mL of deionized water component I into a reaction bottle, and adding glacial acetic acid to adjust the pH to 3 to obtain a solution A; uniformly dispersing 10g of nano silicon dioxide, 100mL of deionized water component II and 100mL of absolute ethyl alcohol to obtain a solution B; adding the solution B into the solution A, controlling the temperature to be 50 ℃, preserving the temperature for 3 hours under the stirring condition, centrifuging, filtering, washing and drying to obtain a component I;
s2: adding 10g of component I and 300mL of N, N-dimethylformamide into a reaction kettle, dispersing uniformly, adding 1g of succinic anhydride, reacting for 6 hours at normal temperature under stirring, washing with water, and drying to obtain the modified silicon dioxide.
Comparative example 3a method for preparing a modified epoxy adhesive comprising the steps of:
A1: adding 10g of modified silicon dioxide prepared in comparative example 1, 2g of 1-thioglycerol, 100mL of tetrahydrofuran and 1mL of deionized water into a reaction kettle, uniformly dispersing, adding 3g of magnesium sulfate, reacting for 24 hours at normal temperature under stirring, filtering, and steaming to obtain sulfhydryl silicon dioxide;
a2: 5g of sulfhydryl silicon dioxide, 2g of 1, 8-diazabicyclo undec-7-ene and 100g of bisphenol A type epoxy resin (the epoxy resin with the brand CYD-127 produced by Baling petrochemical company of China petrochemical group asset management and management effective company) are added into a reaction bottle, and are placed into a vacuum drying box for defoaming, then the mixture is placed into the drying box, the temperature is controlled to be 70 ℃ for heat preservation treatment for 3 hours, and the temperature is controlled to be 150 ℃ for heat preservation treatment for 1 hour, so that the adhesive is obtained.
Comparative example 4a method for preparing a modified epoxy adhesive comprising the steps of:
a1: 10g of the modified silica prepared in comparative example 1 and 2g of 1-thioglycerol were blended, and a modifier;
A2: adding 5g of modifier, 2g of 1, 8-diazabicyclo undec-7-ene and 100g of bisphenol A type epoxy resin (epoxy resin with the brand of CYD-127 produced by Baling petrochemical division of China petrochemical group asset management and management effective company) into a reaction bottle, placing the reaction bottle in a vacuum drying oven for defoaming, then placing the reaction bottle in the drying oven, controlling the temperature to be 70 ℃ for heat preservation treatment for 3 hours, and controlling the temperature to be 150 ℃ for heat preservation treatment for 1 hour to obtain the adhesive.
Comparative example 5 a method for preparing a modified epoxy adhesive comprising the steps of:
a1: adding 10g of modified silicon dioxide prepared in comparative example 2, 2g of 1-thioglycerol, 100mL of tetrahydrofuran and 1mL of deionized water into a reaction kettle, uniformly dispersing, adding 3g of magnesium sulfate, reacting for 24 hours at normal temperature under stirring, filtering, and steaming to obtain sulfhydryl silicon dioxide;
a2: 5g of sulfhydryl silicon dioxide, 2g of 1, 8-diazabicyclo undec-7-ene and 100g of bisphenol A type epoxy resin (the epoxy resin with the brand CYD-127 produced by Baling petrochemical company of China petrochemical group asset management and management effective company) are added into a reaction bottle, and are placed into a vacuum drying box for defoaming, then the mixture is placed into the drying box, the temperature is controlled to be 70 ℃ for heat preservation treatment for 3 hours, and the temperature is controlled to be 150 ℃ for heat preservation treatment for 1 hour, so that the adhesive is obtained.
Performance detection
(1) Impact strength: testing according to GB/T2571-2021 impact test method of resin casting body, detecting by an impact tester, wherein the detection result is shown in Table 1;
(2) Shear strength: testing according to GB/T7124-2008 adhesive tensile shear strength determination method (Metal to Metal), detecting by using a CMT6303 type universal testing machine (tensile speed is 5 mm/min), wherein the detection result is shown in Table 1;
(3) Water resistance: the adhesive films prepared in examples 4 to 6 and comparative examples 3 to 5 were tested for water resistance by a dipping method. Naturally drying the prepared sample in a room temperature environment, selecting 60 ℃ for drying by a dryer until the weight is constant, weighing the weight to be m1, soaking the dried sample in deionized water at the temperature of 22 ℃ for 48 hours, selecting the soaked sample to absorb surface moisture, weighing the weight to be m2, and calculating the water absorption eta according to the following formula:
η=[（m2-m1）/m1]×100%
wherein, eta-water absorption rate,%; m 1-weight of sample when dry, mg; m 1-weight of the sample after soaking, mg; the detection results are shown in Table 1;
table 1: statistical table of performance test data for examples 4-6 and comparative examples 3-5
As can be seen from Table 1, the adhesives prepared in examples 4-6 of the present application have good toughness and mechanical properties, and have excellent water resistance.
(4) T-peel strength: the flexible material is tested according to GB/T2791-1995 adhesive T peel strength test method, the peel strength obtained by carrying out one time of adhesive-peel test is recorded as S1, the adhesive is continuously subjected to the adhesive-peel test and repeated 20 times, the peel strength obtained by carrying out 20 times of repeated adhesive-peel strength test is recorded as S20, and the detection result is shown in Table 2;
table 2: tables for statistics of the test data of adhesion property of examples 4 to 6 and comparative examples 3 to 5
As can be seen from Table 1, the adhesives prepared in examples 4-6 of the present application had excellent bond strength to the substrate, and still maintained high bond strength after multiple peel-bonds.
The foregoing describes one embodiment of the present invention in detail, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (7)
1. A preparation method of a modified epoxy resin adhesive is characterized by comprising the following steps: the method comprises the following steps:
A1: adding modified silicon dioxide, 1-thioglycerol, tetrahydrofuran and deionized water into a reaction kettle, dispersing uniformly, adding magnesium sulfate, reacting for 24-30 hours at normal temperature under stirring, filtering, and steaming in a rotary way to obtain sulfhydryl silicon dioxide;
A2: adding sulfhydrylation silicon dioxide, 1, 8-diazabicyclo undec-7-ene and epoxy resin into a reaction bottle, placing the reaction bottle in a vacuum drying oven for defoaming, and then performing curing treatment in the drying oven to obtain an adhesive;
the preparation method of the modified silicon dioxide comprises the following steps:
S1: adding gamma-aminopropyl triethoxysilane and deionized water component I into a reaction bottle, and regulating the pH to 3-4 to obtain a solution A; uniformly dispersing nano silicon dioxide, deionized water component II and absolute ethyl alcohol to obtain a solution B; adding the solution B into the solution A, controlling the temperature to be 50-60 ℃, preserving the temperature for 3-6 hours under the stirring condition, centrifuging, filtering, washing and drying to obtain a component I;
S2: adding the component I and N, N-dimethylformamide into a reaction kettle, dispersing uniformly, adding succinic anhydride, reacting for 6-9 hours at normal temperature under the stirring condition, washing with water, and drying to obtain a component II;
S3: in nitrogen atmosphere, amino methyl boric acid pinacol ester hydrochloride, component two, 2- (1H-benzo trisazo L-1-yl) -1, 3-tetramethyl urea tetrafluoroborate and N, N-dimethylformamide are added into a reaction bottle, the temperature is controlled to be-20-0 ℃, the reaction is carried out for 1-3 hours at a constant temperature, N-diisopropylamine is added, the reaction is carried out for 1-3 hours at a constant temperature, the solvent is removed in vacuum, and the modified silicon dioxide is obtained after washing and drying.
2. The preparation method of the modified epoxy resin adhesive according to claim 1, wherein the addition ratio of the modified silicon dioxide, the 1-thioglycerol, the tetrahydrofuran, the deionized water and the magnesium sulfate in the A1 is 10g:2-4g:100-200mL:0.5-1mL:3-7g.
3. The preparation method of the modified epoxy resin adhesive according to claim 1, wherein the mass ratio of the mercapto silica to the 1, 8-diazabicyclo undec-7-ene to the epoxy resin in the A2 is 1-10:0.5-2:100.
4. The method for preparing the modified epoxy resin adhesive according to claim 1, wherein the specific steps of the curing treatment in the A2 are as follows: the temperature is controlled to be 70-90 ℃ for heat preservation for 1-3h, and the temperature is controlled to be 120-150 ℃ for heat preservation for 0.5-1h.
5. The preparation method of the modified epoxy resin adhesive according to claim 1, wherein the addition ratio of gamma-aminopropyl triethoxysilane, deionized water component one, nano silicon dioxide, deionized water component two and absolute ethyl alcohol in S1 is 0.1-0.5g:2-5mL:1g:10-50mL:10-50mL.
6. The preparation method of the modified epoxy resin adhesive according to claim 1, wherein the addition ratio of the component I, N-dimethylformamide and succinic anhydride in the S2 is 1g:30-50mL:0.1-0.3g.
7. The method for preparing the modified epoxy resin adhesive according to claim 1, wherein the addition ratio of the aminomethyl boric acid pinacol ester hydrochloride, the component two, the 2- (1H-benzotrisazo L-1-group) -1, 3-tetramethylurea tetrafluoroborate, the N, N-dimethylformamide and the N, N-diisopropylamine in the S3 is 0.4-1g:10g:0.5-1g:10-100mL:0.5-1g.
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| CN112457632A (en) * | 2020-11-18 | 2021-03-09 | 广州凯协科技有限公司 | SiO with high dielectric property2-montmorillonite synergistically modified epoxy resin and preparation method thereof |
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