CN117567962B - High-strength high-toughness adhesive, preparation method thereof and application thereof in paper product processing - Google Patents
High-strength high-toughness adhesive, preparation method thereof and application thereof in paper product processing Download PDFInfo
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- CN117567962B CN117567962B CN202410058712.2A CN202410058712A CN117567962B CN 117567962 B CN117567962 B CN 117567962B CN 202410058712 A CN202410058712 A CN 202410058712A CN 117567962 B CN117567962 B CN 117567962B
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 91
- 239000000853 adhesive Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000012545 processing Methods 0.000 title claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 230
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 111
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 111
- 239000000839 emulsion Substances 0.000 claims abstract description 106
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 86
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 86
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 72
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 117
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 102
- 125000003342 alkenyl group Chemical group 0.000 claims description 84
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 74
- 239000007788 liquid Substances 0.000 claims description 65
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 47
- 239000003999 initiator Substances 0.000 claims description 44
- 239000000178 monomer Substances 0.000 claims description 44
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 31
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 29
- 239000005977 Ethylene Substances 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 20
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 19
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 19
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 13
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000000123 paper Substances 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000012790 adhesive layer Substances 0.000 abstract description 3
- 238000005452 bending Methods 0.000 abstract description 3
- 239000011087 paperboard Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- -1 cartons Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 20
- 238000002791 soaking Methods 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004831 Hot glue Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 235000014528 Pholiota nameko Nutrition 0.000 description 1
- 244000168667 Pholiota nameko Species 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/048—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- 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
Abstract
The invention belongs to the technical field of adhesives, and discloses a high-strength high-toughness adhesive, a preparation method thereof and application thereof in paper product processing. In the invention, the ethylene-vinyl acetate copolymer emulsion is used as a main raw material of the adhesive, has strong adhesive force, and can be used for bonding paper products such as paper, cartons, paperboards and the like; the inorganic toughening material nano silicon dioxide and the organic toughening material nitrile rubber are introduced into the adhesive, so that the toughness of the adhesive can be effectively improved, and the paper product is prevented from being damaged due to brittle fracture of an adhesive layer caused by bending in the use process of the paper product; the tackifying resin emulsion is added into the adhesive, so that the bonding strength of the adhesive can be increased, and the stability of the paper product is improved. The adhesive prepared by the invention has high bonding strength and good toughness, and can be used for bonding and pasting paper products such as paperboards, cartons and the like.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a high-strength high-toughness adhesive, a preparation method thereof and application thereof in paper product processing.
Background
Paper products such as cardboard, cartons and the like have an indispensable role in our production and life, especially in the packaging industry. The paper products need to be glued during processing with adhesives to achieve the desired size, shape and strength. In the prior art, starch adhesives are mostly used for preparing paper products, but gelatinized starch is easy to mildew and needs to be subjected to antibacterial modification treatment.
The ethylene-vinyl acetate copolymer (EVA) emulsion has the advantages of quick solidification, strong adhesive force and the like, and the adhesive prepared by using the ethylene-vinyl acetate copolymer (EVA) emulsion as a raw material can be applied to the processing of paper products. Chinese patent CN115216248B discloses an EVA glue for paper packaging and a preparation method thereof, which uses a high molecular polymer ethylene-vinyl acetate copolymer as a main raw material, and adds tackifier and the like to improve the performances of cohesive strength, mechanical strength, adhesive property and the like of the EVA glue, but the toughness of the adhesive is not modified, and the paper product may be broken due to brittle fracture of the adhesive layer caused by bending in the use process of the paper product. Chinese patent application CN111019559a discloses an EVA hot melt adhesive for quick box sealing and a preparation method thereof, in which a single inorganic filler, silica, is added to improve toughness of the hot melt adhesive, and the dispersion compatibility between silica and resin is poor, so that the improvement effect on performance is to be improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-strength high-toughness adhesive and a preparation method thereof, which are used for solving the problems of poor adhesive strength and low toughness of the adhesive in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a preparation method of a high-strength high-toughness adhesive comprises the following steps:
adding amino-terminated liquid nitrile rubber and glycidyl acrylate into ethanol, adding alkali liquor to adjust the pH value to 10-12, reacting, adding acid liquor to adjust the pH value to 6.5-7.5 after the reaction is finished, and performing rotary evaporation to obtain alkenyl modified liquid nitrile rubber;
adding gamma-methacryloxypropyl trimethoxy silane into an ethanol aqueous solution, adding acid liquor to adjust the pH value to 4-6, adding nano silicon dioxide, reacting, and purifying after the reaction is finished to obtain alkenyl modified nano silicon dioxide; adding alkenyl modified liquid nitrile rubber, alkenyl modified nano silicon dioxide and vinyl acetate into ethyl acetate, uniformly mixing to obtain a mixed monomer solution, and dissolving azodiisobutyronitrile into the ethyl acetate to obtain an initiator solution; mixing a part of mixed monomer solution with a part of initiator solution, introducing ethylene for the first time, reacting, dripping the rest mixed monomer solution and the rest initiator solution after the reaction is finished, introducing ethylene again after the dripping is finished, continuing the reaction, and obtaining the reactive ethylene-vinyl acetate copolymer emulsion after the reaction is finished;
and thirdly, mixing the ethylene-vinyl acetate copolymer emulsion, the reactive ethylene-vinyl acetate copolymer emulsion and the tackifying resin emulsion to obtain the high-strength high-toughness adhesive.
Preferably, in the first step, the mass ratio of the amino-terminated liquid nitrile rubber to the glycidyl acrylate to the ethanol is 35: (1.4-2.8): (300-500), the reaction conditions are: reacting at 30-50 deg.C for 24-48h.
Preferably, the alkaline solution comprises an aqueous sodium hydroxide solution and the acid solution comprises an aqueous hydrochloric acid solution.
Further, the aqueous sodium hydroxide solution was 10wt% aqueous sodium hydroxide solution, and the aqueous hydrochloric acid solution was 5wt% aqueous hydrochloric acid solution.
Preferably, in the second step, when preparing the alkenyl modified nano silicon dioxide, the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the nano silicon dioxide to the ethanol aqueous solution is (5-10): (60-90): (600-800); the reaction conditions are as follows: reacting for 2-3h at 25-35 ℃.
Preferably, the aqueous ethanol solution is a 95wt% aqueous ethanol solution.
Preferably, the nano silicon dioxide is nano silicon dioxide after surface activation, and the nano silicon dioxide after surface activation is prepared by the following steps: and (3) placing the nano silicon dioxide in a mixed solution of 98wt% of concentrated sulfuric acid and 30wt% of hydrogen peroxide, soaking, filtering, washing and drying after the soaking is completed, so as to obtain the nano silicon dioxide with the activated surface.
Further, in the mixed solution of 98wt% of concentrated sulfuric acid and 30wt% of hydrogen peroxide, the volume ratio of 98wt% of concentrated sulfuric acid to 30wt% of hydrogen peroxide is 7:3, a step of; the dipping conditions are as follows: dipping for 2-3h at room temperature.
Preferably, in the second step, when preparing the reactive ethylene-vinyl acetate copolymer emulsion, the mass ratio of the alkenyl modified liquid nitrile rubber, the alkenyl modified nano silicon dioxide, the vinyl acetate and the azodiisobutyronitrile is (365-385): (80-100): (800-1200): 10.
preferably, the mass ratio of the alkenyl modified liquid nitrile rubber, the alkenyl modified nano silicon dioxide, the vinyl acetate and the ethyl acetate in the mixed monomer solution is (365-385): (80-100): (800-1200): (3000-4000); the mass ratio of the azodiisobutyronitrile to the ethyl acetate in the initiator solution is 10: (90-115).
Preferably, in the second step, when preparing the reactive ethylene-vinyl acetate copolymer emulsion, the reaction conditions are as follows: reacting at 75-85deg.C for 30-60min; the conditions for continuing the reaction were: reacting for 3-5h at 75-85 ℃.
Preferably, a part of the mixed monomer solution accounts for 20-30% of the mass of the mixed monomer solution, and a part of the initiator solution accounts for 10-20% of the mass of the initiator solution.
Preferably, the ethylene is continuously introduced in the first time in an amount of keeping the pressure of the reaction system at 3-5MPa in the reaction process, namely, the ethylene is continuously introduced in the first time until the reaction is finished; and continuously introducing ethylene again in an amount of keeping the pressure of the reaction system at 6-8MPa, and continuously introducing ethylene in the reaction process, namely continuously introducing ethylene for the second time until the reaction is finished continuously.
Preferably, in the third step, the mass ratio of the ethylene-vinyl acetate copolymer emulsion, the reactive ethylene-vinyl acetate copolymer emulsion and the tackifying resin emulsion is (81-87): (10-14): (3-5).
Preferably, the high-strength high-toughness adhesive is prepared by the preparation method of the high-strength high-toughness adhesive.
Preferably, the high-strength high-toughness adhesive is applied to paper product processing.
Compared with the prior art, the invention has the beneficial effects that: in the invention, the ethylene-vinyl acetate copolymer emulsion is used as a main raw material of the adhesive, has strong adhesive force, and can be used for bonding and pasting paper products such as paperboards, cartons and the like; the inorganic toughening material nano silicon dioxide and the organic toughening material nitrile rubber are introduced into the adhesive, so that the toughness of the adhesive can be effectively improved, and the paper product is prevented from being damaged due to brittle fracture of an adhesive layer caused by bending in the use process of the paper product; the tackifying resin emulsion is added into the adhesive, so that the bonding strength of the adhesive can be increased, and the stability of the paper product can be improved; according to the invention, the inorganic toughening material nano silicon dioxide and the organic toughening material nitrile rubber are respectively subjected to modification treatment, alkenyl is introduced, then alkenyl modified liquid nitrile rubber, alkenyl modified nano silicon dioxide, vinyl acetate and ethylene are subjected to copolymerization reaction to obtain a reactive ethylene-vinyl acetate copolymer emulsion, the copolymer in the reactive ethylene-vinyl acetate copolymer emulsion has a similar structure to the ethylene-vinyl acetate copolymer in the ethylene-vinyl acetate copolymer emulsion, the compatibility is good, the nano silicon dioxide and the nitrile rubber are grafted to the molecular structure of the acetic acid-vinyl acetate copolymer in the reactive ethylene-vinyl acetate copolymer emulsion in a chemical bond mode through copolymerization reaction, so that the dispersion uniformity of the toughening material in the adhesive is improved, and the toughness of the adhesive is further improved; according to the invention, the tackifying resin emulsion is added, so that the initial adhesion, the peeling strength and the holding strength of the adhesive can be effectively improved, and the adhesive has high bonding strength.
Drawings
FIG. 1 is a flow chart of a preparation process of the high-strength and high-toughness adhesive;
FIG. 2 is a plot of the results of toughness testing of the adhesives prepared in examples 1-5 and comparative examples 1-4 of the present invention;
FIG. 3 is a line graph showing the results of adhesive property test of the adhesives prepared in examples 1 to 5 and comparative examples 1 to 4 according to the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
A preparation method of a high-strength high-toughness adhesive comprises the following steps:
adding amino-terminated liquid nitrile rubber and glycidyl acrylate into ethanol, wherein the mass ratio of the amino-terminated liquid nitrile rubber to the glycidyl acrylate to the ethanol is 35:1.4:300, adding 10wt% of sodium hydroxide aqueous solution to adjust the pH value to 10, reacting for 48 hours at the temperature of 30 ℃, adding 5wt% of hydrochloric acid aqueous solution to adjust the pH value to 6.5 after the reaction is finished, and removing ethanol by rotary evaporation to obtain alkenyl modified liquid nitrile rubber;
adding gamma-methacryloxypropyl trimethoxysilane into 95wt% ethanol water solution, adding 5wt% hydrochloric acid water solution to adjust the pH value to be 4, and adding nano silicon dioxide, wherein the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the nano silicon dioxide to the ethanol water solution is 5:60:600, reacting for 3 hours at 25 ℃, filtering after the reaction is finished, washing filter residues with ethanol, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain alkenyl modified nano silicon dioxide; the nano silicon dioxide is surface-activated nano silicon dioxide, and the surface-activated nano silicon dioxide is prepared by the following steps: the nano silicon dioxide is placed in 98 weight percent of concentrated sulfuric acid and 30 weight percent of hydrogen peroxide according to the volume ratio of 7:3, soaking the mixture in the prepared mixed solution for 2 hours at room temperature, filtering after soaking, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain the nano silicon dioxide with activated surface; adding alkenyl modified liquid nitrile rubber, alkenyl modified nano silicon dioxide and vinyl acetate into ethyl acetate, wherein the mass ratio of the alkenyl modified liquid nitrile rubber to the alkenyl modified nano silicon dioxide to the vinyl acetate is 365:80:800:3000, uniformly mixing to obtain a mixed monomer solution, and dissolving azobisisobutyronitrile into ethyl acetate, wherein the mass ratio of the azobisisobutyronitrile to the ethyl acetate is 10:90, obtaining an initiator solution; mixing a mixed monomer solution accounting for 20% of the mass of the mixed monomer solution with an initiator solution accounting for 10% of the mass of the initiator solution, introducing ethylene for the first time, keeping the pressure of a reaction system at 3MPa, reacting at 75 ℃ for 60min, dripping the rest mixed monomer solution and the rest initiator solution after the reaction is finished, introducing ethylene again after the dripping is finished, keeping the pressure of the reaction system at 6MPa, continuing to react for 5h at 75 ℃, and obtaining the reactive ethylene-vinyl acetate copolymer emulsion after the reaction is finished; the mass ratio of the alkenyl modified liquid nitrile rubber to the alkenyl modified nano silicon dioxide to the vinyl acetate to the azodiisobutyronitrile is 365:80:800:10;
step three, mixing ethylene-vinyl acetate copolymer emulsion, reactive ethylene-vinyl acetate copolymer emulsion and tackifying resin emulsion, wherein the mass ratio of the ethylene-vinyl acetate copolymer emulsion to the reactive ethylene-vinyl acetate copolymer emulsion to the tackifying resin emulsion is 75:20: and 5, obtaining the high-strength high-toughness adhesive.
Example 2
A preparation method of a high-strength high-toughness adhesive comprises the following steps:
adding amino-terminated liquid nitrile rubber and glycidyl acrylate into ethanol, wherein the mass ratio of the amino-terminated liquid nitrile rubber to the glycidyl acrylate to the ethanol is 35:2.8:500, adding 10wt% of sodium hydroxide aqueous solution to adjust the pH value to 12, reacting for 24 hours at 50 ℃, adding 5wt% of hydrochloric acid aqueous solution to adjust the pH value to 7.5 after the reaction is finished, and removing ethanol by rotary evaporation to obtain alkenyl modified liquid nitrile rubber;
adding gamma-methacryloxypropyl trimethoxysilane into 95wt% ethanol water solution, adding 5wt% hydrochloric acid water solution to adjust the pH value to 6, and adding nano silicon dioxide, wherein the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the nano silicon dioxide to the ethanol water solution is 10:90:800, reacting for 2 hours at 35 ℃, filtering after the reaction is finished, washing filter residues with ethanol, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain alkenyl modified nano silicon dioxide; the nano silicon dioxide is surface-activated nano silicon dioxide, and the surface-activated nano silicon dioxide is prepared by the following steps: the nano silicon dioxide is placed in 98 weight percent of concentrated sulfuric acid and 30 weight percent of hydrogen peroxide according to the volume ratio of 7:3, soaking the mixture in the prepared mixed solution for 3 hours at room temperature, filtering after soaking, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain the nano silicon dioxide with activated surface; adding alkenyl modified liquid nitrile rubber, alkenyl modified nano silicon dioxide and vinyl acetate into ethyl acetate, wherein the mass ratio of the alkenyl modified liquid nitrile rubber to the alkenyl modified nano silicon dioxide to the vinyl acetate is 385:100:1200:4000, uniformly mixing to obtain a mixed monomer solution, dissolving azobisisobutyronitrile into ethyl acetate, wherein the mass ratio of the azobisisobutyronitrile to the ethyl acetate is 10:115, obtaining an initiator solution; mixing a mixed monomer solution accounting for 30% of the mass of the mixed monomer solution with an initiator solution accounting for 20% of the mass of the initiator solution, introducing ethylene for the first time, keeping the pressure of a reaction system at 5MPa, reacting for 30min at 85 ℃, dripping the rest mixed monomer solution and the rest initiator solution after the reaction is finished, introducing ethylene again after the dripping is finished, keeping the pressure of the reaction system at 8MPa, continuing to react for 3h at 85 ℃, and obtaining the reactive ethylene-vinyl acetate copolymer emulsion after the reaction is finished; the mass ratio of the alkenyl modified liquid nitrile rubber to the alkenyl modified nano silicon dioxide to the vinyl acetate to the azodiisobutyronitrile is 385:100:1200:10;
step three, mixing ethylene-vinyl acetate copolymer emulsion, reactive ethylene-vinyl acetate copolymer emulsion and tackifying resin emulsion, wherein the mass ratio of the ethylene-vinyl acetate copolymer emulsion to the reactive ethylene-vinyl acetate copolymer emulsion to the tackifying resin emulsion is 81:16: and 3, obtaining the high-strength high-toughness adhesive.
Example 3
A preparation method of a high-strength high-toughness adhesive comprises the following steps:
adding amino-terminated liquid nitrile rubber and glycidyl acrylate into ethanol, wherein the mass ratio of the amino-terminated liquid nitrile rubber to the glycidyl acrylate to the ethanol is 35:1.8:350, adding 10wt% of sodium hydroxide aqueous solution to adjust the pH value to 10.5, reacting for 42 hours at 35 ℃, adding 5wt% of hydrochloric acid aqueous solution to adjust the pH value to 7 after the reaction is finished, and removing ethanol by rotary evaporation to obtain alkenyl modified liquid nitrile rubber;
adding gamma-methacryloxypropyl trimethoxysilane into 95wt% ethanol water solution, adding 5wt% hydrochloric acid water solution to adjust the pH value to 4.5, and adding nano silicon dioxide, wherein the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the nano silicon dioxide to the ethanol water solution is 6:70:650, reacting for 2.5 hours at 30 ℃, filtering after the reaction is finished, washing filter residues with ethanol, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain alkenyl modified nano silicon dioxide; the nano silicon dioxide is surface-activated nano silicon dioxide, and the surface-activated nano silicon dioxide is prepared by the following steps: the nano silicon dioxide is placed in 98 weight percent of concentrated sulfuric acid and 30 weight percent of hydrogen peroxide according to the volume ratio of 7:3, soaking the mixture in the prepared mixed solution for 2.5 hours at room temperature, filtering after soaking, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain the nano silicon dioxide with activated surface; adding alkenyl modified liquid nitrile rubber, alkenyl modified nano silicon dioxide and vinyl acetate into ethyl acetate, wherein the mass ratio of the alkenyl modified liquid nitrile rubber to the alkenyl modified nano silicon dioxide to the vinyl acetate is 370:85:900:3250, uniformly mixing to obtain a mixed monomer solution, dissolving azobisisobutyronitrile into ethyl acetate, wherein the mass ratio of the azobisisobutyronitrile to the ethyl acetate is 10:96, obtaining an initiator solution; mixing a mixed monomer solution accounting for 25% of the mass of the mixed monomer solution with an initiator solution accounting for 15% of the mass of the initiator solution, introducing ethylene for the first time, keeping the pressure of a reaction system at 4MPa, reacting at 80 ℃ for 45min, dripping the rest mixed monomer solution and the rest initiator solution after the reaction is finished, introducing ethylene again after the dripping is finished, keeping the pressure of the reaction system at 7MPa, continuing to react for 4h at 80 ℃, and obtaining the reactive ethylene-vinyl acetate copolymer emulsion after the reaction is finished; the mass ratio of the alkenyl modified liquid nitrile rubber to the alkenyl modified nano silicon dioxide to the vinyl acetate to the azodiisobutyronitrile is 370:85:900:10;
step three, mixing ethylene-vinyl acetate copolymer emulsion, reactive ethylene-vinyl acetate copolymer emulsion and tackifying resin emulsion, wherein the mass ratio of the ethylene-vinyl acetate copolymer emulsion to the reactive ethylene-vinyl acetate copolymer emulsion to the tackifying resin emulsion is 76.5:19:4.5, obtaining the high-strength high-toughness adhesive.
Example 4
A preparation method of a high-strength high-toughness adhesive comprises the following steps:
adding amino-terminated liquid nitrile rubber and glycidyl acrylate into ethanol, wherein the mass ratio of the amino-terminated liquid nitrile rubber to the glycidyl acrylate to the ethanol is 35:2.2:400, adding 10wt% of sodium hydroxide aqueous solution to adjust the pH value to 11, reacting for 36 hours at the temperature of 40 ℃, adding 5wt% of hydrochloric acid aqueous solution to adjust the pH value to 7 after the reaction is finished, and removing ethanol by rotary evaporation to obtain alkenyl modified liquid nitrile rubber;
adding gamma-methacryloxypropyl trimethoxysilane into 95wt% ethanol water solution, adding 5wt% hydrochloric acid water solution to adjust the pH value to 5, and adding nano silicon dioxide, wherein the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the nano silicon dioxide to the ethanol water solution is 7.5:75:700, reacting for 2.5 hours at the temperature of 30 ℃, filtering after the reaction is finished, washing filter residues with ethanol, and drying in a vacuum drying oven at the temperature of 60 ℃ for 10 hours to obtain alkenyl modified nano silicon dioxide; the nano silicon dioxide is surface-activated nano silicon dioxide, and the surface-activated nano silicon dioxide is prepared by the following steps: the nano silicon dioxide is placed in 98 weight percent of concentrated sulfuric acid and 30 weight percent of hydrogen peroxide according to the volume ratio of 7:3, soaking the mixture in the prepared mixed solution for 2.5 hours at room temperature, filtering after soaking, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain the nano silicon dioxide with activated surface; adding alkenyl modified liquid nitrile rubber, alkenyl modified nano silicon dioxide and vinyl acetate into ethyl acetate, wherein the mass ratio of the alkenyl modified liquid nitrile rubber to the alkenyl modified nano silicon dioxide to the vinyl acetate is 375:90:1000:3500, uniformly mixing to obtain a mixed monomer solution, dissolving azobisisobutyronitrile in ethyl acetate, wherein the mass ratio of the azobisisobutyronitrile to the ethyl acetate is 10:102, obtaining an initiator solution; mixing a mixed monomer solution accounting for 25% of the mass of the mixed monomer solution with an initiator solution accounting for 15% of the mass of the initiator solution, introducing ethylene for the first time, keeping the pressure of a reaction system at 4MPa, reacting at 80 ℃ for 45min, dripping the rest mixed monomer solution and the rest initiator solution after the reaction is finished, introducing ethylene again after the dripping is finished, keeping the pressure of the reaction system at 7MPa, continuing to react for 4h at 80 ℃, and obtaining the reactive ethylene-vinyl acetate copolymer emulsion after the reaction is finished; the mass ratio of the alkenyl modified liquid nitrile rubber to the alkenyl modified nano silicon dioxide to the vinyl acetate to the azodiisobutyronitrile is 395:90:1000:10;
step three, mixing ethylene-vinyl acetate copolymer emulsion, reactive ethylene-vinyl acetate copolymer emulsion and tackifying resin emulsion, wherein the mass ratio of the ethylene-vinyl acetate copolymer emulsion to the reactive ethylene-vinyl acetate copolymer emulsion to the tackifying resin emulsion is 78:18:4, obtaining the high-strength high-toughness adhesive.
Example 5
A preparation method of a high-strength high-toughness adhesive comprises the following steps:
adding amino-terminated liquid nitrile rubber and glycidyl acrylate into ethanol, wherein the mass ratio of the amino-terminated liquid nitrile rubber to the glycidyl acrylate to the ethanol is 35:2.5:450, adding 10wt% of sodium hydroxide aqueous solution to adjust the pH value to 11.5, reacting for 30 hours at 45 ℃, adding 5wt% of hydrochloric acid aqueous solution to adjust the pH value to 7 after the reaction is finished, and removing ethanol by rotary evaporation to obtain alkenyl modified liquid nitrile rubber;
adding gamma-methacryloxypropyl trimethoxysilane into 95wt% ethanol water solution, adding 5wt% hydrochloric acid water solution to adjust the pH value to 5.5, and adding nano silicon dioxide, wherein the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the nano silicon dioxide to the ethanol water solution is 9:80:750, reacting for 2.5 hours at 30 ℃, filtering after the reaction is finished, washing filter residues with ethanol, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain alkenyl modified nano silicon dioxide; the nano silicon dioxide is surface-activated nano silicon dioxide, and the surface-activated nano silicon dioxide is prepared by the following steps: the nano silicon dioxide is placed in 98 weight percent of concentrated sulfuric acid and 30 weight percent of hydrogen peroxide according to the volume ratio of 7:3, soaking the mixture in the prepared mixed solution for 2.5 hours at room temperature, filtering after soaking, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain the nano silicon dioxide with activated surface; adding alkenyl modified liquid nitrile rubber, alkenyl modified nano silicon dioxide and vinyl acetate into ethyl acetate, wherein the mass ratio of the alkenyl modified liquid nitrile rubber to the alkenyl modified nano silicon dioxide to the vinyl acetate is 380:95:1100:3700, uniformly mixing to obtain a mixed monomer solution, dissolving azobisisobutyronitrile into ethyl acetate, wherein the mass ratio of the azobisisobutyronitrile to the ethyl acetate is 10:108, obtaining an initiator solution; mixing a mixed monomer solution accounting for 25% of the mass of the mixed monomer solution with an initiator solution accounting for 15% of the mass of the initiator solution, introducing ethylene for the first time, keeping the pressure of a reaction system at 4MPa, reacting at 80 ℃ for 45min, dripping the rest mixed monomer solution and the rest initiator solution after the reaction is finished, introducing ethylene again after the dripping is finished, keeping the pressure of the reaction system at 7MPa, continuing to react for 4h at 80 ℃, and obtaining the reactive ethylene-vinyl acetate copolymer emulsion after the reaction is finished; the mass ratio of the alkenyl modified liquid nitrile rubber to the alkenyl modified nano silicon dioxide to the vinyl acetate to the azodiisobutyronitrile is 380:95:1100:10;
step three, mixing ethylene-vinyl acetate copolymer emulsion, reactive ethylene-vinyl acetate copolymer emulsion and tackifying resin emulsion, wherein the mass ratio of the ethylene-vinyl acetate copolymer emulsion to the reactive ethylene-vinyl acetate copolymer emulsion to the tackifying resin emulsion is 79.5:17: and 3.5, obtaining the high-strength high-toughness adhesive.
Comparative example 1
A preparation method of a high-strength high-toughness adhesive comprises the following steps:
adding amino-terminated liquid nitrile rubber and glycidyl acrylate into ethanol, wherein the mass ratio of the amino-terminated liquid nitrile rubber to the glycidyl acrylate to the ethanol is 35:2.8:500, adding 10wt% of sodium hydroxide aqueous solution to adjust the pH value to 12, reacting for 24 hours at 50 ℃, adding 5wt% of hydrochloric acid aqueous solution to adjust the pH value to 7.5 after the reaction is finished, and removing ethanol by rotary evaporation to obtain alkenyl modified liquid nitrile rubber;
step two, adding alkenyl modified liquid nitrile rubber and vinyl acetate into ethyl acetate, wherein the mass ratio of the alkenyl modified liquid nitrile rubber to the vinyl acetate to the ethyl acetate is 385:1200:4000, uniformly mixing to obtain a mixed monomer solution, dissolving azobisisobutyronitrile into ethyl acetate, wherein the mass ratio of the azobisisobutyronitrile to the ethyl acetate is 10:115, obtaining an initiator solution; mixing a mixed monomer solution accounting for 30% of the mass of the mixed monomer solution with an initiator solution accounting for 20% of the mass of the initiator solution, introducing ethylene for the first time, keeping the pressure of a reaction system at 5MPa, reacting for 30min at 85 ℃, dripping the rest mixed monomer solution and the rest initiator solution after the reaction is finished, introducing ethylene again after the dripping is finished, keeping the pressure of the reaction system at 8MPa, continuing to react for 3h at 85 ℃, and obtaining the reactive ethylene-vinyl acetate copolymer emulsion after the reaction is finished; the mass ratio of the alkenyl modified liquid nitrile rubber to the vinyl acetate to the azodiisobutyronitrile is 385:1200:10;
step three, mixing ethylene-vinyl acetate copolymer emulsion, reactive ethylene-vinyl acetate copolymer emulsion, nano silicon dioxide and tackifying resin emulsion, wherein the mass ratio of the ethylene-vinyl acetate copolymer emulsion to the reactive ethylene-vinyl acetate copolymer emulsion to the nano silicon dioxide to the tackifying resin emulsion is 81.2:15:0.8: and 3, obtaining the high-strength high-toughness adhesive.
Comparative example 2
A preparation method of a high-strength high-toughness adhesive comprises the following steps:
adding gamma-methacryloxypropyl trimethoxysilane into 95wt% ethanol water solution, adding 5wt% hydrochloric acid water solution to adjust the pH value to 6, and adding nano silicon dioxide, wherein the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the nano silicon dioxide to the ethanol water solution is 10:90:800, reacting for 2 hours at 35 ℃, filtering after the reaction is finished, washing filter residues with ethanol, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain alkenyl modified nano silicon dioxide; the nano silicon dioxide is surface-activated nano silicon dioxide, and the surface-activated nano silicon dioxide is prepared by the following steps: the nano silicon dioxide is placed in 98 weight percent of concentrated sulfuric acid and 30 weight percent of hydrogen peroxide according to the volume ratio of 7:3, soaking the mixture in the prepared mixed solution for 3 hours at room temperature, filtering after soaking, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain the nano silicon dioxide with activated surface; adding alkenyl modified nano silicon dioxide and vinyl acetate into ethyl acetate, wherein the mass ratio of the alkenyl modified nano silicon dioxide to the vinyl acetate to the ethyl acetate is 100:1200:4000, uniformly mixing to obtain a mixed monomer solution, dissolving azobisisobutyronitrile into ethyl acetate, wherein the mass ratio of the azobisisobutyronitrile to the ethyl acetate is 10:115, obtaining an initiator solution; mixing a mixed monomer solution accounting for 30% of the mass of the mixed monomer solution with an initiator solution accounting for 20% of the mass of the initiator solution, introducing ethylene for the first time, keeping the pressure of a reaction system at 5MPa, reacting for 30min at 85 ℃, dripping the rest mixed monomer solution and the rest initiator solution after the reaction is finished, introducing ethylene again after the dripping is finished, keeping the pressure of the reaction system at 8MPa, continuing to react for 3h at 85 ℃, and obtaining the reactive ethylene-vinyl acetate copolymer emulsion after the reaction is finished; the mass ratio of the alkenyl modified nano silicon dioxide to the vinyl acetate to the azodiisobutyronitrile is 100:1200:10;
mixing ethylene-vinyl acetate copolymer emulsion, reactive ethylene-vinyl acetate copolymer emulsion, amino-terminated liquid nitrile rubber and tackifying resin emulsion, wherein the mass ratio of the ethylene-vinyl acetate copolymer emulsion to the reactive ethylene-vinyl acetate copolymer emulsion to the amino-terminated liquid nitrile rubber to the tackifying resin emulsion is 81.3:12.2:3.5: and 3, obtaining the high-strength high-toughness adhesive.
Comparative example 3
A preparation method of a high-strength high-toughness adhesive comprises the following steps: mixing ethylene-vinyl acetate copolymer emulsion, amino-terminated liquid nitrile rubber, nano silicon dioxide and tackifying resin emulsion, wherein the mass ratio of the ethylene-vinyl acetate copolymer emulsion to the amino-terminated liquid nitrile rubber to the nano silicon dioxide to the tackifying resin emulsion is 92.7:3.5:0.8: and 3, obtaining the high-strength high-toughness adhesive.
Comparative example 4
A preparation method of a high-strength high-toughness adhesive comprises the following steps:
adding amino-terminated liquid nitrile rubber and glycidyl acrylate into ethanol, wherein the mass ratio of the amino-terminated liquid nitrile rubber to the glycidyl acrylate to the ethanol is 35:2.8:500, adding 10wt% of sodium hydroxide aqueous solution to adjust the pH value to 12, reacting for 24 hours at 50 ℃, adding 5wt% of hydrochloric acid aqueous solution to adjust the pH value to 7.5 after the reaction is finished, and removing ethanol by rotary evaporation to obtain alkenyl modified liquid nitrile rubber;
step two, adding gamma-methacryloxypropyl trimethoxysilane into 95wt% ethanol aqueous solution, adding 5wt% hydrochloric acid aqueous solution to adjust the pH value to 6, and adding nano silicon dioxide, gamma-methacryloxypropyl trimethoxysilane and nano silicon dioxide, wherein the mass ratio of the ethanol aqueous solution is 10:90:800, reacting for 2 hours at 35 ℃, filtering after the reaction is finished, washing filter residues with ethanol, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain alkenyl modified nano silicon dioxide; the nano silicon dioxide is surface-activated nano silicon dioxide, and the surface-activated nano silicon dioxide is prepared by the following steps: the nano silicon dioxide is placed in 98 weight percent of concentrated sulfuric acid and 30 weight percent of hydrogen peroxide according to the volume ratio of 7:3, soaking the mixture in the prepared mixed solution for 3 hours at room temperature, filtering after soaking, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain the nano silicon dioxide with activated surface; adding alkenyl modified liquid nitrile rubber, alkenyl modified nano silicon dioxide and vinyl acetate into ethyl acetate, wherein the mass ratio of the alkenyl modified liquid nitrile rubber to the alkenyl modified nano silicon dioxide to the vinyl acetate is 385:100:1200:4000, uniformly mixing to obtain a mixed monomer solution, dissolving azobisisobutyronitrile into ethyl acetate, wherein the mass ratio of the azobisisobutyronitrile to the ethyl acetate is 10:115, obtaining an initiator solution; mixing a mixed monomer solution accounting for 30% of the mass of the mixed monomer solution with an initiator solution accounting for 20% of the mass of the initiator solution, introducing ethylene for the first time, keeping the pressure of a reaction system at 5MPa, reacting for 30min at 85 ℃, dripping the rest mixed monomer solution and the rest initiator solution after the reaction is finished, introducing ethylene again after the dripping is finished, keeping the pressure of the reaction system at 8MPa, continuing to react for 3h at 85 ℃, and obtaining the reactive ethylene-vinyl acetate copolymer emulsion after the reaction is finished; the mass ratio of the alkenyl modified liquid nitrile rubber to the alkenyl modified nano silicon dioxide to the vinyl acetate to the azodiisobutyronitrile is 385:100:1200:10;
step three, mixing the ethylene-vinyl acetate copolymer emulsion and the reactive ethylene-vinyl acetate copolymer emulsion, wherein the mass ratio of the ethylene-vinyl acetate copolymer emulsion to the reactive ethylene-vinyl acetate copolymer emulsion is 84:16, obtaining the high-strength high-toughness adhesive.
In the above examples and comparative examples, the amino-terminated liquid nitrile rubber was Hycar-ATBN (united states), the number average molecular weight was 3500, and the amino content was 17%; the ethylene-vinyl acetate copolymer emulsion is an ethylene-vinyl acetate copolymer emulsion, and is purchased from Nanjing Nannovixin materials Co., ltd., product number: 512. The tackifying resin emulsion is aqueous rosin tackifying resin emulsion, and is purchased from Guangzhou Masson chemical industry Co., ltd., brand: SB-919; the nanosilica is available from Shanghai Nameko nanotechnology Co., ltd., and has an average particle size of 500nm, cat: NO-O-001-2.
Test examples
Performance tests were performed on the high strength and high toughness adhesives prepared in examples 1-5 and comparative examples 1-4:
(1) Toughness testing: the toughness of the adhesive is measured by referring to the standard GB/T6328-2021, and the measurement results are shown in Table 1:
as shown in Table 1, the adhesive prepared by the invention has good toughness, and the impact strength reaches 34.5kJ/m 2 . The nano silicon dioxide and the nitrile rubber can provide toughness of the adhesive, the amino-terminated liquid nitrile rubber is subjected to epoxy reaction between the amino-terminated and glycidyl acrylate, alkenyl is introduced into the nitrile rubber, the nano silicon dioxide is subjected to reaction with gamma-methacryloxypropyl trimethoxy silane, alkenyl is introduced into the nano silicon dioxide, the alkenyl modified liquid nitrile rubber, the alkenyl modified nano silicon dioxide, vinyl acetate and ethylene are subjected to copolymerization reaction to obtain a reactive ethylene-vinyl acetate copolymer emulsion, the nano silicon dioxide and the nitrile rubber are grafted to the molecular structure of acetic acid-vinyl acetate copolymer in the reactive ethylene-vinyl acetate copolymer emulsion in a chemical bond mode through copolymerization reaction, and the copolymer in the reactive ethylene-vinyl acetate copolymer emulsion is similar to the structure of ethylene-vinyl acetate copolymer in the ethylene-vinyl acetate copolymer emulsion, so that the inorganic polymer is realizedThe effective combination of the organic toughening materials improves the dispersion uniformity of the inorganic toughening materials in the adhesive, thereby improving the toughness of the adhesive. Compared with the example 2, in the comparative example 1, nano silicon dioxide is grafted to the molecular structure of acetic acid-vinyl acetate copolymer in the reactive ethylene-vinyl acetate copolymer emulsion in a chemical bond mode through copolymerization reaction after not being modified by alkenyl, the dispersion compatibility of the nano silicon dioxide and the ethylene-vinyl acetate copolymer emulsion is poor, and the toughening effect of the adhesive is reduced; in comparative example 2, the amino-terminated liquid nitrile rubber is grafted onto the molecular structure of the acetic acid-vinyl acetate copolymer in the reactive ethylene-vinyl acetate copolymer emulsion in a chemical bond mode through copolymerization reaction after being not subjected to alkenyl modification, so that the dispersion compatibility of the amino-terminated liquid nitrile rubber and the ethylene-vinyl acetate copolymer emulsion is slightly reduced, and the toughening effect of the adhesive is also reduced; in comparative example 3, the nano silica and the amino-terminated liquid nitrile rubber are grafted onto the molecular structure of the acetic acid-vinyl acetate copolymer in the reactive ethylene-vinyl acetate copolymer emulsion in a chemical bond mode through copolymerization reaction after being subjected to alkenyl modification, so that the dispersion compatibility with the ethylene-vinyl acetate copolymer emulsion is reduced, and the toughening effect on the adhesive is obviously reduced; in comparative example 4, only the tackifying resin emulsion was not added, and there was no significant effect on the toughness of the adhesive.
(2) Adhesive property measurement: the viscosity of the adhesive was measured by a 4-cup viscometer; the adhesive strength of the adhesive was measured by referring to standard GB/T6548-2011, and the measurement results are shown in Table 2:
as can be seen from Table 2, the adhesive prepared by the present invention has good adhesive properties. In comparison with example 2, in comparative examples 1 to 3, the tackifying resin emulsions were added, and the adhesive properties of the adhesives were not changed; in comparative example 4, since the tackifying resin emulsion was not added, the adhesive property of the adhesive was lowered.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the high-strength high-toughness adhesive is characterized by comprising the following steps of:
adding amino-terminated liquid nitrile rubber and glycidyl acrylate into ethanol, adjusting the pH value to 10-12, reacting, adjusting the pH value to 6.5-7.5 after the reaction is finished, and performing rotary evaporation to obtain alkenyl modified liquid nitrile rubber;
step two, adding gamma-methacryloxypropyl trimethoxy silane into an ethanol water solution, adjusting the pH value to 4-6, adding nano silicon dioxide, reacting, and purifying after the reaction is finished to obtain alkenyl modified nano silicon dioxide; adding alkenyl modified liquid nitrile rubber, alkenyl modified nano silicon dioxide and vinyl acetate into ethyl acetate, uniformly mixing to obtain a mixed monomer solution, and dissolving azodiisobutyronitrile into the ethyl acetate to obtain an initiator solution; mixing a part of mixed monomer solution with a part of initiator solution, introducing ethylene for the first time, reacting, dripping the rest mixed monomer solution and the rest initiator solution after the reaction is finished, introducing ethylene again after the dripping is finished, continuing the reaction, and obtaining the reactive ethylene-vinyl acetate copolymer emulsion after the reaction is finished;
and thirdly, mixing the ethylene-vinyl acetate copolymer emulsion, the reactive ethylene-vinyl acetate copolymer emulsion and the tackifying resin emulsion to obtain the high-strength high-toughness adhesive.
2. The method for preparing the high-strength and high-toughness adhesive according to claim 1, wherein in the first step, the mass ratio of the amino-terminated liquid nitrile rubber to the glycidyl acrylate to the ethanol is 35: (1.4-2.8): (300-500), the reaction conditions are: reacting at 30-50 deg.C for 24-48h.
3. The method for preparing the high-strength and high-toughness adhesive according to claim 1, wherein in the second step, when preparing the alkenyl modified nano silicon dioxide, the mass ratio of gamma-methacryloxypropyl trimethoxysilane to nano silicon dioxide to ethanol aqueous solution is (5-10): (60-90): (600-800); the reaction conditions are as follows: reacting for 2-3h at 25-35 ℃.
4. The method for preparing a high-strength and high-toughness adhesive according to claim 1, wherein in the second step, when preparing the reactive ethylene-vinyl acetate copolymer emulsion, the mass ratio of the alkenyl modified liquid nitrile rubber, the alkenyl modified nano silica, the vinyl acetate and the azobisisobutyronitrile is (365-385): (80-100): (800-1200): 10.
5. the method for preparing the high-strength and high-toughness adhesive according to claim 1, wherein in the second step, when preparing the reactive ethylene-vinyl acetate copolymer emulsion, the mass ratio of the alkenyl modified liquid nitrile rubber, the alkenyl modified nano silicon dioxide, the vinyl acetate and the ethyl acetate in the mixed monomer solution is (365-385): (80-100): (800-1200): (3000-4000); the mass ratio of the azodiisobutyronitrile to the ethyl acetate in the initiator solution is 10: (90-115).
6. The method for preparing a high-strength and high-toughness adhesive according to claim 1, wherein in the second step, when preparing the reactive ethylene-vinyl acetate copolymer emulsion, the reaction conditions are as follows: reacting at 75-85deg.C for 30-60min; the conditions for continuing the reaction were: reacting for 3-5h at 75-85 ℃.
7. The method for preparing a high-strength and high-toughness adhesive according to claim 1, wherein in the second step, when preparing the reactive ethylene-vinyl acetate copolymer emulsion, a part of the mixed monomer solution accounts for 20-30% of the mass of the mixed monomer solution, and a part of the initiator solution accounts for 10-20% of the mass of the initiator solution; the ethylene is introduced for the first time in an amount that the pressure of the reaction system is kept at 3-5MPa; the ethylene was again introduced in an amount to maintain the pressure of the reaction system at 6 to 8MPa.
8. The method for preparing a high-strength and high-toughness adhesive according to claim 1, wherein in the third step, the mass ratio of the ethylene-vinyl acetate copolymer emulsion, the reactive ethylene-vinyl acetate copolymer emulsion and the tackifying resin emulsion is (75-81): (16-20): (3-5).
9. A high-strength high-toughness adhesive prepared by the method for preparing a high-strength high-toughness adhesive according to any one of claims 1 to 8.
10. Use of the high strength, high toughness adhesive of claim 9 in the processing of paper products.
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