CN116445118B - Adhesive with low-temperature toughness and preparation method thereof - Google Patents
Adhesive with low-temperature toughness and preparation method thereof Download PDFInfo
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- CN116445118B CN116445118B CN202310720252.0A CN202310720252A CN116445118B CN 116445118 B CN116445118 B CN 116445118B CN 202310720252 A CN202310720252 A CN 202310720252A CN 116445118 B CN116445118 B CN 116445118B
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- 239000000853 adhesive Substances 0.000 title claims abstract description 39
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 31
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 26
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 16
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims abstract description 12
- CYCBPQPFMHUATH-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)butan-1-ol Chemical compound OCCCCOCC1CO1 CYCBPQPFMHUATH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000009261 D 400 Substances 0.000 claims abstract description 12
- 229960001124 trientine Drugs 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- -1 polysiloxane Polymers 0.000 claims description 42
- 229920001296 polysiloxane Polymers 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 36
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- RGZHEOWNTDJLAQ-UHFFFAOYSA-N 3,4,5-trihydroxybenzaldehyde Chemical compound OC1=CC(C=O)=CC(O)=C1O RGZHEOWNTDJLAQ-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 235000010980 cellulose Nutrition 0.000 claims description 17
- 229920002678 cellulose Polymers 0.000 claims description 17
- 239000001913 cellulose Substances 0.000 claims description 17
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 16
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 16
- 239000001116 FEMA 4028 Substances 0.000 claims description 12
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 12
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 12
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 12
- 229960004853 betadex Drugs 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 12
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 12
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 12
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 11
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-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 9
- 125000003277 amino group Chemical group 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 125000004402 polyphenol group Chemical group 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 229920006332 epoxy adhesive Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 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 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010964 304L stainless steel Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000008442 polyphenolic compounds Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The application discloses an adhesive with low-temperature toughness and a preparation method thereof, and relates to the technical field of adhesive preparation, wherein the adhesive comprises the following raw materials in parts by weight: 70-90 parts of modified epoxy resin, 30-35 parts of modified filler, 1-3 parts of 1, 4-butanediol glycidyl ether, 40-50 parts of polyether amine D-400 and 10-15 parts of triethylene tetramine; the modified epoxy resin is of a hyperbranched structure, the molecular chain contains cyclodextrin cavities, the cyclodextrin has a stable annular structure, so that the mechanical property is enhanced, when the adhesive is acted by external force, the cavities can compress and rebound, so that the toughness of the adhesive is further enhanced, meanwhile, the existence of the cavities can reduce the crosslinking density of the epoxy resin, so that the inter-molecular distance is increased, the segment movement capability is enhanced, and the adhesive is matched with a silica segment, so that the adhesive still has good toughness in a low-temperature environment; the side chain contains a large amount of polyphenol structures, so that the adhesiveness of the adhesive is greatly improved.
Description
Technical Field
The application relates to the technical field of adhesive preparation, in particular to an adhesive with low-temperature toughness and a preparation method thereof.
Background
The molecular structure of the epoxy resin contains more than or equal to 2 epoxy groups, and most commonly is a polycondensation product of epichlorohydrin and bisphenol A or polyalcohol. The epoxy group has certain chemical reactivity, and the compound containing active hydrogen can open the ring and generate solidification and cross-linking to generate macromolecules with three-dimensional network structure, so that the product is insoluble and not molten, has excellent adhesion, thermal stability and good chemical corrosion resistance, is used as a resin matrix of adhesives, coatings, composite materials and the like, and is widely applied to the fields of ships, automobile machinery, civil construction, transportation, sports goods, electronic appliances, aerospace and the like. The epoxy adhesive is a general term of an adhesive taking epoxy resin as a matrix, is called epoxy adhesive for short, has good bonding performance with various materials (such as metal, ceramic, glass, cement, wood, polar plastic and the like), has the advantages of high mechanical property, low curing shrinkage, good dimensional stability, excellent chemical medium resistance, high bonding strength, easy modification, wide application range and the like, and has the advantages of simple and convenient construction process, high work efficiency, low energy consumption, low cost, obvious labor intensity reduction, labor cost saving, wide application prospect, and the brittleness of the epoxy adhesive at the present stage is large, the cracking phenomenon can occur when the epoxy adhesive is used in a low-temperature environment, and the application range is seriously influenced.
Disclosure of Invention
The application aims to provide an adhesive with low-temperature toughness and a preparation method thereof, which solve the problems that the epoxy adhesive in the prior art has large brittleness and the mechanical property is greatly reduced in a low-temperature environment.
The aim of the application can be achieved by the following technical scheme:
the preparation method of the adhesive with low-temperature toughness specifically comprises the following steps:
step S1: weighing the following raw materials in parts by weight: 70-90 parts of modified epoxy resin, 30-35 parts of modified filler, 1-3 parts of 1, 4-butanediol glycidyl ether, 40-50 parts of polyether amine D-400 and 10-15 parts of triethylene tetramine;
step S2: mixing the modified epoxy resin, the modified filler and the 1, 4-butanediol glycidyl ether, and stirring for 1-1.5h under the condition that the rotating speed is 60-120r/min and the vacuum degree is-0.1 MPa to obtain a component A;
step S3: mixing polyetheramine D-400 and triethylene tetramine, and stirring for 30-40min under the condition that the rotating speed is 60-120r/min and the vacuum degree is-0.1 MPa to obtain a component B;
step S4: and uniformly mixing the component A and the component B to obtain the adhesive with low-temperature toughness.
Further, the modified epoxy resin is prepared by the following steps:
step A1: mixing Y-aminopropyl methyl diethoxy silane, diphenyl dichlorosilane and deionized water, stirring at the rotating speed of 200-300r/min and the temperature of 40-50 ℃ for 10-15min, adding concentrated sulfuric acid, heating to 60-70 ℃, adding 1, 3-tetramethyl disiloxane, and reacting for 3-5h to obtain an intermediate 1;
step A2: mixing beta-cyclodextrin and sodium hydroxide solution, stirring and adding an acrylic acid chloride aqueous solution at the rotating speed of 150-200r/min and the temperature of 60-80 ℃, reacting for 6-8 hours, adjusting the pH value to be neutral, precipitating with ethanol to obtain modified cyclodextrin, uniformly mixing the intermediate 1, the modified cyclodextrin and DMF, stirring and adding chloroplatinic acid at the rotating speed of 200-300r/min and the temperature of 60-70 ℃, and reacting for 4-6 hours to obtain hyperbranched polysiloxane;
step A3: uniformly mixing 3,4, 5-trihydroxybenzaldehyde, hyperbranched polysiloxane, DCC and dimethylbenzene, reacting for 4-6 hours at the rotation speed of 150-200r/min and the temperature of 40-45 ℃ to obtain modified polysiloxane, uniformly mixing the modified polysiloxane, allyl alcohol glycidyl ether and DMF, stirring at the rotation speed of 200-300r/min and the temperature of 60-70 ℃ and adding chloroplatinic acid, and reacting for 6-8 hours to obtain the modified epoxy resin.
Further, the dosage ratio of the Y-aminopropyl methyl diethoxy silane, the diphenyl dichlorosilane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A1 is 5mmol:8mmol:20mL:3mmol, and the concentrated sulfuric acid is 10% of the sum of the mass of the Y-aminopropyl methyl diethoxy silane, the diphenyl dichlorosilane and the 1, 3-tetramethyl disiloxane.
Further, the mol ratio of the beta-cyclodextrin to the sodium hydroxide to the acrylic acid chloride in the step A2 is 1:7.5:18.5, the mol ratio of the intermediate 1 to the modified cyclodextrin is 6n+1:n, n is a natural number larger than 0, and the concentration of chloroplatinic acid in the mixed solution of the intermediate 1 and the modified cyclodextrin is 10-15ppm.
Further, the molar ratio of 3,4, 5-trihydroxybenzaldehyde to amino groups on hyperbranched polysiloxane to DCC in the step A3 is 1:1:1.2, the molar ratio of Si-H bonds on the modified polysiloxane to allyl alcohol glycidyl ether is 1:1, and the concentration of chloroplatinic acid in the mixed solution of the modified polysiloxane and allyl alcohol glycidyl ether is 10-15ppm.
Further, the modified filler is prepared by the following steps:
step B1: uniformly mixing microcrystalline cellulose, 2, 6-tetramethylpiperidine oxide, sodium bromide and deionized water, stirring at the rotating speed of 200-300r/min and the temperature of 20-25 ℃, adding sodium hypochlorite, keeping the pH value of the reaction at 10, and reacting for 20-25 hours to obtain modified cellulose;
step B2: dispersing nano titanium dioxide in ethanol, adding deionized water, stirring at a rotating speed of 150-200r/min and a temperature of 40-50 ℃, adding KH550, reacting for 3-5h, adding modified cellulose and EDC, continuing to react for 8-10h, and filtering to remove filtrate to obtain the modified filler.
Further, the microcrystalline cellulose, 2, 6-tetramethylpiperidine oxide, sodium bromide and sodium hypochlorite described in step B1 were used in a 1g:0.1mmol:1mmol:5mmol ratio.
Further, the dosage ratio of nano titanium dioxide, KH550, modified cellulose and EDC in step B2 is 150g:3mol:100g:3.2mol.
An adhesive having low temperature toughness, prepared using any one of the preparation methods described above.
The application has the beneficial effects that: the adhesive with low-temperature toughness prepared by the application comprises the following raw materials: modified epoxy resin, modified filler, 1, 4-butanediol glycidyl ether, polyether amine D-400 and triethylene tetramine; the modified epoxy resin takes Y-aminopropyl methyl diethoxy silane and diphenyl dichlorosilane as raw materials for hydrolysis, and then is polymerized with 1, 3-tetramethyl disiloxane to form polysiloxane with Si-H bond end capping, thus preparing an intermediate 1; reacting beta-cyclodextrin with acrylic acid chloride to form modified cyclodextrin containing double bonds; reacting the modified cyclodextrin with the intermediate 1 to enable double bonds on the modified cyclodextrin to react with Si-H on the intermediate 1, and controlling the dosage to form Si-H terminated hyperbranched polysiloxane; under the action of DCC, 3,4, 5-trihydroxybenzaldehyde and hyperbranched polysiloxane are dehydrated and condensed to obtain modified polysiloxane; finally, capping the modified polysiloxane with allyl alcohol glycidyl ether, and finishing the reaction of Si-H bond to prepare modified epoxy resin; the modified filler takes microcrystalline cellulose as a raw material, and is treated by 2, 6-tetramethyl piperidine oxide and sodium hypochlorite to convert primary hydroxyl into carboxyl, so as to prepare modified cellulose; the nano titanium dioxide is subjected to surface treatment by KH550 to ensure that the surface contains active amino groups, and then is dehydrated and condensed with carboxyl groups on modified cellulose to prepare the modified filler. The modified epoxy resin is of a hyperbranched structure, the molecular chain contains cyclodextrin cavities, the cyclodextrin has a stable annular structure, so that the mechanical property is enhanced, when the adhesive is acted by external force, the cavities can compress and rebound, so that the toughness of the adhesive is further enhanced, meanwhile, the existence of the cavities can reduce the crosslinking density of the epoxy resin, so that the inter-molecular distance is increased, the segment movement capability is enhanced, and the adhesive is matched with a silica segment, so that the adhesive still has good toughness in a low-temperature environment; the addition of the reinforcing filler can form a core-shell structure with the modified epoxy resin molecules, so that the mechanical property is further improved; the side chain contains a large amount of polyphenol structures, so that the adhesiveness of the adhesive is greatly improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
The preparation method of the adhesive with low-temperature toughness specifically comprises the following steps:
step S1: weighing the following raw materials in parts by weight: 70 parts of modified epoxy resin, 30 parts of modified filler, 1 part of 1, 4-butanediol glycidyl ether, 40 parts of polyether amine D-400 and 10 parts of triethylene tetramine;
step S2: mixing the modified epoxy resin, the modified filler and the 1, 4-butanediol glycidyl ether, and stirring for 1h under the condition that the rotating speed is 60r/min and the vacuum degree is-0.1 MPa to obtain a component A;
step S3: mixing polyetheramine D-400 and triethylene tetramine, and stirring for 30min under the condition that the rotating speed is 60r/min and the vacuum degree is-0.1 MPa to obtain a component B;
step S4: and uniformly mixing the component A and the component B to obtain the adhesive with low-temperature toughness.
The modified epoxy resin is prepared by the following steps:
step A1: mixing Y-aminopropyl methyl diethoxy silane, diphenyl dichlorosilane and deionized water, stirring at a rotating speed of 200r/min and a temperature of 40 ℃ for 10min, adding concentrated sulfuric acid, heating to 60 ℃, adding 1, 3-tetramethyl disiloxane, and reacting for 3h to obtain an intermediate 1;
step A2: mixing beta-cyclodextrin and sodium hydroxide solution, stirring and adding an acryloyl chloride aqueous solution at the rotating speed of 150r/min and the temperature of 60 ℃, reacting for 6 hours, adjusting the pH value to be neutral, precipitating with ethanol to obtain modified cyclodextrin, uniformly mixing the intermediate 1, the modified cyclodextrin and DMF, stirring and adding chloroplatinic acid at the rotating speed of 200r/min and the temperature of 60 ℃, and reacting for 4 hours to obtain hyperbranched polysiloxane;
step A3: 3,4, 5-trihydroxybenzaldehyde, hyperbranched polysiloxane, DCC and dimethylbenzene are uniformly mixed, the reaction is carried out for 4 hours under the conditions of the rotating speed of 150r/min and the temperature of 40 ℃ to obtain modified polysiloxane, the modified polysiloxane, allyl alcohol glycidyl ether and DMF are uniformly mixed, and the mixture is stirred and added with chloroplatinic acid under the conditions of the rotating speed of 200r/min and the temperature of 60 ℃ to react for 6 hours to obtain the modified epoxy resin.
The dosage ratio of the Y-aminopropyl methyl diethoxy silane, the diphenyl dichlorosilane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A1 is 5mmol, 8mmol, 20mL, 3mmol, and the concentrated sulfuric acid is 10% of the sum of the mass of the Y-aminopropyl methyl diethoxy silane, the diphenyl dichlorosilane and the 1, 3-tetramethyl disiloxane.
The mol ratio of the beta-cyclodextrin to the sodium hydroxide to the acryloyl chloride in the step A2 is 1:7.5:18.5, the mol ratio of the intermediate 1 to the modified cyclodextrin is 7:1, and the concentration of chloroplatinic acid in the mixed solution of the intermediate 1 and the modified cyclodextrin is 10ppm.
The molar ratio of 3,4, 5-trihydroxybenzaldehyde to amino groups on hyperbranched polysiloxane to DCC in the step A3 is 1:1:1.2, the molar ratio of Si-H bonds on the modified polysiloxane to allyl alcohol glycidyl ether is 1:1, and the concentration of chloroplatinic acid in the mixed solution of the modified polysiloxane and allyl alcohol glycidyl ether is 10ppm.
The modified filler is prepared by the following steps:
step B1: uniformly mixing microcrystalline cellulose, 2, 6-tetramethylpiperidine oxide, sodium bromide and deionized water, stirring at a rotating speed of 200r/min and a temperature of 20 ℃, adding sodium hypochlorite, keeping a reaction pH value of 10, and reacting for 20 hours to obtain modified cellulose;
step B2: dispersing nano titanium dioxide in ethanol, adding deionized water, stirring at a rotating speed of 150r/min and a temperature of 40 ℃, adding KH550, reacting for 3 hours, adding modified cellulose and EDC, continuing to react for 8 hours, and filtering to remove filtrate to obtain the modified filler.
The microcrystalline cellulose, 2, 6-tetramethylpiperidine oxide, sodium bromide and sodium hypochlorite described in step B1 were used in a 1g:0.1mmol:1mmol:5mmol ratio.
The dosage ratio of nano titanium dioxide, KH550, modified cellulose and EDC in the step B2 is 150 g/3 mol/100 g/3.2 mol.
Example 2
The preparation method of the adhesive with low-temperature toughness specifically comprises the following steps:
step S1: weighing the following raw materials in parts by weight: 80 parts of modified epoxy resin, 33 parts of modified filler, 2 parts of 1, 4-butanediol glycidyl ether, 45 parts of polyether amine D-400 and 13 parts of triethylene tetramine;
step S2: mixing the modified epoxy resin, the modified filler and the 1, 4-butanediol glycidyl ether, and stirring for 1.5 hours under the condition that the rotating speed is 60r/min and the vacuum degree is-0.1 MPa to obtain a component A;
step S3: mixing polyetheramine D-400 and triethylene tetramine, and stirring for 35min under the condition that the rotating speed is 60r/min and the vacuum degree is-0.1 MPa to obtain a component B;
step S4: and uniformly mixing the component A and the component B to obtain the adhesive with low-temperature toughness.
The modified epoxy resin is prepared by the following steps:
step A1: mixing Y-aminopropyl methyl diethoxy silane, diphenyl dichlorosilane and deionized water, stirring at a rotating speed of 200r/min and a temperature of 45 ℃ for 15min, adding concentrated sulfuric acid, heating to 65 ℃, adding 1, 3-tetramethyl disiloxane, and reacting for 4h to obtain an intermediate 1;
step A2: mixing beta-cyclodextrin and sodium hydroxide solution, stirring and adding an acryloyl chloride aqueous solution at the rotating speed of 150r/min and the temperature of 70 ℃, reacting for 7 hours, adjusting the pH value to be neutral, precipitating with ethanol to obtain modified cyclodextrin, uniformly mixing the intermediate 1, the modified cyclodextrin and DMF, stirring and adding chloroplatinic acid at the rotating speed of 200r/min and the temperature of 65 ℃, and reacting for 5 hours to obtain hyperbranched polysiloxane;
step A3: 3,4, 5-trihydroxybenzaldehyde, hyperbranched polysiloxane, DCC and dimethylbenzene are uniformly mixed, the reaction is carried out for 5 hours under the conditions of the rotating speed of 150r/min and the temperature of 43 ℃ to obtain modified polysiloxane, the modified polysiloxane, allyl alcohol glycidyl ether and DMF are uniformly mixed, and chloroplatinic acid is added after stirring under the conditions of the rotating speed of 200r/min and the temperature of 65 ℃ to react for 7 hours to obtain the modified epoxy resin.
The dosage ratio of the Y-aminopropyl methyl diethoxy silane, the diphenyl dichlorosilane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A1 is 5mmol, 8mmol, 20mL, 3mmol, and the concentrated sulfuric acid is 10% of the sum of the mass of the Y-aminopropyl methyl diethoxy silane, the diphenyl dichlorosilane and the 1, 3-tetramethyl disiloxane.
The mol ratio of the beta-cyclodextrin to the sodium hydroxide to the acryloyl chloride in the step A2 is 1:7.5:18.5, the mol ratio of the intermediate 1 to the modified cyclodextrin is 13:2, and the concentration of chloroplatinic acid in the mixed solution of the intermediate 1 and the modified cyclodextrin is 13ppm.
The molar ratio of 3,4, 5-trihydroxybenzaldehyde to amino groups on hyperbranched polysiloxane to DCC in the step A3 is 1:1:1.2, the molar ratio of Si-H bonds on the modified polysiloxane to allyl alcohol glycidyl ether is 1:1, and the concentration of chloroplatinic acid in the mixed solution of the modified polysiloxane and allyl alcohol glycidyl ether is 13ppm.
The modified filler is prepared by the following steps:
step B1: uniformly mixing microcrystalline cellulose, 2, 6-tetramethylpiperidine oxide, sodium bromide and deionized water, stirring at a rotating speed of 200r/min and a temperature of 23 ℃, adding sodium hypochlorite, keeping a reaction pH value of 10, and reacting for 23 hours to obtain modified cellulose;
step B2: dispersing nano titanium dioxide in ethanol, adding deionized water, stirring at a rotation speed of 150r/min and a temperature of 45 ℃, adding KH550, reacting for 4 hours, adding modified cellulose and EDC, continuing to react for 9 hours, and filtering to remove filtrate to obtain the modified filler.
The microcrystalline cellulose, 2, 6-tetramethylpiperidine oxide, sodium bromide and sodium hypochlorite described in step B1 were used in a 1g:0.1mmol:1mmol:5mmol ratio.
The dosage ratio of nano titanium dioxide, KH550, modified cellulose and EDC in the step B2 is 150 g/3 mol/100 g/3.2 mol.
Example 3
The preparation method of the adhesive with low-temperature toughness specifically comprises the following steps:
step S1: weighing the following raw materials in parts by weight: 90 parts of modified epoxy resin, 35 parts of modified filler, 3 parts of 1, 4-butanediol glycidyl ether, 50 parts of polyether amine D-400 and 15 parts of triethylene tetramine;
step S2: mixing the modified epoxy resin, the modified filler and the 1, 4-butanediol glycidyl ether, and stirring for 1.5 hours under the condition that the rotating speed is 120r/min and the vacuum degree is-0.1 MPa to obtain a component A;
step S3: mixing polyetheramine D-400 and triethylene tetramine, and stirring for 40min under the condition that the rotating speed is 120r/min and the vacuum degree is-0.1 MPa to obtain a component B;
step S4: and uniformly mixing the component A and the component B to obtain the adhesive with low-temperature toughness.
The modified epoxy resin is prepared by the following steps:
step A1: mixing Y-aminopropyl methyl diethoxy silane, diphenyl dichlorosilane and deionized water, stirring at a rotating speed of 300r/min and a temperature of 50 ℃ for 15min, adding concentrated sulfuric acid, heating to 70 ℃, adding 1, 3-tetramethyl disiloxane, and reacting for 5h to obtain an intermediate 1;
step A2: mixing beta-cyclodextrin and sodium hydroxide solution, stirring and adding an acryloyl chloride aqueous solution at the rotating speed of 200r/min and the temperature of 80 ℃, reacting for 8 hours, adjusting the pH value to be neutral, precipitating with ethanol to obtain modified cyclodextrin, uniformly mixing the intermediate 1, the modified cyclodextrin and DMF, stirring and adding chloroplatinic acid at the rotating speed of 300r/min and the temperature of 70 ℃, and reacting for 6 hours to obtain hyperbranched polysiloxane;
step A3: 3,4, 5-trihydroxybenzaldehyde, hyperbranched polysiloxane, DCC and dimethylbenzene are uniformly mixed, the reaction is carried out for 6 hours under the conditions of 200r/min of rotating speed and 45 ℃ to obtain modified polysiloxane, the modified polysiloxane, allyl alcohol glycidyl ether and DMF are uniformly mixed, and chloroplatinic acid is stirred and added under the conditions of 300r/min of rotating speed and 70 ℃ to react for 8 hours to obtain the modified epoxy resin.
The dosage ratio of the Y-aminopropyl methyl diethoxy silane, the diphenyl dichlorosilane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A1 is 5mmol, 8mmol, 20mL, 3mmol, and the concentrated sulfuric acid is 10% of the sum of the mass of the Y-aminopropyl methyl diethoxy silane, the diphenyl dichlorosilane and the 1, 3-tetramethyl disiloxane.
The mol ratio of the beta-cyclodextrin to the sodium hydroxide to the acryloyl chloride in the step A2 is 1:7.5:18.5, the mol ratio of the intermediate 1 to the modified cyclodextrin is 19:3, and the concentration of chloroplatinic acid in the mixed solution of the intermediate 1 and the modified cyclodextrin is 15ppm.
The molar ratio of 3,4, 5-trihydroxybenzaldehyde to amino groups on hyperbranched polysiloxane to DCC in the step A3 is 1:1:1.2, the molar ratio of Si-H bonds on the modified polysiloxane to allyl alcohol glycidyl ether is 1:1, and the concentration of chloroplatinic acid in the mixed solution of the modified polysiloxane and allyl alcohol glycidyl ether is 15ppm.
The modified filler is prepared by the following steps:
step B1: uniformly mixing microcrystalline cellulose, 2, 6-tetramethylpiperidine oxide, sodium bromide and deionized water, stirring at a rotating speed of 300r/min and a temperature of 25 ℃, adding sodium hypochlorite, keeping a reaction pH value of 10, and reacting for 25 hours to obtain modified cellulose;
step B2: dispersing nano titanium dioxide in ethanol, adding deionized water, stirring at a rotating speed of 200r/min and a temperature of 50 ℃, adding KH550, reacting for 5 hours, adding modified cellulose and EDC, continuing to react for 10 hours, and filtering to remove filtrate to obtain the modified filler.
The microcrystalline cellulose, 2, 6-tetramethylpiperidine oxide, sodium bromide and sodium hypochlorite described in step B1 were used in a 1g:0.1mmol:1mmol:5mmol ratio.
The dosage ratio of nano titanium dioxide, KH550, modified cellulose and EDC in the step B2 is 150 g/3 mol/100 g/3.2 mol.
Comparative example 1
This comparative example uses starch instead of beta-cyclodextrin as compared to example 1, the rest of the procedure being the same.
Comparative example 2
In this comparative example, intermediate 1 replaces the hyperbranched polysiloxane as compared to example 1, with the remainder of the procedure being the same.
Comparative example 3
This comparative example uses nano titanium dioxide instead of modified filler in comparison with example 1, the rest of the procedure being the same.
Comparative example 4
In this comparative example, microcrystalline cellulose was used instead of the modified filler as in example 1, and the rest of the procedure was the same.
The adhesives prepared in examples 1-3 and comparative examples 1-4 were prepared into 2 dumbbell-shaped bars according to the standard of ASTM D638-08, with dimensions of 75mm 4mm 2mm, a tensile rate of 5mm/min, a test temperature of-25℃and, according to the standard of GB/T7124-2008, a 304L stainless steel plate was used as a base material of lap shear strength, dimensions of 100mm 25mm 2mm, a bonding thickness of 0.5mm, a loading rate of 10mm/min, a test temperature of-25℃and the test results were shown in Table 1.
TABLE 1 results of Performance measurements for examples 1-3 and comparative examples 1-4
As can be seen from Table 1, the application has excellent tensile strength and low temperature resistance.
The foregoing is merely illustrative and explanatory of the principles of the application, 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 application or beyond the scope of the appended claims.
Claims (7)
1. A method for preparing an adhesive with low-temperature toughness, which is characterized by comprising the following steps: the method specifically comprises the following steps:
step S1: weighing the following raw materials in parts by weight: 70-90 parts of modified epoxy resin, 30-35 parts of modified filler, 1-3 parts of 1, 4-butanediol glycidyl ether, 40-50 parts of polyether amine D-400 and 10-15 parts of triethylene tetramine;
step S2: uniformly mixing modified epoxy resin, modified filler and 1, 4-butanediol glycidyl ether to prepare a component A;
step S3: uniformly mixing polyether amine D-400 and triethylene tetramine to prepare a component B;
step S4: uniformly mixing the component A and the component B to prepare an adhesive with low-temperature toughness;
the modified epoxy resin is prepared by the following steps:
step A1: mixing and stirring Y-aminopropyl methyl diethoxy silane, diphenyl dichlorosilane and deionized water, adding concentrated sulfuric acid, heating, adding 1, 3-tetramethyl disiloxane, and reacting to obtain an intermediate 1;
step A2: mixing and stirring beta-cyclodextrin and sodium hydroxide solution, adding an acrylic chloride aqueous solution, reacting, adjusting pH to be neutral, precipitating with ethanol to obtain modified cyclodextrin, mixing and stirring intermediate 1, modified cyclodextrin and DMF, adding chloroplatinic acid, and reacting to obtain hyperbranched polysiloxane;
step A3: mixing 3,4, 5-trihydroxybenzaldehyde, hyperbranched polysiloxane, DCC and xylene for reaction to obtain modified polysiloxane, mixing and stirring the modified polysiloxane, allyl alcohol glycidyl ether and DMF, adding chloroplatinic acid, and reacting to obtain modified epoxy resin;
the modified filler is prepared by the following steps:
step B1: mixing microcrystalline cellulose, 2, 6-tetramethyl piperidine oxide, sodium bromide and deionized water, stirring, adding sodium hypochlorite, keeping the pH value of the reaction at 10, and reacting to obtain modified cellulose;
step B2: dispersing nano titanium dioxide in ethanol, adding deionized water, stirring, adding KH550, reacting, adding modified cellulose and EDC, continuing the reaction, and filtering to remove filtrate to obtain the modified filler.
2. The method for preparing an adhesive with low temperature toughness according to claim 1, wherein: the dosage ratio of the Y-aminopropyl methyl diethoxy silane, the diphenyl dichlorosilane, the deionized water and the 1, 3-tetramethyl disiloxane in the step A1 is 5mmol, 8mmol, 20mL, 3mmol, and the concentrated sulfuric acid is 10% of the sum of the mass of the Y-aminopropyl methyl diethoxy silane, the diphenyl dichlorosilane and the 1, 3-tetramethyl disiloxane.
3. The method for preparing an adhesive with low temperature toughness according to claim 1, wherein: the mol ratio of the beta-cyclodextrin to the sodium hydroxide to the acrylic acid chloride in the step A2 is 1:7.5:18.5, the mol ratio of the intermediate 1 to the modified cyclodextrin is 6n+1:n, n is a natural number larger than 0, and the concentration of chloroplatinic acid in the mixed solution of the intermediate 1 and the modified cyclodextrin is 10-15ppm.
4. The method for preparing an adhesive with low temperature toughness according to claim 1, wherein: the molar ratio of 3,4, 5-trihydroxybenzaldehyde to amino groups on hyperbranched polysiloxane to DCC in the step A3 is 1:1:1.2, the molar ratio of Si-H bonds on the modified polysiloxane to allyl alcohol glycidyl ether is 1:1, and the concentration of chloroplatinic acid in the mixed solution of the modified polysiloxane and allyl alcohol glycidyl ether is 10-15ppm.
5. The method for preparing an adhesive with low temperature toughness according to claim 1, wherein: the microcrystalline cellulose, 2, 6-tetramethylpiperidine oxide, sodium bromide and sodium hypochlorite described in step B1 were used in a 1g:0.1mmol:1mmol:5mmol ratio.
6. The method for preparing an adhesive with low temperature toughness according to claim 1, wherein: the dosage ratio of nano titanium dioxide, KH550, modified cellulose and EDC in the step B2 is 150 g/3 mol/100 g/3.2 mol.
7. An adhesive having low temperature toughness, characterized by: prepared using the preparation method according to any one of claims 1 to 6.
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| CN108003824A (en) * | 2017-12-06 | 2018-05-08 | 成都精湛科技有限公司 | A kind of reinforcing steel bonding glue of low temperature resistant toughness reinforcing and preparation method thereof |
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| CN105062396A (en) * | 2015-08-21 | 2015-11-18 | 卡本复合材料（天津）有限公司 | Double-component high-strength building epoxy structural adhesive and preparing method thereof |
| CN108003824A (en) * | 2017-12-06 | 2018-05-08 | 成都精湛科技有限公司 | A kind of reinforcing steel bonding glue of low temperature resistant toughness reinforcing and preparation method thereof |
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