CN116589960B - Weather-resistant epoxy-based structural adhesive and preparation method thereof - Google Patents
Weather-resistant epoxy-based structural adhesive and preparation method thereof Download PDFInfo
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- CN116589960B CN116589960B CN202310565235.4A CN202310565235A CN116589960B CN 116589960 B CN116589960 B CN 116589960B CN 202310565235 A CN202310565235 A CN 202310565235A CN 116589960 B CN116589960 B CN 116589960B
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- 239000000853 adhesive Substances 0.000 title claims abstract description 38
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 38
- 239000004593 Epoxy Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 117
- 238000002156 mixing Methods 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 44
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 35
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 claims description 30
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 23
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 22
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 22
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 22
- 229920002545 silicone oil Polymers 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- KDXKERNSBIXSRK-UHFFFAOYSA-N lysine Chemical compound NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 21
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000004472 Lysine Substances 0.000 claims description 16
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 16
- PELGKMTVNFFDDL-UHFFFAOYSA-N dodecyl-dimethoxy-methylsilane Chemical compound CCCCCCCCCCCC[Si](C)(OC)OC PELGKMTVNFFDDL-UHFFFAOYSA-N 0.000 claims description 16
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical group BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 claims description 12
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 11
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 7
- 238000007792 addition Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- -1 paratoluenesulfonic acid monohydrate Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- LYLHOKOTRWUGIF-UHFFFAOYSA-N 4-(4-hydroxyphenyl)-2H-phthalazin-1-one Chemical compound C1=CC(O)=CC=C1C1=NNC(=O)C2=CC=CC=C12 LYLHOKOTRWUGIF-UHFFFAOYSA-N 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
- 239000002994 raw material Substances 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- ZETHHMPKDUSZQQ-UHFFFAOYSA-N Betulafolienepentol Natural products C1C=C(C)CCC(C(C)CCC=C(C)C)C2C(OC)OC(OC)C2=C1 ZETHHMPKDUSZQQ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- HEOKFDGOFROELJ-UHFFFAOYSA-N diacetal Natural products COc1ccc(C=C/c2cc(O)cc(OC3OC(COC(=O)c4cc(O)c(O)c(O)c4)C(O)C(O)C3O)c2)cc1O HEOKFDGOFROELJ-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007789 sealing Methods 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
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention discloses a weather-proof epoxy-based structural adhesive and a preparation method thereof, wherein the weather-proof epoxy-based structural adhesive comprises a component A and a component B, the component A is modified epoxy resin, the component B is a curing agent, the component A and the component B are mixed according to the mass ratio of 10:1-3 when the weather-proof epoxy-based structural adhesive is used, a compact grid structure can be formed after the modified epoxy resin and the curing agent are mixed and cured, and a flexible chain segment and a rigid chain segment are matched, so that the prepared structural adhesive has good mechanical property, meanwhile, a hindered phenol structure is contained in a molecular chain, the ageing resistance is improved, and compared with the traditional ageing resistance, the problem of precipitation of an ageing resistance component does not occur, so that the service life of the structural adhesive is prolonged, meanwhile, the single molecular chain contains an organosilicon chain segment, the water resistance and the heat ageing resistance of the structure are further improved, and the toughness of the structural adhesive is further improved.
Description
Technical Field
The invention relates to the technical field of preparation of epoxy structural adhesives, in particular to a weather-resistant epoxy structural adhesive and a preparation method thereof.
Background
Building construction adhesives can be classified into inorganic and organic types by composition. Inorganic substances are currently classified into silicate and phosphate. The organic species are now mainly epoxy resins, acrylic and polyurethane. Because epoxy resins have properties incomparable with other thermosetting resins in addition to the numerous advantages of the general polymers, they are most used as host binders. At present, the epoxy structural adhesive is applied to various engineering constructions such as house reinforcement, highway bridges, anchoring and sealing, etc. In particular to the aspects of steel plate adhesion reinforcement, highway rapid repair technology, carbon fiber cloth reinforcement, bar planting technology and the like. However, unmodified epoxy resin cured products are generally rigid, have poor initial properties, and have low impact strength and peel strength of the glued joint, and thus are often required to be modified by an appropriate method to alleviate the disadvantages of epoxy resins.
Disclosure of Invention
The invention aims to provide a weather-proof epoxy-based structural adhesive and a preparation method thereof, which solve the problem that the weather-proof effect of the epoxy structural adhesive at the present stage is poor.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the weather-resistant epoxy-based structural adhesive specifically comprises the following steps:
weighing the component A and the component B, and mixing according to the mass ratio of 10:1-3 to prepare the weather-resistant epoxy structural adhesive;
the component A is modified epoxy resin, and the modified epoxy resin is prepared by the following steps:
uniformly mixing a modified monomer, benzyl triethyl ammonium chloride and epoxy chloropropane, reacting for 2-4 hours at the rotation speed of 200-300 r/min and the temperature of 80-90 ℃, adding sodium hydroxide solution, and continuing to react for 1-1.5 hours to obtain the modified epoxy resin.
The component B is a curing agent.
Further, the dosage ratio of the modified monomer to the benzyl triethyl ammonium chloride to the epoxy chloropropane to the sodium hydroxide solution is 30mmo l:3mmo l:2.4mo l:4.5mL, and the mass fraction of the sodium hydroxide solution is 40%.
Further, the modified monomer is prepared by the following steps:
step A1: uniformly mixing pentaerythritol, 4-carboxybenzaldehyde, paratoluenesulfonic acid monohydrate, DMF and petroleum ether, reacting for 10-15 hours at the rotation speed of 200-300 r/min and the temperature of 90-95 ℃ to obtain an intermediate 1, uniformly mixing the intermediate 1, diethanolamine, 4-dimethylaminopyridine and benzene, reacting for 6-8 hours at the rotation speed of 150-200 r/min and the temperature of 25-30 ℃, adding paratoluenesulfonic acid and acrylic acid, heating to 100-110 ℃, and reacting for 3-5 hours to obtain an intermediate 2;
step A2: adding dodecyl methyl dimethoxy silane and dimethyl dichloro silane into deionized water, stirring at the rotation speed of 200-300 r/min and the temperature of 25-30 ℃, adding tetrahydrofuran and concentrated sulfuric acid, heating to 55-65 ℃, preserving heat for 5-10 min, adding 1, 3-tetramethyl disiloxane, reacting for 3-5h to obtain an intermediate 3, uniformly mixing the intermediate 2, the intermediate 3 and dimethylbenzene, stirring at the rotation speed of 200-300 r/min and the temperature of 50-60 ℃, adding chloroplatinic acid, heating to 60-65 ℃, and reacting for 6-8h to obtain hyperbranched silicone oil;
step A3: uniformly mixing 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-ketone, sodium hydroxide and deionized water, stirring and adding bromoethylene at the rotation speed of 150-200 r/min and the temperature of 50-60 ℃, heating to 70-75 ℃ after the addition, reacting for 10-12 hours to obtain an intermediate 4, mixing the intermediate 4 and 1, 4-dioxane, stirring and adding a Kasite catalyst and hyperbranched silicone oil at the rotation speed of 200-300 r/min and the temperature of 60-70 ℃, reacting for 1-1.5 hours, heating to 80-85 ℃, and reacting for 20-25 hours to obtain the modified monomer.
Further, the dosage ratio 1mo l:2mo l:150mL:75mL of pentaerythritol, 4-carboxybenzaldehyde, DMF and petroleum ether in the step A1 is that the dosage of the p-toluenesulfonic acid monohydrate is 2% of the sum of the mass of the pentaerythritol and the 4-carboxybenzaldehyde, the molar ratio of the intermediate 1, diethanolamine, 4-dimethylaminopyridine and acrylic acid is 1:2:2.1:4, and the dosage of the p-toluenesulfonic acid is 3-5% of the mass of the acrylic acid.
Further, the dosage ratio of the dodecyl methyl dimethoxy silane, the dimethyl dichloro silane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A2 is 2mmo l:3mmo l:5mL:1mmo l, the dosage of the concentrated sulfuric acid is 6-8% of the sum of the mass of the dodecyl methyl dimethoxy silane, the mass of the dimethyl dichloro silane and the mass of the 1, 3-tetramethyl disiloxane, the molar ratio of the intermediate 2 to the intermediate 3 is n:3n+1, n is a natural number larger than 0, and the dosage of the chloroplatinic acid is 0.3-0.5 per mill of the mass of the intermediate 2 and the mass of the intermediate 3.
Further, the dosage ratio of 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-one, sodium hydroxide, deionized water and bromoethylene in the step A3 is 2mmo l:3mmo l:2mL:3mmo l, the molar ratio of S i-H bonds on the intermediate 4 and hyperbranched silicone oil is 1:1, and the dosage of the Kasite catalyst is 0.3-0.5 per mill of the mass of the intermediate 4 and the hyperbranched silicone oil.
Further, the curing agent is prepared by the following steps:
step B1: mixing 2, 6-di-tert-butylphenol and potassium hydroxide, introducing nitrogen for protection, reacting for 1-1.5 hours at the rotation speed of 150-200 r/min and the temperature of 50-60 ℃, heating to 90-95 ℃, adding methyl acrylate, heating to 130-140 ℃, reacting for 4-6 hours to obtain an intermediate 5, dissolving the intermediate 5 in ethanol, stirring and adding sodium hydroxide solution at the rotation speed of 200-300 r/min and the temperature of 20-25 ℃, heating to 40-50 ℃, and reacting for 3-6 hours to obtain an intermediate 6;
step B2: dissolving the intermediate 6 in chloroform, stirring and adding thionyl chloride at the rotation speed of 150-200 r/min and the temperature of 40-50 ℃, reacting for 4-6h, distilling and removing low-boiling substances at the temperature of 80-90 ℃, mixing a substrate, diethanolamine and DMF, stirring for 30-40 min at the rotation speed of 200-300 r/min, adding lysine and p-toluenesulfonic acid, heating to 100-110 ℃, and continuously reacting for 5-7h to obtain the curing agent.
Further, the dosage ratio of 2, 6-di-tert-butylphenol, potassium hydroxide and methyl acrylate in the step B1 is 24g:0.9g:15mL, the dosage ratio of the intermediate 5, ethanol and sodium hydroxide solution is 6g:10mL:11mL, and the mass fraction of the sodium hydroxide solution is 10%.
Further, the dosage ratio of the intermediate 6 to the thionyl chloride in the step B2 is 5g to 12mL, the molar ratio of the substrate to the diethanolamine to the lysine is 1:1:2.1, and the dosage of the p-toluenesulfonic acid is 3-5% of the mass of the substrate to the diethanolamine to the lysine.
The invention has the beneficial effects that: the invention discloses a weather-proof epoxy structural adhesive, which comprises a component A and a component B, wherein the component A is modified epoxy resin, the component B is curing agent, the modified epoxy resin takes modified monomer and epoxy chloropropane as raw materials, under the action of benzyl triethyl ammonium chloride, imine on the modified monomer and epoxy group on the epoxy chloropropane react, then ring closure is carried out under alkaline condition to prepare modified epoxy resin, the modified epoxy resin takes pentaerythritol and 4-carboxylic benzaldehyde as raw materials, and under the action of p-toluenesulfonic acid monohydrate, diacetal reaction is carried out to prepare intermediate 1, under the action of 4-dimethylaminopyridine, carboxyl on the intermediate 1 and imine on the diethanolamine are dehydrated and condensed, and then the intermediate 1 is acrylated with acrylic acid, preparing an intermediate 2, hydrolyzing dodecyl methyl dimethoxy silane and dimethyl dichloro silane, polymerizing with 1, 3-tetramethyl disiloxane to prepare an intermediate 3, reacting a double bond on the intermediate 2 with S i-H bond on the intermediate 3 under the action of chloroplatinic acid to form a S i-H end-capped hyperbranched structure, reacting 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-one with bromoethylene to react a hydroxyl group on the 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-one with a bromine atom site of bromoethylene to prepare an intermediate 4, reacting the intermediate 4 with the hyperbranched silicone oil to react a double bond on the intermediate 4 with S i-H bond on the hyperbranched silicone oil to prepare a modified monomer, the curing agent is prepared by carrying out Michael addition reaction on raw materials of 2, 6-di-tert-butylphenol and methyl acrylate under the action of potassium hydroxide to obtain an intermediate 5, hydrolyzing the intermediate 5 under the action of sodium hydroxide solution to convert ester groups into carboxyl groups to obtain an intermediate 6, reacting the intermediate 6 with thionyl chloride to generate acyl chloride, then reacting with ethyleneglycol amine imine, adding lysine to carry out esterification reaction under the action of p-toluenesulfonic acid to obtain the curing agent, and when the modified epoxy resin and the curing agent are mixed and cured, a compact grid structure can be formed, and the flexible chain segment and the rigid chain segment are matched, so that the prepared structural adhesive has good mechanical properties, meanwhile, the molecular chain contains a hindered phenol structure, the ageing resistance is improved, and compared with the traditional ageing resistance agent, the problem of precipitation of ageing resistance components does not occur, the service life of the structural adhesive is further prolonged, meanwhile, the single molecular chain contains an organosilicon chain segment, the water resistance, the ageing resistance and the heat resistance performance are further improved, and the toughness of the structural adhesive is further improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but 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.
Example 1
The preparation method of the weather-resistant epoxy-based structural adhesive specifically comprises the following steps:
weighing the component A and the component B, and mixing according to the mass ratio of 10:1 to prepare the weather-resistant epoxy-based structural adhesive;
the component A is modified epoxy resin, and the modified epoxy resin is prepared by the following steps:
uniformly mixing a modified monomer, benzyl triethyl ammonium chloride and epichlorohydrin, reacting for 2 hours at the rotating speed of 200 r/min and the temperature of 80 ℃, adding sodium hydroxide solution, and continuing to react for 1 hour to obtain the modified epoxy resin.
The component B is a curing agent.
The dosage ratio of the modified monomer to the benzyl triethyl ammonium chloride to the epoxy chloropropane to the sodium hydroxide solution is 30mmo l:3mmo l:2.4mo l:4.5mL, and the mass fraction of the sodium hydroxide solution is 40%.
The modified monomer is prepared by the following steps:
step A1: uniformly mixing pentaerythritol, 4-carboxybenzaldehyde, paratoluenesulfonic acid monohydrate, DMF and petroleum ether, reacting for 10 hours at the rotation speed of 200 r/min and the temperature of 90 ℃ to obtain an intermediate 1, uniformly mixing the intermediate 1, diethanolamine, 4-dimethylaminopyridine and benzene, reacting for 6 hours at the rotation speed of 150 r/min and the temperature of 25 ℃, adding paratoluenesulfonic acid and acrylic acid, heating to 100 ℃, and reacting for 3 hours to obtain an intermediate 2;
step A2: adding dodecyl methyl dimethoxy silane and dimethyl dichloro silane into deionized water, stirring for 20 min at the rotation speed of 200 r/min and the temperature of 25 ℃, adding tetrahydrofuran and concentrated sulfuric acid, heating to 55 ℃, preserving heat for 5 min, adding 1, 3-tetramethyl disiloxane, reacting for 3h to obtain an intermediate 3, uniformly mixing the intermediate 2, the intermediate 3 and dimethylbenzene, stirring and adding chloroplatinic acid at the rotation speed of 200 r/min and the temperature of 50 ℃, heating to 60 ℃, and reacting for 6h to obtain hyperbranched silicone oil;
step A3: uniformly mixing 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-ketone, sodium hydroxide and deionized water, stirring and adding bromoethylene at the rotation speed of 150 r/min and the temperature of 50 ℃, heating to 70 ℃ after the addition, reacting for 10 hours to obtain an intermediate 4, mixing the intermediate 4 and 1, 4-dioxane, stirring and adding a Kasite catalyst and hyperbranched silicone oil at the rotation speed of 200 r/min and the temperature of 60 ℃, reacting for 1 hour, heating to 80 ℃, and reacting for 20 hours to obtain the modified monomer.
The dosage ratio 1mo l:2mo l:150mL:75mL of pentaerythritol, 4-carboxybenzaldehyde, DMF and petroleum ether in the step A1 is 2% of the mass sum of pentaerythritol and 4-carboxybenzaldehyde, the molar ratio of the intermediate 1, diethanolamine, 4-dimethylaminopyridine and acrylic acid is 1:2:2.1:4, and the dosage of the p-toluenesulfonic acid is 3% of the mass sum of acrylic acid.
The dosage ratio of the dodecyl methyl dimethoxy silane, the dimethyl dichloro silane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A2 is 2mmo l:3mmo l:5mL:1mmo l, the dosage of the concentrated sulfuric acid is 6 percent of the sum of the mass of the dodecyl methyl dimethoxy silane, the mass of the dimethyl dichloro silane and the mass of the 1, 3-tetramethyl disiloxane, the molar ratio of the intermediate 2 to the intermediate 3 is 1:4, and the dosage of the chloroplatinic acid is 0.3 per mill of the mass of the intermediate 2 and the mass of the intermediate 3.
The dosage ratio of 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-ketone, sodium hydroxide, deionized water and bromoethylene in the step A3 is 2mmo l:3mmo l:2mL:3mmo l, the molar ratio of S i-H bonds on the intermediate 4 and hyperbranched silicone oil is 1:1, and the dosage of the Kasite catalyst is 0.3 per mill of the mass of the intermediate 4 and the hyperbranched silicone oil.
The curing agent is prepared by the following steps:
step B1: mixing 2, 6-di-tert-butylphenol and potassium hydroxide, introducing nitrogen for protection, reacting for 1h at the temperature of 50 ℃ at the rotation speed of 150 r/min, heating to 90 ℃, adding methyl acrylate, heating to 130 ℃, reacting for 4h to obtain an intermediate 5, dissolving the intermediate 5 in ethanol, stirring and adding sodium hydroxide solution at the temperature of 20 ℃ at the rotation speed of 200 r/min, heating to 40 ℃, and reacting for 3h to obtain an intermediate 6;
step B2: dissolving the intermediate 6 in chloroform, stirring and adding thionyl chloride at the rotation speed of 150 r/min and the temperature of 40 ℃, reacting for 4 hours, distilling at the temperature of 80 ℃, removing low-boiling substances, mixing a substrate, diethanolamine and DMF, stirring for 30 min at the rotation speed of 200 r/min, adding lysine and p-toluenesulfonic acid, heating to 100 ℃, and continuously reacting for 5 hours to obtain the curing agent.
The dosage ratio of the 2, 6-di-tert-butylphenol to the potassium hydroxide to the methyl acrylate in the step B1 is 24g to 0.9g to 15mL, the dosage ratio of the intermediate 5 to the ethanol to the sodium hydroxide solution is 6g to 10mL to 11mL, and the mass fraction of the sodium hydroxide solution is 10%.
The dosage ratio of the intermediate 6 to the thionyl chloride in the step B2 is 5g to 12mL, the molar ratio of the substrate to the diethanolamine to the lysine is 1:1:2.1, and the dosage of the p-toluenesulfonic acid is 3% of the mass of the substrate to the diethanolamine to the lysine.
Example 2
The preparation method of the weather-resistant epoxy-based structural adhesive specifically comprises the following steps:
weighing the component A and the component B, and mixing according to the mass ratio of 10:2 to prepare the weather-resistant epoxy-based structural adhesive;
the component A is modified epoxy resin, and the modified epoxy resin is prepared by the following steps:
uniformly mixing a modified monomer, benzyl triethyl ammonium chloride and epichlorohydrin, reacting for 3 hours at the rotation speed of 200 r/min and the temperature of 85 ℃, adding sodium hydroxide solution, and continuously reacting for 1.5 hours to obtain the modified epoxy resin.
The component B is a curing agent.
The dosage ratio of the modified monomer to the benzyl triethyl ammonium chloride to the epoxy chloropropane to the sodium hydroxide solution is 30mmo l:3mmo l:2.4mo l:4.5mL, and the mass fraction of the sodium hydroxide solution is 40%.
The modified monomer is prepared by the following steps:
step A1: uniformly mixing pentaerythritol, 4-carboxybenzaldehyde, paratoluenesulfonic acid monohydrate, DMF and petroleum ether, reacting for 10 hours at the temperature of 95 ℃ at the rotation speed of 200 r/min to obtain an intermediate 1, uniformly mixing the intermediate 1, diethanolamine, 4-dimethylaminopyridine and benzene, reacting for 7 hours at the temperature of 30 ℃ at the rotation speed of 150 r/min, adding paratoluenesulfonic acid and acrylic acid, heating to 100 ℃, and reacting for 3 hours to obtain an intermediate 2;
step A2: adding dodecyl methyl dimethoxy silane and dimethyl dichloro silane into deionized water, stirring at the rotation speed of 300 r/min and the temperature of 25 ℃ for 25 min, adding tetrahydrofuran and concentrated sulfuric acid, heating to 60 ℃, preserving heat for 8 min, adding 1, 3-tetramethyl disiloxane, reacting for 4h to obtain an intermediate 3, uniformly mixing the intermediate 2, the intermediate 3 and dimethylbenzene, stirring and adding chloroplatinic acid at the rotation speed of 200 r/min and the temperature of 55 ℃, heating to 65 ℃, and reacting for 7h to obtain hyperbranched silicone oil;
step A3: uniformly mixing 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-ketone, sodium hydroxide and deionized water, stirring and adding bromoethylene at the rotation speed of 150 r/min and the temperature of 55 ℃, heating to 75 ℃ after the addition, reacting for 11 hours to obtain an intermediate 4, mixing the intermediate 4 and 1, 4-dioxane, stirring and adding a Kasite catalyst and hyperbranched silicone oil at the rotation speed of 200 r/min and the temperature of 65 ℃, reacting for 1.5 hours, heating to 80 ℃, and reacting for 25 hours to obtain the modified monomer.
The dosage ratio 1mo l:2mo l:150mL:75mL of pentaerythritol, 4-carboxybenzaldehyde, DMF and petroleum ether in the step A1 is 2% of the sum of the mass of pentaerythritol and 4-carboxybenzaldehyde, the molar ratio of the intermediate 1, diethanolamine, 4-dimethylaminopyridine and acrylic acid is 1:2:2.1:4, and the dosage of the p-toluenesulfonic acid is 4% of the mass of acrylic acid.
The dosage ratio of the dodecyl methyl dimethoxy silane, the dimethyl dichloro silane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A2 is 2mmo l:3mmo l:5mL:1mmo l, the dosage of the concentrated sulfuric acid is 7 percent of the sum of the mass of the dodecyl methyl dimethoxy silane, the mass of the dimethyl dichloro silane and the mass of the 1, 3-tetramethyl disiloxane, the molar ratio of the intermediate 2 to the intermediate 3 is 2:7, and the dosage of the chloroplatinic acid is 0.4 per mill of the mass of the intermediate 2 and the intermediate 3.
The dosage ratio of 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-ketone, sodium hydroxide, deionized water and bromoethylene in the step A3 is 2mmo l:3mmo l:2mL:3mmo l, the molar ratio of S i-H bonds on the intermediate 4 and hyperbranched silicone oil is 1:1, and the dosage of the Kasite catalyst is 0.4 per mill of the mass of the intermediate 4 and the hyperbranched silicone oil.
The curing agent is prepared by the following steps:
step B1: mixing 2, 6-di-tert-butylphenol and potassium hydroxide, introducing nitrogen for protection, reacting for 1.5 hours at the rotation speed of 150 r/min and the temperature of 55 ℃, heating to 93 ℃, adding methyl acrylate, heating to 135 ℃, reacting for 5 hours to obtain an intermediate 5, dissolving the intermediate 5 in ethanol, stirring and adding sodium hydroxide solution at the rotation speed of 200 r/min and the temperature of 25 ℃, heating to 45 ℃, and reacting for 4 hours to obtain the intermediate 6;
step B2: dissolving the intermediate 6 in chloroform, stirring and adding thionyl chloride at the rotation speed of 150 r/min and the temperature of 45 ℃ for reaction for 5 hours, distilling to remove low-boiling substances at the temperature of 85 ℃, mixing a substrate, diethanolamine and DMF, stirring for 35 min at the rotation speed of 200 r/min, adding lysine and p-toluenesulfonic acid, heating to 105 ℃, and continuing to react for 6 hours to obtain the curing agent.
The dosage ratio of the 2, 6-di-tert-butylphenol to the potassium hydroxide to the methyl acrylate in the step B1 is 24g to 0.9g to 15mL, the dosage ratio of the intermediate 5 to the ethanol to the sodium hydroxide solution is 6g to 10mL to 11mL, and the mass fraction of the sodium hydroxide solution is 10%.
The dosage ratio of the intermediate 6 to the thionyl chloride in the step B2 is 5g to 12mL, the molar ratio of the substrate to the diethanolamine to the lysine is 1:1:2.1, and the dosage of the p-toluenesulfonic acid is 4% of the mass of the substrate to the diethanolamine to the lysine.
Example 3
The preparation method of the weather-resistant epoxy-based structural adhesive specifically comprises the following steps:
weighing the component A and the component B, and mixing according to the mass ratio of 10:3 to prepare the weather-resistant epoxy-based structural adhesive;
the component A is modified epoxy resin, and the modified epoxy resin is prepared by the following steps:
uniformly mixing a modified monomer, benzyl triethyl ammonium chloride and epichlorohydrin, reacting for 4 hours at the rotation speed of 300 r/min and the temperature of 90 ℃, adding sodium hydroxide solution, and continuously reacting for 1.5 hours to obtain the modified epoxy resin.
The component B is a curing agent.
The dosage ratio of the modified monomer to the benzyl triethyl ammonium chloride to the epoxy chloropropane to the sodium hydroxide solution is 30mmo l:3mmo l:2.4mo l:4.5mL, and the mass fraction of the sodium hydroxide solution is 40%.
The modified monomer is prepared by the following steps:
step A1: uniformly mixing pentaerythritol, 4-carboxybenzaldehyde, paratoluenesulfonic acid monohydrate, DMF and petroleum ether, reacting for 15 hours at the rotation speed of 300 r/min and the temperature of 95 ℃ to obtain an intermediate 1, uniformly mixing the intermediate 1, diethanolamine, 4-dimethylaminopyridine and benzene, reacting for 8 hours at the rotation speed of 200 r/min and the temperature of 30 ℃, adding paratoluenesulfonic acid and acrylic acid, heating to 110 ℃, and reacting for 5 hours to obtain an intermediate 2;
step A2: adding dodecyl methyl dimethoxy silane and dimethyl dichloro silane into deionized water, stirring for 30 min at the rotation speed of 300 r/min and the temperature of 30 ℃, adding tetrahydrofuran and concentrated sulfuric acid, heating to 65 ℃, preserving heat for 10 min, adding 1, 3-tetramethyl disiloxane, reacting for 5h to obtain an intermediate 3, uniformly mixing the intermediate 2, the intermediate 3 and dimethylbenzene, stirring and adding chloroplatinic acid at the rotation speed of 300 r/min and the temperature of 60 ℃, heating to 65 ℃, and reacting for 8h to obtain hyperbranched silicone oil;
step A3: uniformly mixing 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-ketone, sodium hydroxide and deionized water, stirring and adding bromoethylene at the rotation speed of 200 r/min and the temperature of 60 ℃, heating to 75 ℃ after the addition, reacting for 12 hours to obtain an intermediate 4, mixing the intermediate 4 and 1, 4-dioxane, stirring and adding a Kasite catalyst and hyperbranched silicone oil at the rotation speed of 300 r/min and the temperature of 70 ℃, reacting for 1.5 hours, heating to 85 ℃, and reacting for 25 hours to obtain the modified monomer.
The dosage ratio 1mo l:2mo l:150mL:75mL of pentaerythritol, 4-carboxybenzaldehyde, DMF and petroleum ether in the step A1 is 2% of the sum of the mass of pentaerythritol and 4-carboxybenzaldehyde, the molar ratio of the intermediate 1, diethanolamine, 4-dimethylaminopyridine and acrylic acid is 1:2:2.1:4, and the dosage of the p-toluenesulfonic acid is 5% of the mass of acrylic acid.
The dosage ratio of the dodecyl methyl dimethoxy silane, the dimethyl dichloro silane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A2 is 2mmo l:3mmo l:5mL:1mmo l, the dosage of the concentrated sulfuric acid is 8 percent of the sum of the mass of the dodecyl methyl dimethoxy silane, the mass of the dimethyl dichloro silane and the mass of the 1, 3-tetramethyl disiloxane, the molar ratio of the intermediate 2 to the intermediate 3 is 3:10, and the dosage of the chloroplatinic acid is 0.5 per mill of the mass of the intermediate 2 and the intermediate 3.
The dosage ratio of 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-ketone, sodium hydroxide, deionized water and bromoethylene in the step A3 is 2mmo l:3mmo l:2mL:3mmo l, the molar ratio of S i-H bonds on the intermediate 4 and hyperbranched silicone oil is 1:1, and the dosage of the Kasite catalyst is 0.5 per mill of the mass of the intermediate 4 and the hyperbranched silicone oil.
The curing agent is prepared by the following steps:
step B1: mixing 2, 6-di-tert-butylphenol and potassium hydroxide, introducing nitrogen for protection, reacting for 1.5 hours at the rotation speed of 200 r/min and the temperature of 60 ℃, heating to 95 ℃, adding methyl acrylate, heating to 140 ℃, reacting for 6 hours to obtain an intermediate 5, dissolving the intermediate 5 in ethanol, stirring and adding sodium hydroxide solution at the rotation speed of 300 r/min and the temperature of 25 ℃, heating to 50 ℃, and reacting for 6 hours to obtain the intermediate 6;
step B2: dissolving the intermediate 6 in chloroform, stirring and adding thionyl chloride at the rotation speed of 200 r/min and the temperature of 50 ℃, reacting for 6 hours, distilling to remove low-boiling substances at the temperature of 90 ℃, mixing a substrate, diethanolamine and DMF, stirring for 40 min at the rotation speed of 300 r/min, adding lysine and p-toluenesulfonic acid, heating to 110 ℃, and continuously reacting for 7 hours to obtain the curing agent.
The dosage ratio of the 2, 6-di-tert-butylphenol to the potassium hydroxide to the methyl acrylate in the step B1 is 24g to 0.9g to 15mL, the dosage ratio of the intermediate 5 to the ethanol to the sodium hydroxide solution is 6g to 10mL to 11mL, and the mass fraction of the sodium hydroxide solution is 10%.
The dosage ratio of the intermediate 6 to the thionyl chloride in the step B2 is 5g to 12mL, the molar ratio of the substrate to the diethanolamine to the lysine is 1:1:2.1, and the dosage of the p-toluenesulfonic acid is 5% of the mass of the substrate to the diethanolamine to the lysine.
Comparative example 1
This comparative example uses bisphenol A epoxy resin instead of modified epoxy resin as compared with example 1, and the rest of the procedure is the same.
Comparative example 2
This comparative example uses diethylenetriamine instead of curing agent as compared to example 1, the rest of the procedure being the same.
The structural adhesives prepared in examples 1 to 3 and comparative examples 1 to 2 were coated on the surfaces of two steel sheets of 2 mm. Times.25 mm. Times.100 mm, respectively, and the adhesive areas were 12.5 mm. Times.25 mm, and the temperatures were 25℃and the loudness humidity was 50%, and cured for 7 days to prepare test pieces.
The tensile shear strength of the test specimen was measured by an electronic universal tester at a speed of 5 mm/min.
The tensile shear strength was measured by placing the sample in a constant temperature and humidity test box at a temperature of 50℃and a relative humidity of 95% for 60d and 90 d.
The test pieces were immersed in a constant temperature water bath at 95℃for 3d and 7d, and the tensile shear strength was measured.
The epoxy structural adhesive prepared in examples 1-3 has good weather-proof effect.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (8)
1. A preparation method of weather-resistant epoxy structural adhesive is characterized in that: the method specifically comprises the following steps:
weighing the component A and the component B, and mixing according to the mass ratio of 10:1-3 to prepare the weather-resistant epoxy structural adhesive;
the component A is modified epoxy resin, and the modified epoxy resin is prepared by the following steps:
mixing and reacting a modified monomer, benzyl triethyl ammonium chloride and epichlorohydrin, adding a sodium hydroxide solution, and continuing to react to prepare modified epoxy resin;
the component B is a curing agent;
the modified monomer is prepared by the following steps:
step A1: mixing pentaerythritol, 4-carboxybenzaldehyde, p-toluenesulfonic acid monohydrate, DMF and petroleum ether for reaction to prepare an intermediate 1, mixing intermediate 1, diethanolamine, 4-dimethylaminopyridine and benzene for reaction, adding p-toluenesulfonic acid and acrylic acid, and heating for reaction to prepare an intermediate 2;
step A2: adding dodecyl methyl dimethoxy silane and dimethyl dichloro silane into deionized water, stirring, adding tetrahydrofuran and concentrated sulfuric acid, heating and preserving heat, adding 1, 3-tetramethyl disiloxane, reacting to obtain an intermediate 3, mixing and stirring the intermediate 2, the intermediate 3 and dimethylbenzene, adding chloroplatinic acid, and heating to react to obtain hyperbranched silicone oil;
step A3: mixing 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-ketone, sodium hydroxide and deionized water, stirring, adding bromoethylene, heating to react to obtain an intermediate 4, mixing and stirring the intermediate 4 and 1, 4-dioxane, adding a Caster catalyst and hyperbranched silicone oil, reacting, and heating to react to obtain a modified monomer;
the curing agent is prepared by the following steps:
step B1: mixing 2, 6-di-tert-butylphenol and potassium hydroxide for reaction, heating, adding methyl acrylate for reaction to obtain an intermediate 5, dissolving the intermediate 5 in ethanol, stirring, adding sodium hydroxide solution, and heating for reaction to obtain an intermediate 6;
step B2: dissolving the intermediate 6 in chloroform, stirring, adding sulfoxide chloride, reacting, distilling to remove low-boiling substances, mixing a substrate, diethanolamine and DMF, stirring, adding lysine and p-toluenesulfonic acid, heating, and continuing to react to obtain the curing agent.
2. The method for preparing the weather-resistant epoxy-based structural adhesive according to claim 1, which is characterized in that: the dosage ratio of the modified monomer to the benzyl triethyl ammonium chloride to the epichlorohydrin to the sodium hydroxide solution is 30 mmol/3 mmol/2.4 mol/4.5 mL.
3. The method for preparing the weather-resistant epoxy-based structural adhesive according to claim 1, which is characterized in that: the dosage of pentaerythritol, 4-carboxybenzaldehyde, DMF and petroleum ether in the step A1 is 1mol:2mol:150mL:75mL, the dosage of p-toluenesulfonic acid monohydrate is 2% of the sum of the masses of pentaerythritol and 4-carboxybenzaldehyde, the molar ratio of the intermediate 1, diethanolamine, 4-dimethylaminopyridine and acrylic acid is 1:2:2.1:4, and the dosage of p-toluenesulfonic acid is 3-5% of the mass of acrylic acid.
4. The method for preparing the weather-resistant epoxy-based structural adhesive according to claim 1, which is characterized in that: the dosage ratio of the dodecyl methyl dimethoxy silane, the dimethyl dichloro silane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A2 is 2mmol, 3mmol, 5mL, 1mmol, the dosage of the concentrated sulfuric acid is 6-8% of the sum of the dodecyl methyl dimethoxy silane, the dimethyl dichloro silane and the 1, 3-tetramethyl disiloxane, the molar ratio of the intermediate 2 to the intermediate 3 is n, 3n+1, n is a natural number larger than 0, and the dosage of the chloroplatinic acid is 0.3-0.5 per mill of the mass of the intermediate 2 to the intermediate 3.
5. The method for preparing the weather-resistant epoxy-based structural adhesive according to claim 1, which is characterized in that: the dosage ratio of 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-ketone, sodium hydroxide, deionized water and bromoethylene in the step A3 is 2mmol:3mmol:2mL:3mmol, the molar ratio of the intermediate 4 to Si-H bond on the hyperbranched silicone oil is 1:1, and the dosage of the Kasite catalyst is 0.3-0.5 per mill of the mass of the intermediate 4 and the hyperbranched silicone oil.
6. The method for preparing the weather-resistant epoxy-based structural adhesive according to claim 1, which is characterized in that: the dosage ratio of 2, 6-di-tert-butylphenol, potassium hydroxide and methyl acrylate in the step B1 is 24g:0.9g:15mL, and the dosage ratio of the intermediate 5, ethanol and sodium hydroxide solution is 6g:10mL:11mL.
7. The method for preparing the weather-resistant epoxy-based structural adhesive according to claim 1, which is characterized in that: the dosage ratio of the intermediate 6 to the thionyl chloride in the step B2 is 5g to 12mL, the molar ratio of the substrate to the diethanolamine to the lysine is 1:1:2.1, and the dosage of the p-toluenesulfonic acid is 3-5% of the mass of the substrate to the diethanolamine to the lysine.
8. A weather-resistant epoxy-based structural adhesive is characterized in that: the preparation method according to any one of claims 1 to 7.
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| CN114752038A (en) * | 2022-03-16 | 2022-07-15 | 黄山天马新材料科技有限公司 | Halogen-free flame-retardant epoxy resin and preparation method thereof |
| CN115558237A (en) * | 2022-09-16 | 2023-01-03 | 深圳新红进科技有限公司 | Epoxy-based insulating heat-conducting composite material and preparation method thereof |
| CN115558240A (en) * | 2022-10-08 | 2023-01-03 | 深圳新红进科技有限公司 | High-heat-resistance composite epoxy resin and preparation method thereof |
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