CN113444480A - Low-temperature cured epoxy resin adhesive and preparation method thereof - Google Patents
Low-temperature cured epoxy resin adhesive and preparation method thereof Download PDFInfo
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- CN113444480A CN113444480A CN202110574160.7A CN202110574160A CN113444480A CN 113444480 A CN113444480 A CN 113444480A CN 202110574160 A CN202110574160 A CN 202110574160A CN 113444480 A CN113444480 A CN 113444480A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 69
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 69
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 40
- 239000000853 adhesive Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 15
- 239000004593 Epoxy Substances 0.000 claims abstract description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910000077 silane Inorganic materials 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 125000000524 functional group Chemical group 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004952 Polyamide Substances 0.000 claims abstract description 10
- 229920002647 polyamide Polymers 0.000 claims abstract description 10
- 229920006295 polythiol Polymers 0.000 claims abstract description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007792 addition Methods 0.000 claims abstract description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 9
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001723 curing Methods 0.000 claims description 19
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 7
- 238000013035 low temperature curing Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 4
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 229920006332 epoxy adhesive Polymers 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 239000012790 adhesive layer Substances 0.000 abstract description 3
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 abstract 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007598 dipping method 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
- 238000009863 impact test Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
- C08G59/60—Amines together with other curing agents with amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
-
- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Abstract
The invention discloses a low-temperature cured epoxy resin adhesive and a preparation method thereof, relating to the technical field of adhesives and comprising the following steps: mixing propylene glycol ether, epoxy resin, dibenzoyl peroxide and part of organic silicon resin, heating, stirring, dripping epoxy functional group silane, and adding the rest organic silicon resin when the dripping amount is 60-70%; after the dropwise addition, heating, stirring for reaction, adding liquid hydroxyl-terminated butadiene-acrylonitrile rubber, stirring for reaction, and performing rotary evaporation to remove the solvent to obtain the modified epoxy resin; adding fumed silica, filler, plasticizer and cyclohexanone into the modified epoxy resin, and stirring to obtain a component A; mixing diethylenetriamine, a polythiol curing agent, low molecular polyamide and an accelerant to obtain a component B; when in use, the adhesive is obtained by mixing the component A and the component B. The adhesive has good adhesive effect on various base materials at low temperature, is not brittle after being cured, has good hardness and toughness of the obtained adhesive layer, and has good stripping resistance.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a low-temperature cured epoxy resin adhesive and a preparation method thereof.
Background
The epoxy resin is a generic name of a polymer having two or more epoxy groups in a molecule. Because of the chemical activity of the epoxy group, a plurality of compounds containing active hydrogen can be used for ring opening, curing and crosslinking to generate a network structure, and the cured epoxy resin has good physical and chemical properties, has excellent bonding strength to the surfaces of metal and nonmetal materials, is widely applied to the fields of machinery, electronics, aerospace, ship industry, building industry and the like, and can be used for casting, dipping, laminating materials, adhesives, coatings and the like.
Epoxy resin has excellent adhesive property, which is called as universal glue, however, due to high crosslinking density and poor toughness of a cured product, the adhesive layer of the epoxy resin cured at low temperature is easy to crack, thereby limiting the further application of the epoxy resin.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the low-temperature cured epoxy resin adhesive and the preparation method thereof.
The invention provides a preparation method of a low-temperature cured epoxy resin adhesive, which comprises the following steps:
s1, preparation of modified epoxy resin: adding propylene glycol ether into a reaction container, then adding epoxy resin, dibenzoyl peroxide and part of organic silicon resin, heating to 100-120 ℃, stirring, dropwise adding epoxy functional group silane, controlling the dropwise adding within 1-2 h to be finished, and adding the rest organic silicon resin when the epoxy functional group silane is dropwise added to 60-70% of the total amount of the epoxy functional group silane; after the dropwise addition, heating to 160-180 ℃, stirring and reacting for 1-2 h, adding liquid hydroxy nitrile rubber, stirring and reacting for 1-2 h, and performing rotary evaporation to remove the solvent to obtain the modified epoxy resin;
s2, preparation of component A: adding fumed silica, filler, plasticizer and cyclohexanone into the modified epoxy resin, and stirring to obtain a component A;
s3, preparation of component B: mixing diethylenetriamine, a polythiol curing agent, low molecular weight polyamide and an accelerant to obtain a component B;
s4, preparing glue: when in use, the adhesive is obtained by mixing the component A and the component B.
Preferably, in S1, the weight ratio of the epoxy resin, the silicone resin, the epoxy functional silane and the liquid hydroxyl-terminated nitrile rubber is 100: 25-32: 5-10: 4 to 7.
Preferably, in S1, the weight percentage of the two additions of the organic silicon resin is 50-60: 40 to 50.
Preferably, in S2, the weight ratio of the modified epoxy resin, the fumed silica, the filler, the plasticizer and the cyclohexanone is 50-60: 1-3: 30-40: 0.5-2: 4 to 7.
Preferably, in S2, the filler is formed by compounding any one or more of talc, kaolin, and calcium carbonate with alumina.
Preferably, in S3, the weight ratio of diethylenetriamine, polythiol curing agent, low molecular polyamide and accelerator is 65-75: 7-14: 7-14: 5 to 10.
Preferably, in S3, the accelerator is accelerator DMP30 or accelerator DMBA.
Preferably, in S4, the ratio of component A to component B is 1.5-1.8: 1 to obtain the adhesive.
The invention also provides the low-temperature cured epoxy resin adhesive prepared by the method.
Has the advantages that: the invention provides a preparation method of a low-temperature cured epoxy resin adhesive, which takes modified epoxy resin as a bonding material, wherein the modified epoxy resin is prepared by simultaneously modifying epoxy functional group silane and organic silicon resin, the epoxy functional group silane and the epoxy resin both have epoxy groups, and the similar structure can reduce the surface tension between the organic silicon resin and the epoxy resin and improve the compatibility of the organic silicon resin and the epoxy resin; the modification effect is better by controlling the dropping speed of the epoxy functional group silane and adding the organic silicon resin in two times, which is probably because the organic silicon resin and the epoxy functional group silane react and polymerize with active sites on the epoxy resin in a limited reaction space under the initiation of dibenzoyl peroxide, and the dispersibility and compatibility among the organic silicon resin and the epoxy functional group silane are better improved by adding in several times on the basis of continuously consuming the modification raw materials; finally, liquid hydroxy nitrile rubber is added to further improve the toughness of the epoxy resin, and the modified epoxy resin has excellent flexibility and cohesiveness.
The curing agent is mainly low-temperature curing agent diethylenetriamine, low-molecular polyamide is added to further improve the curing brittleness of the epoxy resin, the curing efficiency can be improved by adding the polythiol curing agent, the three components are compounded to have good low-temperature curing performance, and the added accelerator can enable the curing agent to better exert the curing performance and shorten the curing time.
The epoxy resin adhesive prepared by the invention has the advantages that the toughness is improved on the basis of ensuring the mechanical property, the adhesive has good adhesive effect on base materials such as metal, wood, glass, ceramic and the like at low temperature, the brittle fracture is not easy to occur after the curing, the two components are independently stored, the storage and the transportation are convenient, the hardness and the toughness of the obtained adhesive layer are good, and the peeling resistance is good.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The invention provides a preparation method of a low-temperature cured epoxy resin adhesive, which comprises the following steps:
s1, preparation of modified epoxy resin: adding 20 parts of propylene glycol ether into a reaction container, then adding 100 parts of epoxy resin, 0.2 part of dibenzoyl peroxide and 12.5 parts of organic silicon resin, heating to 100 ℃, stirring, dripping 5 parts of silane coupling agent KH-560, controlling the dripping within 1 hour to be finished, and adding 12.5 parts of organic silicon resin when the dripping is up to 60 percent of the total amount; after the dropwise addition, heating to 160 ℃, stirring and reacting for 1h, adding 4 parts of liquid end hydroxy nitrile rubber, stirring and reacting for 1h, and removing the solvent by rotary evaporation to obtain the modified epoxy resin;
s2, preparation of component A: adding 1 part of fumed silica, 40 parts of filler, 0.5 part of plasticizer and 4 parts of cyclohexanone into 50 parts of modified epoxy resin, and stirring to obtain a component A; wherein, the filler is prepared from talcum powder and alumina according to the proportion of 1: 3 in a weight ratio;
s3, preparation of component B: mixing 65 parts of diethylenetriamine, 7 parts of polythiol curing agent, 14 parts of low molecular polyamide and 5 parts of accelerator DMP30 to obtain a component B;
s4, preparing glue: when in use, the components A and B are mixed according to the ratio of 1.5: 1 to obtain the adhesive.
Example 2
The invention provides a preparation method of a low-temperature cured epoxy resin adhesive, which comprises the following steps:
s1, preparation of modified epoxy resin: adding 24 parts of propylene glycol ether into a reaction container, then adding 100 parts of epoxy resin, 0.3 part of dibenzoyl peroxide and 15.4 parts of organic silicon resin, heating to 110 ℃, stirring, dropwise adding 6 parts of silane coupling agent KH-560, controlling the dropwise adding within 1.5h, and adding 12.6 parts of organic silicon resin when the dropwise adding is carried out to 65% of the total amount; after the dropwise addition, heating to 160 ℃, stirring and reacting for 1.5h, then adding 5 parts of liquid end hydroxy nitrile rubber, stirring and reacting for 1.5h, and removing the solvent by rotary evaporation to obtain the modified epoxy resin;
s2, preparation of component A: adding 1.5 parts of fumed silica, 38 parts of filler, 1 part of plasticizer and 5 parts of cyclohexanone into 54 parts of modified epoxy resin, and stirring to obtain a component A; wherein, the filler is prepared from kaolin and alumina according to the weight ratio of 1: 2 in a weight ratio;
s3, preparation of component B: mixing 68 parts of diethylenetriamine, 10 parts of polythiol curing agent, 10 parts of low molecular polyamide and 7 parts of accelerator DMP30 to obtain a component B;
s4, preparing glue: when in use, the components A and B are mixed according to the ratio of 1.6: 1 to obtain the adhesive.
Example 3
The invention provides a preparation method of a low-temperature cured epoxy resin adhesive, which comprises the following steps:
s1, preparation of modified epoxy resin: adding 27 parts of propylene glycol ethyl ether into a reaction container, then adding 100 parts of epoxy resin, 0.5 part of dibenzoyl peroxide and 17 parts of organic silicon resin, heating to 115 ℃, stirring, dropwise adding 8 parts of silane coupling agent KH-560, controlling the dropwise adding within 1.5h, and adding 13 parts of organic silicon resin when the dropwise adding is up to 60% of the total amount; after the dropwise addition, heating to 170 ℃, stirring for reaction for 1h, adding 6 parts of liquid end hydroxy nitrile rubber, stirring for reaction for 2h, and removing the solvent by rotary evaporation to obtain the modified epoxy resin;
s2, preparation of component A: adding 2 parts of fumed silica, 35 parts of filler, 1.5 parts of plasticizer and 6 parts of cyclohexanone into 57 parts of modified epoxy resin, and stirring to obtain a component A; wherein, the filler is prepared from kaolin and alumina according to the weight ratio of 1: 1 in a weight ratio;
s3, preparation of component B: mixing 72 parts of diethylenetriamine, 12 parts of polythiol curing agent, 9 parts of low molecular polyamide and 8 parts of accelerator DMBA to obtain a component B;
s4, preparing glue: when in use, the components A and B are mixed according to the ratio of 1.7: 1 to obtain the adhesive.
Example 4
The invention provides a preparation method of a low-temperature cured epoxy resin adhesive, which comprises the following steps:
s1, preparation of modified epoxy resin: adding 30 parts of propylene glycol ether into a reaction container, then adding 100 parts of epoxy resin, 0.5 part of dibenzoyl peroxide and 22.4 parts of organic silicon resin, heating to 120 ℃, stirring, dripping 10 parts of silane coupling agent KH-560, controlling the dripping within 2 hours, and adding 9.6 parts of organic silicon resin when the dripping is controlled to be 70% of the total amount; after the dropwise addition, heating to 180 ℃, stirring for reaction for 2h, adding 7 parts of liquid end hydroxy nitrile rubber, stirring for reaction for 2h, and removing the solvent by rotary evaporation to obtain the modified epoxy resin;
s2, preparation of component A: adding 3 parts of fumed silica, 30 parts of filler, 2 parts of plasticizer and 7 parts of cyclohexanone into 60 parts of modified epoxy resin, and stirring to obtain a component A; wherein, the filler is prepared by mixing calcium carbonate and alumina according to the proportion of 1: 4 in a weight ratio;
s3, preparation of component B: mixing 75 parts of diethylenetriamine, 14 parts of polythiol curing agent, 7 parts of low molecular polyamide and 10 parts of accelerator DMBA to obtain a component B;
s4, preparing glue: when in use, the components A and B are mixed according to the ratio of 1.8: 1 to obtain the adhesive.
Comparative example
Compared with the embodiment 1, the difference is only that S1 is different, and the specific difference is as follows:
s1, preparation of modified epoxy resin: adding 20 parts of propylene glycol ether into a reaction container, then adding 100 parts of epoxy resin, 0.2 part of dibenzoyl peroxide and 25 parts of organic silicon resin, heating to 100 ℃, stirring, dropwise adding 5 parts of silane coupling agent KH-560, and controlling the dropwise adding within 1 hour to be finished; after the dropwise addition, heating to 160 ℃, stirring and reacting for 1h, adding 4 parts of liquid end hydroxy nitrile rubber, stirring and reacting for 1h, and removing the solvent by rotary evaporation to obtain the modified epoxy resin;
the epoxy resin adhesives prepared in examples 1 to 4 and comparative example were examined for their performance.
Test standards: self-made tensile and impact test pieces are prepared according to GB2567-81, the shear strength is detected at room temperature according to GB7124-86 standard, the peel strength (90 ℃) is detected according to GB7122-86 standard, and the bending impact strength (adhesive) is detected according to the common method of the adhesive impact strength; the curing condition is 120 ℃ and curing is 1.5 h.
Table 1 performance data for epoxy adhesives
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example | |
| Shear strength MPa | 28.5 | 32.1 | 30.8 | 29.3 | 28.7 |
| Peel strength kN/m | 7.7 | 7.7 | 7.3 | 6.9 | 7.5 |
| Flexural impact strength kJ/m2 | 6.4 | 6.9 | 7.0 | 6.9 | 6.0 |
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. The preparation method of the low-temperature cured epoxy resin adhesive is characterized by comprising the following steps of:
s1, preparation of modified epoxy resin: adding propylene glycol ether into a reaction container, then adding epoxy resin, dibenzoyl peroxide and part of organic silicon resin, heating to 100-120 ℃, stirring, dropwise adding epoxy functional group silane, controlling the dropwise adding within 1-2 h to be finished, and adding the rest organic silicon resin when the epoxy functional group silane is dropwise added to 60-70% of the total amount of the epoxy functional group silane; after the dropwise addition, heating to 160-180 ℃, stirring and reacting for 1-2 h, adding liquid hydroxy nitrile rubber, stirring and reacting for 1-2 h, and performing rotary evaporation to remove the solvent to obtain the modified epoxy resin;
s2, preparation of component A: adding fumed silica, filler, plasticizer and cyclohexanone into the modified epoxy resin, and stirring to obtain a component A;
s3, preparation of component B: mixing diethylenetriamine, a polythiol curing agent, low molecular weight polyamide and an accelerant to obtain a component B;
s4, preparing glue: when in use, the adhesive is obtained by mixing the component A and the component B.
2. The method for preparing the low-temperature-curing epoxy resin adhesive according to claim 1, wherein in S1, the weight ratio of the epoxy resin, the silicone resin, the epoxy functional silane and the liquid hydroxyl-terminated nitrile rubber is 100: 25-32: 5-10: 4 to 7.
3. The preparation method of the low-temperature curing epoxy resin adhesive according to claim 1, wherein in S1, the weight percentage of the added organic silicon resin for two times is 50-60: 40 to 50.
4. The preparation method of the low-temperature-curing epoxy resin adhesive according to claim 1, wherein in S2, the weight ratio of the modified epoxy resin, the fumed silica, the filler, the plasticizer and the cyclohexanone is 50-60: 1-3: 30-40: 0.5-2: 4 to 7.
5. The method for preparing the low-temperature cured epoxy resin adhesive according to claim 1, wherein in S2, the filler is formed by compounding any one or more of talcum powder, kaolin and calcium carbonate with alumina.
6. The preparation method of the low-temperature-curing epoxy resin adhesive according to claim 1, wherein in S3, the weight ratio of diethylenetriamine, the polythiol curing agent, the low-molecular polyamide and the accelerator is 65-75: 7-14: 7-14: 5 to 10.
7. The method of claim 1, wherein the accelerator in S3 is accelerator DMP30 or accelerator DMBA.
8. The method for preparing the low-temperature-curing epoxy resin adhesive according to claim 1, wherein in S4, the ratio of the component A to the component B is 1.5-1.8: 1 to obtain the adhesive.
9. A low temperature cured epoxy adhesive prepared by the method of any one of claims 1-8.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957923A (en) * | 2021-12-29 | 2022-08-30 | 江苏志纤复能科技有限公司 | Vinyl organic silicon toughening modified epoxy resin and preparation method thereof |
| CN115491167A (en) * | 2022-09-23 | 2022-12-20 | 深圳斯多福新材料科技有限公司 | Epoxy modified organic silicon elastic adhesive and preparation method thereof |
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| CN102732209A (en) * | 2012-07-06 | 2012-10-17 | 郑州大学 | High-temperature-resistant flexible adhesive cured at normal temperature and preparation method thereof |
| CN105778849A (en) * | 2014-12-17 | 2016-07-20 | 党庆风 | Polysiloxane pressure-sensitive adhesive and preparation method therefor |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732209A (en) * | 2012-07-06 | 2012-10-17 | 郑州大学 | High-temperature-resistant flexible adhesive cured at normal temperature and preparation method thereof |
| CN105778849A (en) * | 2014-12-17 | 2016-07-20 | 党庆风 | Polysiloxane pressure-sensitive adhesive and preparation method therefor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114957923A (en) * | 2021-12-29 | 2022-08-30 | 江苏志纤复能科技有限公司 | Vinyl organic silicon toughening modified epoxy resin and preparation method thereof |
| CN114957923B (en) * | 2021-12-29 | 2023-08-18 | 江苏志纤复能科技有限公司 | Vinyl organosilicon toughened and modified epoxy resin and preparation method thereof |
| CN115491167A (en) * | 2022-09-23 | 2022-12-20 | 深圳斯多福新材料科技有限公司 | Epoxy modified organic silicon elastic adhesive and preparation method thereof |
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