CN117025149B - Aldehyde-free adhesive for non-stick steel plate and preparation method thereof - Google Patents
Aldehyde-free adhesive for non-stick steel plate and preparation method thereof Download PDFInfo
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- 239000000853 adhesive Substances 0.000 title claims abstract description 36
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 36
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 24
- 239000010959 steel Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 37
- 239000011258 core-shell material Substances 0.000 claims abstract description 34
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 26
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000013530 defoamer Substances 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 239000003085 diluting agent Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 75
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 72
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 60
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 59
- 239000011259 mixed solution Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 239000013207 UiO-66 Substances 0.000 claims description 48
- 239000000843 powder Substances 0.000 claims description 47
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 21
- 229940125904 compound 1 Drugs 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 20
- 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 20
- 238000005406 washing Methods 0.000 claims description 20
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 16
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 16
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 13
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- YMFOWIJFFPALOW-UHFFFAOYSA-N 2-(methylamino)propane-1,3-diol Chemical compound CNC(CO)CO YMFOWIJFFPALOW-UHFFFAOYSA-N 0.000 claims description 11
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 11
- OHLSHRJUBRUKAN-UHFFFAOYSA-N 2,3-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1O OHLSHRJUBRUKAN-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 claims description 10
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 10
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 8
- 238000010025 steaming Methods 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010335 hydrothermal treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 7
- 229960001701 chloroform Drugs 0.000 claims 6
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 18
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 239000000945 filler Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 description 17
- 229920000647 polyepoxide Polymers 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 6
- HLXIDAJQKLNFQS-UHFFFAOYSA-N [chloro-bis(hydroxymethyl)silyl]methanol Chemical compound C(O)[Si](Cl)(CO)CO HLXIDAJQKLNFQS-UHFFFAOYSA-N 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 6
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000010125 resin casting Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- C09J11/08—Macromolecular additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses an aldehyde-free adhesive for a non-stick steel plate and a preparation method thereof. The formaldehyde-free adhesive is prepared from the following raw materials in parts by weight: 60-80 parts of bisphenol A epoxy resin, 2-6 parts of antioxidant, 15-25 parts of core-shell nano particles, 3-10 parts of diluent, 2-6 parts of defoamer, 6-8 parts of amine curing agent and 4-7 parts of curing accelerator. The adhesive prepared by the invention takes bisphenol A epoxy resin as a matrix, and the hyperbranched polymer is grafted on the surface of the rigid organic metal frame through modification treatment of the filler to form core-shell nanoparticles, so that the compatibility of the nanoparticles and the matrix can be improved, the interfacial adhesion force can be improved, the brittleness of the matrix can be improved, and the toughness and mechanical properties of the matrix can be improved.
Description
Technical Field
The invention relates to the technical field of adhesive preparation, in particular to an aldehyde-free adhesive for a non-stick steel plate and a preparation method thereof.
Background
The adhesive prepared by taking the epoxy resin as a matrix is widely applied to the fields of aviation, aerospace, electronic devices, machinery, buildings, vehicles and daily life of people, wherein the adhesive bonded with steel is called as steel adhesive, is widely applied to the fields of buildings, bridges, machinery and the like, and becomes one of important components in modern buildings and engineering. The epoxy resin adhesive has the advantages of strong binding power, high mechanical strength, good chemical stability, good insulating property, small curing shrinkage, strong adaptability, good oxidation resistance, no volatile organic matters and the like, but because the epoxy resin contains a plurality of benzene ring structures or heterocyclic rings, the flexibility of molecular chains is small, and the toughness of the cured crosslinked structure is poor, the flexibility requirement of specific industries can not be met, so that the adhesive with high tensile strength, high elongation at break, strong binding property and environmental protection needs to be developed.
At present, modification of the epoxy resin adhesive mainly comprises modification of adding elastic liquid crystal rubber, toughening of introducing a 'soft segment', modification of adding nano filler and the like, but the modification modes have respective problems, for example, the modification of adding the elastic liquid crystal rubber and the toughening modification of introducing the 'soft segment' can greatly reduce the elastic modulus and the glass transition temperature of a curing system; the added nano filler is modified, and the defect of poor dispersibility of the nano filler and poor performance of a curing system exists. Therefore, in order to overcome the disadvantages of the above modification methods, a method for improving the disadvantages of the epoxy resin while retaining the advantages of the epoxy resin itself is required.
Disclosure of Invention
In order to solve the technical problems, the invention provides an aldehyde-free adhesive for a non-stick steel plate and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
an aldehyde-free adhesive for a non-stick steel plate comprises the following raw materials in parts by weight: 60-80 parts of bisphenol A epoxy resin, 2-6 parts of antioxidant, 15-25 parts of core-shell nano particles, 3-10 parts of diluent, 2-6 parts of defoamer, 6-8 parts of amine curing agent and 4-7 parts of curing accelerator;
the core-shell nanoparticle is prepared by the following steps:
step A1, adding tris (hydroxymethyl) aminomethane into a mixed solution of chloroform and acetonitrile, stirring and mixing uniformly, adding trimethylchlorosilane at room temperature, refluxing for 2 hours, cooling to 0 ℃, adding triethylamine and trityl chloride dissolved in chloroform into a reactor, stirring the obtained mixture for 1 hour, adding methanol, concentrating, extracting and drying to obtain a compound 1;
in the step A1, an amino group in the trimethylol aminomethane is protected by introducing a trityl protecting group, and deprotection is carried out in a subsequent experiment to realize ring-opening reaction of the amino group and the epoxy group, so that a hyperbranched polymer is grafted on the surface of an organic metal frame to obtain a nano filler with a core-shell structure, and the toughness of a matrix is improved;
further, in the step A1, the usage ratio of the mixed solution of the tris (hydroxymethyl) aminomethane, the trimethylchlorosilane, the chloroform and the acetonitrile, the triethylamine, the trityl chloride, the chloroform and the methanol is 0.01mol:0.01mol:18-20mL:0.02-0.03mol:0.01 to 0.025mol:10mL: the volume ratio of the chloroform to the acetonitrile in the mixed solution of 2mL of the chloroform to the acetonitrile is 5:1.
step A2, adding 2- (methylamino) propane-1, 3-diol into a flask containing methanol, stirring and mixing uniformly under the condition of nitrogen, then dropwise adding ethyl acrylate while stirring, heating to 35 ℃ after the dropwise adding is finished, reacting for 4-5h, transferring to a vacuum rotary evaporator to remove methanol and excessive ethyl acrylate after the reaction is finished, and obtaining a hydroxyl-terminated monomer, wherein the structural formula is as follows:
the secondary amine in the 2- (methylamino) propane-1, 3-diol and the double bond in the ethyl acrylate are connected through Michael addition reaction in the step A2 to prepare a hydroxyl-terminated monomer;
further, the ratio of the amount of 2- (methylamino) propane-1, 3-diol, ethyl acrylate and methanol was 1mol:1.5-2.5mol:100mL.
Step A3, placing the compound 1 and the p-toluenesulfonic acid into a reactor, uniformly mixing, heating to 110 ℃, slowly dropwise adding hydroxyl-terminated monomers, keeping the temperature at 120 ℃ for reaction for 4 hours, after the reaction is finished, reducing the temperature to 60 ℃, adding boron trifluoride diethyl ether complex, dropwise adding epoxy chloropropane, reacting for 2 hours, distilling under reduced pressure to remove excessive epoxy chloropropane, adding sodium hydroxide solution into the reactant, heating to 80 ℃ for reaction for 3 hours, after the reaction is finished, steaming for 1 hour at 100 ℃, cooling to 30 ℃, and adding 40mL acetic acid solution for reflux for 10 minutes to obtain the hyperbranched polymer;
the hyperbranched polymer in the step A3 contains high-density epoxy-terminated functional groups in the molecular structure, so that the compatibility of the hyperbranched polymer molecules and epoxy resin can be improved; the formed network structure contains a large amount of free space, so that the impact energy can be absorbed when the epoxy resin is impacted, and the toughness of the resin is improved; the nano particles grafted by the hyperbranched molecules have a unique spherical structure, can be stretched during the curing reaction, and reduce the curing shrinkage of the epoxy resin; in addition, the amino protecting group Trt is removed after the amino protecting group Trt is refluxed in an acetic acid solution for a plurality of minutes, so that the amino can be combined with the MOF structure in subsequent experiments to form core-shell nano particles, and the toughness of the epoxy resin is improved;
further, the compound 1, the hydroxyl-terminated monomer, epichlorohydrin, sodium hydroxide solution and boron trifluoride diethyl etherate were used in an amount ratio of 0.1mol:0.3-2.1mol:3-6mol:2-4mol:0.002-0.01mol, the dosage of the p-toluenesulfonic acid is 2% of the sum of the mass of the compound 1 and the mass of the hydroxyl-terminated monomer, and the mass ratio of acetic acid to deionized water in the acetic acid solution is 1:1, the mass fraction of the sodium hydroxide solution is 25%.
Step A4, dispersing 1, 4-terephthalic acid in the mixed solution 1, stirring uniformly, adding zirconium tetrachloride, carrying out ultrasonic treatment for 30min, transferring the mixed solution into an autoclave, carrying out hydrothermal treatment at 120 ℃ for 12h, cooling to room temperature after the reaction is finished, centrifuging, washing, drying at 60 ℃ for 12h to obtain UiO-66 powder, dispersing 2, 3-dihydroxyterephthalic acid in the mixed solution 2, adding UiO-66 powder, heating to 85 ℃, stirring for 48h, centrifuging and washing after the reaction is finished, and drying at 60 ℃ for 12h to obtain hydroxylated UiO-66 powder;
wherein the mixed solution 1 is a mixed solution of N, N-dimethylformamide and acetic acid, and the mixed solution 2 is a mixed solution of N, N-dimethylformamide and water.
In the step A4, a rigid metal-organic framework structure with hydroxyl groups on the surface is synthesized, the rigid metal-organic framework structure has excellent hydrothermal stability and chemical stability, a crystal structure can be kept stable at 500 ℃, the framework structure has excellent compressive strength, the framework structure is used as a core structure in core-shell nano particles, hyperbranched polymers are grafted on the surface of the framework structure, the mechanical property and fracture toughness of a system can be effectively improved, and in addition, the hydroxylated UiO-66 has the rigid metal-organic framework structure, so that the fragment of epoxy resin matrix molecules can be prevented from moving, and the glass transition temperature of a matrix is further improved;
further, the dosage ratio of the 1, 4-terephthalic acid, the mixed solution 1 and the zirconium tetrachloride is 1-2g:1g:3-5g of the total weight of the powder,
the dosage ratio of the UiO-66 powder, the 2, 3-dihydroxyterephthalic acid and the mixed solution 2 is 2-3g:0.5-5g:20mL of the solution, in which the concentration of the active component is 20,
the dosage ratio of N, N-dimethylformamide to acetic acid in the mixed solution 1 is 15mL:4mL, the dosage ratio of N, N-dimethylformamide to water in the mixed solution 2 is 2mL:1mL.
Step A5, adding hydroxylated UiO-66 powder into a reactor containing toluene, carrying out ultrasonic treatment for 30min, then adding gamma- (2, 3-glycidoxy) propyl trimethoxy silane, heating to 80 ℃ and stirring for 24h, centrifuging and washing after the reaction is finished, and drying at 60 ℃ for 12h to obtain epoxidized UiO-66 powder;
further, the ratio of the amount of hydroxylated UiO-66 powder, toluene and gamma- (2, 3-glycidoxy) propyltrimethoxysilane was 2g:16mL:1g.
Step A6, placing the epoxidized UiO-66 powder into a reactor containing dichloromethane, adding sodium hydroxide, stirring and mixing uniformly, adding hyperbranched polymer, stirring for 3-6 hours at room temperature, centrifuging and washing after the reaction is finished, and drying for 6 hours at 80 ℃ to obtain core-shell nanoparticles;
in the step A6, the hyperbranched polymer is grafted on the surface of the UiO-66 through ring-opening reaction between amino groups, so that the surface of the hyperbranched polymer contains a large number of epoxy groups, and when the core-shell nano particles are blended with epoxy resin, the epoxy groups in the shell structure can improve the compatibility between the core-shell nano particles and the epoxy resin matrix, improve the interfacial adhesion force and fully distribute the core-shell nano particles in the resin matrix, thereby achieving the purpose of toughening; in addition, the epoxy groups on the surfaces of the core-shell nanoparticles can carry out a crosslinking reaction with amino groups in the curing agent, so that the core-shell nanoparticles can enter a network structure of the curing body, the network node function is exerted, and the tensile property of the curing body is improved;
further, the dosage ratio of the epoxidized UiO-66 powder, the hyperbranched polymer, the sodium hydroxide and the methylene dichloride is 1 to 3g:2-6g:0.1g:40mL.
The preparation method of the formaldehyde-free adhesive for the non-stick steel plate comprises the following steps:
step S1, weighing raw materials according to parts by weight, adding bisphenol A epoxy resin and core-shell nano particles into a reactor, stirring for 2-4 hours at 80-100 ℃ to uniformly mix the materials, cooling to 50 ℃, adding a diluent and a defoaming agent into the reactor, continuously stirring for 30 minutes, and then performing vacuum defoaming for 10-20 minutes to obtain a premix 1;
s2, placing an amine curing agent, an antioxidant and a curing accelerator in a reactor, and stirring for 1h at 50-60 ℃ to uniformly mix the materials to obtain a premix 2;
and step S3, adding the premix 1 and the premix 2 into a reactor, uniformly mixing, pouring the mixture into a device by a machine, and curing the mixture for 24 hours at 25 ℃ to obtain the formaldehyde-free adhesive.
The invention has the beneficial effects that:
according to the formaldehyde-free adhesive for the non-stick steel plate and the preparation method thereof, bisphenol A epoxy resin is used as a matrix, the filler is modified, and hyperbranched polymer is grafted on the surface of the rigid organic metal frame to form core-shell nano particles, so that the compatibility of the nano particles and the matrix can be improved, the interfacial adhesion can be improved, the brittleness of the matrix can be improved, the toughness and the mechanical property of the matrix can be improved, and in addition, no volatile organic matters such as formaldehyde and the like are released in the process, so that the formaldehyde-free adhesive has environmental protection.
The hyperbranched polymer prepared by the invention contains high-density epoxy-terminated functional groups in the molecular structure, so that the compatibility of hyperbranched polymer molecules and epoxy resin can be improved, the interfacial adhesion between particles and a matrix can be improved, and core-shell nano particles can be fully distributed in the resin matrix, thereby achieving the purpose of toughening; the formed network structure contains a large amount of free space, so that the impact energy can be absorbed when the epoxy resin is impacted, and the toughness of the resin is improved; the nano particles grafted by the hyperbranched molecules have a unique spherical structure, can be stretched during the curing reaction, and reduce the curing shrinkage of the epoxy resin; in addition, the epoxy groups can generate a crosslinking reaction with amino groups in the curing agent, so that core-shell nano particles can enter a network structure of the curing body, the network node function is exerted, and the tensile property of the curing body is improved.
According to the invention, the rigid metal-organic framework structure with the surface containing hydroxyl is taken as a core, and the hyperbranched polymer is grafted on the surface of the rigid metal-organic framework structure, so that the mechanical property and fracture toughness of the system can be effectively improved, and the framework structure has excellent compressive strength, and in addition, the framework structure can prevent fragments of epoxy resin matrix molecules from moving, so that the glass transition temperature of the matrix is 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 core-shell nanoparticle is prepared by the following steps:
step A1, adding trimethylol aminomethane into a mixed solution of chloroform and acetonitrile, stirring and mixing uniformly, adding trimethylol chlorosilane into the mixed solution at room temperature, refluxing for 2 hours, cooling to 0 ℃, adding triethylamine and trityl chloride dissolved in chloroform into a reactor, stirring the obtained mixture for 1 hour, adding methanol, concentrating, extracting and drying to obtain a compound 1, wherein the dosage ratio of trimethylol aminomethane, the mixed solution of trimethylol chlorosilane, chloroform and acetonitrile, triethylamine, trityl chloride, chloroform and methanol is 0.01mol:0.01mol:18mL:0.02mol:0.01mol:10mL: the volume ratio of the chloroform to the acetonitrile in the mixed solution of 2mL of the chloroform to the acetonitrile is 5:1, a step of;
step A2, adding 2- (methylamino) propane-1, 3-diol into a flask containing methanol, stirring and mixing uniformly at room temperature under the condition of introducing nitrogen, then dropwise adding ethyl acrylate while stirring, heating to 35 ℃ after the dropwise adding is finished, reacting for 4 hours, transferring to a vacuum rotary evaporator to remove methanol and excessive ethyl acrylate after the reaction is finished, and obtaining a hydroxyl-terminated monomer, wherein the dosage ratio of 2- (methylamino) propane-1, 3-diol, ethyl acrylate and methanol is 1mol:1.5mol:100mL;
step A3, placing the compound 1 and the p-toluenesulfonic acid into a reactor, uniformly mixing, heating to 110 ℃, slowly dropwise adding hydroxyl-terminated monomers, keeping the temperature at 120 ℃ for reaction for 4 hours, after the reaction is finished, reducing the temperature to 60 ℃, adding boron trifluoride diethyl ether complex, dropwise adding epoxy chloropropane, reacting for 2 hours, distilling under reduced pressure to remove excessive epoxy chloropropane, adding sodium hydroxide solution into the reactant, heating to 80 ℃ for reaction for 3 hours, after the reaction is finished, steaming for 1 hour at 100 ℃, cooling to 30 ℃, adding 40mL of acetic acid solution, refluxing for 10 minutes, and obtaining the hyperbranched polymer, wherein the dosage ratio of the compound 1, the hydroxyl-terminated monomers, the epoxy chloropropane, the sodium hydroxide solution and the boron trifluoride diethyl ether complex is 0.1mol:0.3mol:3mol:2mol:0.002mol, the dosage of the p-toluenesulfonic acid is 2% of the sum of the mass of the compound 1 and the mass of the hydroxyl-terminated monomer, and the mass ratio of acetic acid to deionized water in the acetic acid solution is 1:1, 25% of sodium hydroxide solution by mass;
step A4, dispersing 1, 4-terephthalic acid in the mixed solution 1, stirring uniformly, adding zirconium tetrachloride, carrying out ultrasonic treatment for 30min, transferring the mixed solution into an autoclave, carrying out hydrothermal treatment at 120 ℃ for 12h, cooling to room temperature after the reaction is finished, centrifuging, washing, drying at 60 ℃ for 12h to obtain UiO-66 powder, dispersing 2, 3-dihydroxyterephthalic acid in the mixed solution 2, adding UiO-66 powder, heating to 85 ℃, stirring for 48h, centrifuging and washing after the reaction is finished, and drying at 60 ℃ for 12h to obtain hydroxylated UiO-66 powder, wherein the dosage ratio of 1, 4-terephthalic acid, the mixed solution 1 and zirconium tetrachloride is 1g:1g:3g of UiO-66 powder, 2, 3-dihydroxyterephthalic acid and 2 in a ratio of 2g:0.5g:20mL of a mixture 1, the dosage ratio of N, N-dimethylformamide to acetic acid was 15mL:4mL, the dosage ratio of N, N-dimethylformamide to water in the mixed solution 2 is 2mL:1mL;
step A5, adding the hydroxylated UiO-66 powder into a reactor containing toluene, carrying out ultrasonic treatment for 30min, then adding gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, heating to 80 ℃ and stirring for 24h, centrifuging and washing after the reaction is finished, and drying at 60 ℃ for 12h to obtain the epoxidized UiO-66 powder, wherein the dosage ratio of the hydroxylated UiO-66 powder to the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is 2g:16mL:1g;
step A6, placing the epoxidized UiO-66 powder into a reactor containing dichloromethane, adding sodium hydroxide, stirring and mixing uniformly, adding hyperbranched polymer, stirring for 3 hours at room temperature, centrifuging and washing after the reaction is finished, and drying for 6 hours at 80 ℃ to obtain core-shell nano particles, wherein the dosage ratio of the epoxidized UiO-66 powder to the hyperbranched polymer to the sodium hydroxide to the dichloromethane is 1g:2g:0.1g:40mL.
Example 2
The core-shell nanoparticle is prepared by the following steps:
step A1, adding trimethylol aminomethane into a mixed solution of chloroform and acetonitrile, stirring and mixing uniformly, adding trimethylol chlorosilane into the mixed solution at room temperature, refluxing for 2 hours, cooling to 0 ℃, adding triethylamine and trityl chloride dissolved in chloroform into a reactor, stirring the obtained mixture for 1 hour, adding methanol, concentrating, extracting and drying to obtain a compound 1, wherein the dosage ratio of trimethylol aminomethane, the mixed solution of trimethylol chlorosilane, chloroform and acetonitrile, triethylamine, trityl chloride, chloroform and methanol is 0.01mol:0.01mol:19mL:0.025mol:0.02mol:10mL: the volume ratio of the chloroform to the acetonitrile in the mixed solution of 2mL of the chloroform to the acetonitrile is 5:1, a step of;
step A2, adding 2- (methylamino) propane-1, 3-diol into a flask containing methanol, stirring and mixing uniformly at room temperature under the condition of introducing nitrogen, then dropwise adding ethyl acrylate while stirring, heating to 35 ℃ after the dropwise adding is finished, reacting for 4.5h, transferring to a vacuum rotary evaporator to remove methanol and excessive ethyl acrylate after the reaction is finished, and obtaining a hydroxyl-terminated monomer, wherein the dosage ratio of 2- (methylamino) propane-1, 3-diol, ethyl acrylate and methanol is 1mol:2mol:100mL;
step A3, placing the compound 1 and the p-toluenesulfonic acid into a reactor, uniformly mixing, heating to 110 ℃, slowly dropwise adding hydroxyl-terminated monomers, keeping the temperature at 120 ℃ for reaction for 4 hours, after the reaction is finished, reducing the temperature to 60 ℃, adding boron trifluoride diethyl ether complex, dropwise adding epoxy chloropropane, reacting for 2 hours, distilling under reduced pressure to remove excessive epoxy chloropropane, adding sodium hydroxide solution into the reactant, heating to 80 ℃ for reaction for 3 hours, after the reaction is finished, steaming for 1 hour at 100 ℃, cooling to 30 ℃, adding 40mL of acetic acid solution, refluxing for 10 minutes, and obtaining the hyperbranched polymer, wherein the dosage ratio of the compound 1, the hydroxyl-terminated monomers, the epoxy chloropropane, the sodium hydroxide solution and the boron trifluoride diethyl ether complex is 0.1mol:1.2mol:4mol:3mol:0.008mol, the dosage of the p-toluenesulfonic acid is 2% of the sum of the mass of the compound 1 and the mass of the hydroxyl-terminated monomer, and the mass ratio of acetic acid to deionized water in the acetic acid solution is 1:1, 25% of sodium hydroxide solution by mass;
step A4, dispersing 1, 4-terephthalic acid in the mixed solution 1, stirring uniformly, adding zirconium tetrachloride, carrying out ultrasonic treatment for 30min, transferring the mixed solution into an autoclave, carrying out hydrothermal treatment at 120 ℃ for 12h, cooling to room temperature after the reaction is finished, centrifuging, washing, drying at 60 ℃ for 12h to obtain UiO-66 powder, dispersing 2, 3-dihydroxyterephthalic acid in the mixed solution 2, adding UiO-66 powder, heating to 85 ℃, stirring for 48h, centrifuging and washing after the reaction is finished, and drying at 60 ℃ for 12h to obtain hydroxylated UiO-66 powder, wherein the dosage ratio of 1, 4-terephthalic acid, the mixed solution 1 and zirconium tetrachloride is 1.5g:1g:4g of UiO-66 powder, 2, 3-dihydroxyterephthalic acid and 2 were used in a ratio of 2.5g:3g:20mL of a mixture 1, the dosage ratio of N, N-dimethylformamide to acetic acid was 15mL:4mL, the dosage ratio of N, N-dimethylformamide to water in the mixed solution 2 is 2mL:1mL;
step A5, adding the hydroxylated UiO-66 powder into a reactor containing toluene, carrying out ultrasonic treatment for 30min, then adding gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, heating to 80 ℃ and stirring for 24h, centrifuging and washing after the reaction is finished, and drying at 60 ℃ for 12h to obtain the epoxidized UiO-66 powder, wherein the dosage ratio of the hydroxylated UiO-66 powder to the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is 2g:16mL:1g;
step A6, placing the epoxidized UiO-66 powder into a reactor containing dichloromethane, adding sodium hydroxide, stirring and mixing uniformly, adding hyperbranched polymer, stirring for 5 hours at room temperature, centrifuging and washing after the reaction is finished, and drying for 6 hours at 80 ℃ to obtain core-shell nano particles, wherein the dosage ratio of the epoxidized UiO-66 powder to the hyperbranched polymer to the sodium hydroxide to the dichloromethane is 2g:4g:0.1g:40mL.
Example 3
The core-shell nanoparticle is prepared by the following steps:
step A1, adding trimethylol aminomethane into a mixed solution of chloroform and acetonitrile, stirring and mixing uniformly, adding trimethylol chlorosilane into the mixed solution at room temperature, refluxing for 2 hours, cooling to 0 ℃, adding triethylamine and trityl chloride dissolved in chloroform into a reactor, stirring the obtained mixture for 1 hour, adding methanol, concentrating, extracting and drying to obtain a compound 1, wherein the dosage ratio of trimethylol aminomethane, the mixed solution of trimethylol chlorosilane, chloroform and acetonitrile, triethylamine, trityl chloride, chloroform and methanol is 0.01mol:0.01mol:20mL:0.03mol:0.025mol:10mL: the volume ratio of the chloroform to the acetonitrile in the mixed solution of 2mL of the chloroform to the acetonitrile is 5:1, a step of;
step A2, adding 2- (methylamino) propane-1, 3-diol into a flask containing methanol, stirring and mixing uniformly at room temperature under the condition of introducing nitrogen, then dropwise adding ethyl acrylate while stirring, heating to 35 ℃ after the dropwise adding is finished, reacting for 4-5h, transferring to a vacuum rotary evaporator to remove methanol and excessive ethyl acrylate after the reaction is finished, and obtaining a hydroxyl-terminated monomer, wherein the dosage ratio of 2- (methylamino) propane-1, 3-diol, ethyl acrylate and methanol is 1mol:2.5mol:100mL;
step A3, placing the compound 1 and the p-toluenesulfonic acid into a reactor, uniformly mixing, heating to 110 ℃, slowly dropwise adding hydroxyl-terminated monomers, keeping the temperature at 120 ℃ for reaction for 4 hours, after the reaction is finished, reducing the temperature to 60 ℃, adding boron trifluoride diethyl ether complex, dropwise adding epoxy chloropropane, reacting for 2 hours, distilling under reduced pressure to remove excessive epoxy chloropropane, adding sodium hydroxide solution into the reactant, heating to 80 ℃ for reaction for 3 hours, after the reaction is finished, steaming for 1 hour at 100 ℃, cooling to 30 ℃, adding 40mL of acetic acid solution, refluxing for 10 minutes, and obtaining the hyperbranched polymer, wherein the dosage ratio of the compound 1, the hydroxyl-terminated monomers, the epoxy chloropropane, the sodium hydroxide solution and the boron trifluoride diethyl ether complex is 0.1mol:2.1mol:6mol:4mol:0.01mol, the dosage of the p-toluenesulfonic acid is 2% of the sum of the mass of the compound 1 and the mass of the hydroxyl-terminated monomer, and the mass ratio of acetic acid to deionized water in the acetic acid solution is 1:1, 25% of sodium hydroxide solution by mass;
step A4, dispersing 1, 4-terephthalic acid in the mixed solution 1, stirring uniformly, adding zirconium tetrachloride, carrying out ultrasonic treatment for 30min, transferring the mixed solution into an autoclave, carrying out hydrothermal treatment at 120 ℃ for 12h, cooling to room temperature after the reaction is finished, centrifuging, washing, drying at 60 ℃ for 12h to obtain UiO-66 powder, dispersing 2, 3-dihydroxyterephthalic acid in the mixed solution 2, adding UiO-66 powder, heating to 85 ℃, stirring for 48h, centrifuging and washing after the reaction is finished, and drying at 60 ℃ for 12h to obtain hydroxylated UiO-66 powder, wherein the dosage ratio of 1, 4-terephthalic acid, the mixed solution 1 and zirconium tetrachloride is 2g:1g:5g of UiO-66 powder, 2, 3-dihydroxyterephthalic acid and the mixture 2 in a dose ratio of 3g:05g:20mL of a mixture 1, the dosage ratio of N, N-dimethylformamide to acetic acid was 15mL:4mL, the dosage ratio of N, N-dimethylformamide to water in the mixed solution 2 is 2mL:1mL;
step A5, adding the hydroxylated UiO-66 powder into a reactor containing toluene, carrying out ultrasonic treatment for 30min, then adding gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, heating to 80 ℃ and stirring for 24h, centrifuging and washing after the reaction is finished, and drying at 60 ℃ for 12h to obtain the epoxidized UiO-66 powder, wherein the dosage ratio of the hydroxylated UiO-66 powder to the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is 2g:16mL:1g;
step A6, placing the epoxidized UiO-66 powder into a reactor containing dichloromethane, adding sodium hydroxide, stirring and mixing uniformly, adding hyperbranched polymer, stirring for 6 hours at room temperature, centrifuging and washing after the reaction is finished, and drying for 6 hours at 80 ℃ to obtain core-shell nano particles, wherein the dosage ratio of the epoxidized UiO-66 powder to the hyperbranched polymer to the sodium hydroxide to the dichloromethane is 3g:6g:0.1g:40mL.
Example 4
An aldehyde-free adhesive for non-stick steel plates comprises the following raw materials:
60 parts of bisphenol A epoxy resin, 2 parts of antioxidant V72-P, 3 parts of trimethylolethane triglycidyl ether, 15 parts of core-shell nano particles prepared in example 3, 500 parts of defoamer BYK-A, 6 parts of diethylenetriamine and 4 parts of 2,4, 6-tris (dimethylaminomethyl) phenol;
the preparation method of the formaldehyde-free adhesive for the non-stick steel plate comprises the following steps:
step S1, weighing raw materials according to parts by weight, adding bisphenol A epoxy resin and core-shell nano particles prepared in example 3 into a reactor, stirring for 2 hours at 80 ℃ to uniformly mix the materials, cooling to 50 ℃, adding trimethylolethane triglycidyl ether and a defoaming agent BYK-A500 into the reactor, continuously stirring for 30 minutes, and then carrying out vacuum defoaming for 20 minutes to obtain a premix 1;
s2, placing diethylenetriamine, an antioxidant V72-P and 2,4, 6-tris (dimethylaminomethyl) phenol into a reactor, and stirring for 1h at 50 ℃ to uniformly mix the materials to obtain a premix 2;
and step S3, adding the premix 1 and the premix 2 into a reactor, uniformly mixing, pouring the mixture into a device by a machine, and curing the mixture for 24 hours at 25 ℃ to obtain the formaldehyde-free adhesive.
Example 5
An aldehyde-free adhesive for non-stick steel plates comprises the following raw materials:
70 parts of bisphenol A epoxy resin, 6 parts of trimethylolethane triglycidyl ether, 20 parts of core-shell nanoparticles prepared in example 3, 500 parts of defoamer BYK-A, 7 parts of diethylenetriamine and 6 parts of 2,4, 6-tris (dimethylaminomethyl) phenol;
the preparation method of the formaldehyde-free adhesive for the non-stick steel plate comprises the following steps:
step S1, weighing raw materials according to parts by weight, adding bisphenol A epoxy resin and core-shell nano particles prepared in example 3 into a reactor, stirring for 3 hours at 90 ℃ to uniformly mix the materials, cooling to 50 ℃, adding trimethylolethane triglycidyl ether and a defoaming agent BYK-A500 into the reactor, continuously stirring for 30 minutes, and then carrying out vacuum defoaming for 20 minutes to obtain a premix 1;
s2, placing diethylenetriamine, an antioxidant V72-P and 2,4, 6-tris (dimethylaminomethyl) phenol into a reactor, and stirring for 1h at 50 ℃ to uniformly mix the materials to obtain a premix 2;
and step S3, adding the premix 1 and the premix 2 into a reactor, uniformly mixing, pouring the mixture into a device by a machine, and curing the mixture for 24 hours at 25 ℃ to obtain the formaldehyde-free adhesive.
Example 6
An aldehyde-free adhesive for non-stick steel plates comprises the following raw materials:
80 parts of bisphenol A epoxy resin, 6 parts of antioxidant V72-P, 10 parts of trimethylolethane triglycidyl ether, 25 parts of core-shell nano particles prepared in example 3, 500 parts of defoamer BYK-A, 8 parts of diethylenetriamine and 7 parts of 2,4, 6-tris (dimethylaminomethyl) phenol;
the preparation method of the formaldehyde-free adhesive for the non-stick steel plate comprises the following steps:
step S1, weighing raw materials according to parts by weight, adding bisphenol A epoxy resin and core-shell nano particles prepared in example 3 into a reactor, stirring for 4 hours at 100 ℃, uniformly mixing the materials, cooling to 50 ℃, adding trimethylolethane triglycidyl ether and a defoaming agent BYK-A500 into the reactor, continuously stirring for 30 minutes, and then carrying out vacuum defoaming for 20 minutes to obtain a premix 1;
s2, placing diethylenetriamine, an antioxidant V72-P and 2,4, 6-tris (dimethylaminomethyl) phenol into a reactor, and stirring for 1h at 60 ℃ to uniformly mix the materials to obtain a premix 2;
and step S3, adding the premix 1 and the premix 2 into a reactor, uniformly mixing, pouring the mixture into a device by a machine, and curing the mixture for 24 hours at 25 ℃ to obtain the formaldehyde-free adhesive.
Comparative example 1
This comparative example is the MegaGlue 2102/1 series of a commercially available epoxy adhesive.
Comparative example 2
This comparative example is an adhesive, differing from example 5 in the core-shell nanoparticles replaced with epoxidized UiO-66 powder, all the others being identical.
The adhesives prepared in examples 4-6 and comparative examples 1-2 were subjected to performance testing, and the test results are shown in Table 1:
TABLE 1
As can be seen from Table 1, the shear strength of the adhesive reaches more than 40.21MPa and the peel strength reaches more than 4.12MPa at 25 ℃, which indicates that the adhesive prepared by the invention has strong cohesiveness and high peel strength; the tensile strength reaches more than 18.97MPa, which indicates that the adhesive prepared by the invention has high tensile strength and good mechanical property, and the elongation at break reaches more than 74.9%, which indicates that the prepared adhesive has good flexibility.
Tensile strength test: the curing conditions are 170 ℃/3h+200 ℃/1h according to GB/T2567-2008 standard; elongation at break test method: the test is carried out in GB-T2568-1995 method for testing tensile properties of resin casting body; shear strength and 90℃peel strength were carried out according to GB7124-86 and GB7122-86 respectively, and curing conditions were 170℃per 3h.
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. An aldehyde-free adhesive for a non-stick steel plate is characterized by comprising the following raw materials in parts by weight: 60-80 parts of bisphenol A epoxy resin, 2-6 parts of antioxidant, 15-25 parts of core-shell nano particles, 3-10 parts of diluent, 2-6 parts of defoamer, 6-8 parts of amine curing agent and 4-7 parts of curing accelerator;
the core-shell nanoparticle is prepared by the following steps:
step A1, adding tris (hydroxymethyl) aminomethane into a mixed solution of chloroform and acetonitrile, stirring and mixing uniformly, adding trimethylchlorosilane into the mixed solution at room temperature, refluxing for 2 hours, cooling to 0 ℃, adding triethylamine and trityl chloride dissolved in chloroform into a reactor, stirring the obtained mixture for 1 hour, adding methanol, concentrating, extracting and drying to obtain a compound 1;
step A2, adding 2- (methylamino) propane-1, 3-diol into a flask containing methanol, stirring and mixing uniformly at room temperature under the condition of introducing nitrogen, then dropwise adding ethyl acrylate while stirring, heating to 35 ℃ after the dropwise adding is finished, reacting for 4-5h, and transferring to a vacuum rotary steaming instrument to remove methanol and excessive ethyl acrylate after the reaction is finished, thus obtaining a hydroxyl-terminated monomer;
step A3, placing the compound 1 and the p-toluenesulfonic acid into a reactor, uniformly mixing, heating to 110 ℃, slowly dropwise adding hydroxyl-terminated monomers, keeping the temperature at 120 ℃ for reaction for 4 hours, after the reaction is finished, reducing the temperature to 60 ℃, adding boron trifluoride diethyl ether complex, dropwise adding epoxy chloropropane, reacting for 2 hours, distilling under reduced pressure to remove excessive epoxy chloropropane, adding sodium hydroxide solution into the reactant, heating to 80 ℃ for reaction for 3 hours, after the reaction is finished, steaming for 1 hour at 100 ℃, cooling to 30 ℃, and adding 40mL acetic acid solution for reflux for 10 minutes to obtain the hyperbranched polymer;
step A4, dispersing 1, 4-terephthalic acid in a mixed solution 1, stirring uniformly, adding zirconium tetrachloride, carrying out ultrasonic treatment for 30min, transferring the mixed solution into an autoclave, carrying out hydrothermal treatment at 120 ℃ for 12h, cooling to room temperature after the reaction is finished, centrifuging, washing, drying at 60 ℃ for 12h to obtain UiO-66 powder, dispersing 2, 3-dihydroxyterephthalic acid in a mixed solution 2, adding UiO-66 powder, heating to 85 ℃, stirring for 48h, centrifuging and washing after the reaction is finished, and drying at 60 ℃ for 12h to obtain hydroxylated UiO-66 powder, wherein the mixed solution 1 is a mixed solution of N, N-dimethylformamide and acetic acid, and the mixed solution 2 is a mixed solution of N, N-dimethylformamide and water;
step A5, adding hydroxylated UiO-66 powder into a reactor containing toluene, carrying out ultrasonic treatment for 30min, then adding gamma- (2, 3-glycidoxy) propyl trimethoxy silane, heating to 80 ℃ and stirring for 24h, centrifuging and washing after the reaction is finished, and drying at 60 ℃ for 12h to obtain epoxidized UiO-66 powder;
and A6, placing the epoxidized UiO-66 powder into a reactor containing dichloromethane, adding sodium hydroxide, stirring and mixing uniformly, adding the hyperbranched polymer, stirring for 3-6 hours at room temperature, centrifuging and washing after the reaction is finished, and drying for 6 hours at 80 ℃ to obtain the core-shell nanoparticle.
2. The aldehyde-free binder for non-stick steel sheets according to claim 1, wherein the amount ratio of the mixed solution of tris (hydroxymethyl) aminomethane, trimethylchlorosilane, trichloromethane and acetonitrile, triethylamine, trityl chloride, chloroform and methanol in step A1 is 0.01mol:0.01mol:18-20mL:0.02-0.03mol:0.01 to 0.025mol:10mL: the volume ratio of the chloroform to the acetonitrile in the mixed solution of 2mL of the chloroform to the acetonitrile is 5:1.
3. the aldehyde-free binder for non-stick steel sheets according to claim 1, wherein the amount ratio of 2- (methylamino) propane-1, 3-diol, ethyl acrylate and methanol in step A2 is 1mol:1.5-2.5mol:100mL.
4. The aldehyde-free binder for non-stick steel sheets according to claim 1, wherein the compound 1, hydroxyl-terminated monomer, epichlorohydrin, sodium hydroxide solution, boron trifluoride etherate and acetic acid in the step A3 are used in an amount ratio of 0.1mol:0.3-2.1mol:3-6mol:2-4mol:0.002-0.01mol:40mL of p-toluenesulfonic acid is used in an amount of 2% of the sum of the mass of the compound 1 and the mass of the hydroxyl-terminated monomer, and the mass ratio of acetic acid to deionized water in the acetic acid solution is 1:1, the mass fraction of the sodium hydroxide solution is 25%.
5. The aldehyde-free binder for non-stick steel sheets according to claim 1, wherein the ratio of 1, 4-terephthalic acid, mixed liquor 1 and zirconium tetrachloride in step A4 is 1-2g:1g:3-5g of UiO-66 powder, 2, 3-dihydroxyterephthalic acid and 2 of mixed solution with the dosage ratio of 2-3g:0.5-5g:20mL of a mixture 1, the dosage ratio of N, N-dimethylformamide to acetic acid was 15mL:4mL, the dosage ratio of N, N-dimethylformamide to water in the mixed solution 2 is 2mL:1mL.
6. An aldehyde-free binder for non-stick steel sheets according to claim 1, wherein the ratio of the amounts of hydroxylated UiO-66 powder, toluene and γ - (2, 3-glycidoxy) propyltrimethoxysilane in step A5 is 2g:16mL:1g.
7. An aldehyde-free binder for non-stick steel sheets according to claim 1, characterized in that the ratio of the amounts of epoxidized UiO-66 powder, hyperbranched polymer, sodium hydroxide and methylene chloride used in step A6 is 1-3g:2-6g:0.1g:40mL.
8. A method for producing the aldehyde-free binder for non-stick steel sheet according to claim 1, comprising the steps of:
step S1, weighing raw materials according to parts by weight, adding bisphenol A epoxy resin and core-shell nano particles into a reactor, stirring for 2-4 hours at 80-100 ℃ to uniformly mix the materials, cooling to 50 ℃, adding a diluent and a defoaming agent into the reactor, continuously stirring for 30 minutes, and then performing vacuum defoaming for 10-20 minutes to obtain a premix 1;
s2, placing an amine curing agent, an antioxidant and a curing accelerator in a reactor, and stirring for 1h at 50-60 ℃ to uniformly mix the materials to obtain a premix 2;
and step S3, adding the premix 1 and the premix 2 into a reactor, uniformly mixing, pouring the mixture into a device by a machine, and curing the mixture for 24 hours at 25 ℃ to obtain the formaldehyde-free adhesive.
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| JP2003012837A (en) * | 2001-06-27 | 2003-01-15 | Toray Ind Inc | Epoxy resin composition for fiber-reinforced composite material, prepreg and fiber-reinforced composition material |
| CN101691419A (en) * | 2009-10-10 | 2010-04-07 | 中山大学 | Hyperbranched polymer surface grafted and modified inorganic nanoparticle/epoxy resin anti-friction wear-resistant composite material and preparation method thereof |
| CN112680072A (en) * | 2020-12-27 | 2021-04-20 | 山东齐鲁漆业有限公司 | Low-viscosity high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin and preparation method thereof |
| CN113943473A (en) * | 2021-11-23 | 2022-01-18 | 广东盈骅新材料科技有限公司 | High-toughness epoxy resin composition and preparation process thereof |
| CN114395353A (en) * | 2021-12-31 | 2022-04-26 | 建滔(江阴)复合材料有限公司 | Epoxy resin glue solution with uniformly dispersed filler and copper-clad plate prepared from epoxy resin glue solution |
| CN114163959A (en) * | 2022-01-19 | 2022-03-11 | 徐海燕 | Epoxy resin modified adhesive and preparation method thereof |
| CN115216119A (en) * | 2022-07-05 | 2022-10-21 | 上海冷盟精密电机有限公司 | Epoxy resin composite material and preparation method thereof |
| CN116178734A (en) * | 2023-03-13 | 2023-05-30 | 黑龙江省科学院石油化学研究院 | Hydroxyl-terminated hyperbranched polyurethane modified epoxy resin and preparation method thereof |
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