CN116731666B - Waterproof quick-drying adhesive and preparation method thereof - Google Patents
Waterproof quick-drying adhesive and preparation method thereof Download PDFInfo
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- CN116731666B CN116731666B CN202311022790.9A CN202311022790A CN116731666B CN 116731666 B CN116731666 B CN 116731666B CN 202311022790 A CN202311022790 A CN 202311022790A CN 116731666 B CN116731666 B CN 116731666B
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- 239000004819 Drying adhesive Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000012745 toughening agent Substances 0.000 claims abstract description 27
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 11
- 239000002562 thickening agent Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- 229920013822 aminosilicone Polymers 0.000 claims description 28
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 17
- 238000002390 rotary evaporation Methods 0.000 claims description 16
- VGJWVEYTYIBXIA-UHFFFAOYSA-N 2,2,2-trifluoroethane-1,1-diol Chemical compound OC(O)C(F)(F)F VGJWVEYTYIBXIA-UHFFFAOYSA-N 0.000 claims description 14
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 239000005871 repellent Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 21
- 230000001070 adhesive effect Effects 0.000 abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 2
- 239000003292 glue Substances 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 12
- 238000007792 addition Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010907 mechanical stirring Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000004830 Super Glue Substances 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000012047 saturated solution Substances 0.000 description 4
- 229920001651 Cyanoacrylate Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 2
- 206010052428 Wound Diseases 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- -1 polysiloxane Polymers 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010998 test method Methods 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a waterproof quick-drying adhesive and a preparation method thereof, belonging to the technical field of adhesives. The waterproof quick-drying adhesive comprises the following components in parts by weight: 1000 parts of alpha-ethyl cyanoacrylate, 140-220 parts of waterproof toughening agent, 0.35-0.5 part of polymerization inhibitor, 0.05-0.07 part of stabilizer, 60-70 parts of thickener, 0.12-0.17 part of thixotropic agent and 40-50 parts of dispersing agent. The waterproof toughening agent is a chain macromolecular compound modified by fluorine-containing silicon long chains and double bonds, is inserted in a polymerization network to play roles in toughening and reducing shrinkage stress of a glue layer, effectively solves the problem of solidification brittleness of an alpha-cyanoacrylate-based quick-drying adhesive, has good water resistance for a silicon-containing chain, and has good water repellency for fluorine groups introduced by side chains, so that the adhesive is endowed with good water resistance.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a waterproof quick-drying adhesive and a preparation method thereof.
Background
The alpha-cyanoacrylate adhesive has good fluidity and single component use, can be widely applied to the adhesion of metals, rubber, plastics, ceramics and the like, and has the greatest characteristic of quick curing speed compared with other adhesives, and can finish curing within tens of seconds; the characteristic of the alpha-cyanoacrylate is that the alpha-cyanoacrylate has quick curing property, which is determined by the structure, because-CN and-COOR are strong electron-withdrawing groups, under the action of induction effect, on one hand, the electron cloud density of C atoms of alpha position is reduced, the alpha-cyanoacrylate is positive, and C atoms of beta position are easily attacked by nucleophilic reagents such as hydroxyl, amino and trace moisture, and then are used as active centers to attack C=C bonds in another molecule, so that polymerization curing is completed.
The 502 adhesive is a common cyanoacrylate adhesive in life, is simple and convenient to use and is favored, but has the following defects: firstly, the shrinkage stress of the adhesive layer after solidification is large, so that the mechanical property of the adhesive layer is poor, and the tensile shear strength is generally about 15 MPa; secondly, the ester group of the solidified layer is easily hydrolyzed by cyano and adsorbed water, so that the water stability is poor, the application shows that the construction bonding strength is low under high humidity or water environment, and the bonding performance is rapidly reduced to failure after soaking in water.
In order to solve the brittleness problem of cyanoacrylate adhesives, a certain toughening agent such as dioctyl phthalate is mainly compounded into the adhesives in the prior art, and the toughening agent achieves the purpose of toughening by reducing acting force among polymer chains, however, the addition of the plasticizing toughening agent damages a crosslinked network structure and is not easy to uniformly disperse, so that the adhesive performance is deteriorated. There are few reports on the waterproof performance of cyanoacrylate adhesives, szanka et al introduce cyanoacrylate acyloxy into long-chain polysiloxane and apply it to the protection of local wounds on skin surface, and the waterproof performance of the adhesive is improved by utilizing the waterproof performance of the polysiloxane. However, the cyanoacrylate has a low density of acyloxy groups and a low adhesive strength, and is only satisfactory for wound-covering adhesion, and is difficult to use as a high-strength adhesive. Therefore, the invention aims to provide a waterproof quick-drying adhesive.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide a waterproof quick-drying adhesive and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the waterproof quick-drying adhesive comprises the following components in parts by weight: 1000 parts of alpha-ethyl cyanoacrylate, 140-220 parts of waterproof toughening agent, 0.35-0.5 part of polymerization inhibitor, 0.05-0.07 part of stabilizer, 60-70 parts of thickener, 0.12-0.17 part of thixotropic agent and 40-50 parts of dispersing agent;
the waterproof toughening agent is prepared by the following method:
step A1: mixing trifluoroacetaldehyde hydrate, triethylamine and dioxane, mechanically stirring at 120-180rpm, heating to 80-90 ℃, intermittently adding epichlorohydrin, carrying out reflux reaction, controlling the total adding reaction time to be 1.5-2h, adding sodium hydroxide solution, mixing, steaming at 100 ℃ in a rotary way to remove low-boiling substances such as dioxane, water and the like, and filtering to obtain filtrate to obtain an intermediate 1;
further, the amount ratio of trifluoroacetaldehyde hydrate, epichlorohydrin, triethylamine, sodium hydroxide and dioxane was 0.1mol:0.23-0.25mol:3-4mL:6-9g:100-150mL, and performing ring opening reaction on hydroxyl in epichlorohydrin and trifluoroacetaldehyde hydrate under the catalysis of triethylamine, and then performing ring closure under the catalysis of strong alkali sodium hydroxide to form a terminal epoxy group, wherein the specific reaction process is as follows:
；
step A2: mixing amino silicone oil, N-diisopropylethylamine and tetrahydrofuran, mechanically stirring with 480-600rpm, keeping the temperature in a water bath at 35-45 ℃, slowly adding the intermediate 1, controlling the total adding reaction time to be 40-60min, and removing tetrahydrofuran by reduced pressure rotary evaporation after the reaction is finished to obtain an intermediate 2;
further, the amino content of the amino silicone oil and the molar ratio of the intermediate 1 are 1:1, N-diisopropylethylamine is 1.4-1.8wt% of amino silicone oil and intermediate 1, tetrahydrofuran is 1.2-1.5 times the volume of the amino silicone oil, wherein the amino silicone oil is preferably low viscosity terminal amino silicone oil supplied by Suzhou Jian-dao electronic Co., ltd, model PAM-E, viscosity at 25 ℃ of about 4mm 2 S; n, N-diisopropylethylamine is used as a catalyst, epoxy groups in the intermediate 1 and amino groups in amino silicone oil are subjected to ring opening reaction to form a fluorine-containing silicon chain polymer, and the specific reaction process is as follows:
；
step A3: mixing the intermediate 2 with butanone, keeping the temperature in an ice water bath at 0-5 ℃, adding ultrasonic vibration, slowly dropwise adding allyl chloride, stirring for reaction after dropwise adding, controlling the total adding reaction time to be 2-3h, and removing butanone and carrying out excessive allyl chloride after the reaction is finished by rotary evaporation to obtain the waterproof toughening agent.
Further, the ratio of the amount of intermediate 2, allyl chloride and butanone was 100g:10-14mL:150-200mL, the ultrasonic oscillation frequency is preferably 28-33kHz, the allyl chloride with high reactivity is substituted and reacted with the secondary amine group in the intermediate 2, and double bond modification is introduced into the intermediate 2, and the specific reaction process is as follows:
；
a preparation method of a waterproof quick-drying adhesive comprises the following specific operations: and (3) premixing the waterproof toughening agent, the polymerization inhibitor, the stabilizer, the thickener, the thixotropic agent and the dispersing agent uniformly, and then adding the premix into the ethyl alpha-cyanoacrylate for uniform mixing under the protection of dry nitrogen flow to obtain the waterproof quick-drying adhesive.
Further, the polymerization inhibitor is selected from hydroquinone.
Further, the stabilizer is selected from p-toluene sulfonic acid.
Further, the thickener is selected from polymethyl methacrylate.
Further, the thixotropic agent is selected from fumed silica.
Further, the dispersant is selected from acetone.
The invention has the beneficial effects that:
according to the invention, alpha-ethyl cyanoacrylate is used as a main material, and the anionic polymerization reaction can be initiated by water in the air, so that the curing and bonding effects are achieved, and the bonding performance of a curing layer is improved by doping a self-made waterproof toughening agent; the waterproof toughening agent comprises epichlorohydrin and trifluoroacetaldehyde hydrate which are taken as raw materials, and is prepared into an intermediate 1 containing fluorine and double-end epoxy groups through ring opening and ring closing reaction, then the intermediate 1 is subjected to ring opening polymerization with silicone oil containing terminal amino groups to prepare an intermediate 2 containing fluorine-silicon long chain structure, finally, the intermediate is substituted by high-activity allyl chloride and secondary amine groups in the chain, and double bond modification is introduced; the silicon-containing long chain has good compatibility with the alpha-ethyl cyanoacrylate matrix, and the silicon-containing long chain and the alpha-ethyl cyanoacrylate matrix are inserted into a polymerization network to play a role in toughening and reducing shrinkage stress of a glue layer, so that the problem of solidification brittleness of the alpha-ethyl cyanoacrylate-based quick-drying adhesive is effectively solved; in addition, the silicon-containing chain has good water resistance, and the fluorine group introduced by the side chain has good water repellency, so that the adhesive has good water resistance, and the adhesive has the tensile shear strength in water of 23.7-24.7MPa and the strength retention rate of 89.6-93.3% after being tested; in addition, the introduced double bond modification improves the compatibility with the alpha-ethyl cyanoacrylate, and meanwhile, the alpha-ethyl cyanoacrylate can participate in anionic polymerization, and the initial tensile shear strength of the adhesive is 25.4-27.1MPa and the bonding strength is higher than that of a comparative example.
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, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
For a full and clear description of the implementation process, the information of part of the raw materials is disclosed as follows:
ethyl α -cyanoacrylate, supplied by guangdong Weng Jiang chemical company, inc;
the polymerization inhibitor is selected from hydroquinone, which is provided by Hunan Chen technology Co., ltd;
stabilizers, all selected from p-toluenesulfonic acid, supplied by Nanjing Datang chemical industry Limited company;
the thickener is selected from polymethyl methacrylate, which is obtained from Hubei Wande chemical industry Co., ltd;
thixotropic agents, all selected from fumed silica, model number QS-102, supplied by Shenzhen Yi Punuo chemical industry Co., ltd;
dispersing agents, all selected from acetone, commercial AR grade reagent;
amino silicone oils, all selected from low viscosity amino terminated silicone oils, available from Suzhou Jian dao electronics Inc., model PAM-E,25℃viscosity of about 4mm 2 /s；
The remaining non-mentioned raw materials are commercial industrial raw materials.
Example 1
The waterproof quick-drying adhesive is prepared by the embodiment, and the specific implementation process is as follows:
1) Preparation of waterproof toughening agent
1.1, taking trifluoroacetaldehyde hydrate, triethylamine and dioxane as mixed materials, adding 180rpm for mechanical stirring, heating the raw materials to 90 ℃, adding epichlorohydrin into a reaction system for 3 times, wherein the intermittent time of each addition is 30min, continuing constant-temperature reflux reaction after the addition is completed, controlling the total addition reaction time of epichlorohydrin to be 1.5h, after the reaction is completed, dissolving sodium hydroxide into deionized water at room temperature to prepare saturated solution, adding sodium hydroxide into the reaction system, continuously heating to 100 ℃ for constant-temperature rotary evaporation, removing low-boiling-point substances such as dioxane, moisture and the like, and filtering the reaction solution to prepare an intermediate 1, wherein in the above reaction, the dosage ratio of trifluoroacetaldehyde hydrate, epichlorohydrin, triethylamine, sodium hydroxide and dioxane is 0.1mol:0.25mol:4mL:9g:150mL.
1.2, taking amino silicone oil, N-diisopropylethylamine and tetrahydrofuran, mixing and feeding, mechanically stirring at 600rpm, heating in a water bath, controlling the temperature to be constant at 45 ℃, slowly adding the intermediate 1 within 20min, keeping constant temperature stirring for reaction, controlling the total adding reaction time of the intermediate 1 to be 40min, and removing tetrahydrofuran by reduced pressure rotary evaporation after the reaction is finished to obtain an intermediate 2, wherein in the reaction, the molar ratio of the amino content of the amino silicone oil to the intermediate 1 is 1:1, N-diisopropylethylamine was 1.8% by weight of the aminosilicone and intermediate 1, and tetrahydrofuran was 1.5 times the volume of the aminosilicone.
1.3, taking intermediate 2 and butanone for mixing and feeding, adopting ice water bath to control the temperature to be constant at 0-5 ℃, assisting 33kHz ultrasonic vibration, slowly dropwise adding allyl chloride in 20min, removing ultrasonic vibration after adding, applying 360rpm mechanical stirring, controlling the total adding reaction time of the allyl chloride to be 2h, ending the reaction, steaming to remove butanone, and simultaneously removing excessive allyl chloride to obtain the waterproof toughening agent, wherein in the reaction, the dosage ratio of the intermediate 2, the allyl chloride and the butanone is 100g:14mL:200mL.
2) Preparation of waterproof quick-drying adhesive
2.1, 140 parts of waterproof toughening agent, 0.35 part of polymerization inhibitor, 0.06 part of stabilizer, 65 parts of thickener, 0.12 part of thixotropic agent and 40 parts of dispersing agent are calculated, and the raw materials are added into a stirrer and stirred and mixed for 1h at 240rpm to obtain premix;
2.2, feeding the alpha-ethyl cyanoacrylate under the protection of dry nitrogen, adding premix under the protection of dry nitrogen flow, and stirring at 120rpm for 30min to obtain the waterproof quick-drying adhesive.
Example 2
The waterproof quick-drying adhesive is prepared by the embodiment, and the specific implementation process is as follows:
1) Preparation of waterproof toughening agent
1.1, taking trifluoroacetaldehyde hydrate, triethylamine and dioxane mixture, adding materials by mechanical stirring at 120rpm, heating the raw materials to 80 ℃, adding epichlorohydrin into a reaction system for 4 times, wherein the intermittent time of each addition is 20min, continuing constant-temperature reflux reaction after the addition is completed, controlling the total addition reaction time of epichlorohydrin to be 2h, ending the reaction, taking sodium hydroxide to dissolve in deionized water at room temperature to prepare saturated solution, adding the sodium hydroxide into the reaction system, continuing heating to 100 ℃ for constant-temperature rotary evaporation, removing low-boiling-point substances such as dioxane, water and the like, and filtering the reaction solution to obtain an intermediate 1, wherein in the reaction, the dosage ratio of trifluoroacetaldehyde hydrate, epichlorohydrin, triethylamine, sodium hydroxide and dioxane is 0.1mol:0.23mol:3mL:6g:100mL.
1.2, taking amino silicone oil, N-diisopropylethylamine and tetrahydrofuran, mixing and feeding, adding 480rpm mechanical stirring, heating in a water bath, controlling the temperature to be constant at 35 ℃, slowly adding the intermediate 1 within 30min, keeping constant temperature stirring for reaction, controlling the total adding reaction time of the intermediate 1 to be 60min, and removing tetrahydrofuran by reduced pressure rotary evaporation after the reaction is finished to obtain an intermediate 2, wherein in the reaction, the molar ratio of the amino content of the amino silicone oil to the intermediate 1 is 1:1, N-diisopropylethylamine was 1.4% by weight of the aminosilicone and intermediate 1, and tetrahydrofuran was 1.2 times the volume of the aminosilicone.
1.3, taking intermediate 2 and butanone for mixing and feeding, adopting ice water bath to control the temperature to be constant at 0-5 ℃, assisting in 28kHz ultrasonic vibration, slowly dropwise adding allyl chloride in 30min, removing ultrasonic vibration after adding, applying 240rpm mechanical stirring, controlling the total adding reaction time of the allyl chloride to be 3h, and removing butanone by rotary evaporation after the reaction is finished, and simultaneously removing excessive allyl chloride to obtain the waterproof toughening agent, wherein in the reaction, the dosage ratio of the intermediate 2, the allyl chloride and the butanone is 100g:10mL:150mL.
2) Preparation of waterproof quick-drying adhesive
2.1, 220 parts of waterproof toughening agent, 0.5 part of polymerization inhibitor, 0.05 part of stabilizer, 60 parts of thickener, 0.17 part of thixotropic agent and 50 parts of dispersing agent are calculated, and the raw materials are added into a stirrer and stirred and mixed for 1h at 240rpm to obtain premix;
2.2, feeding the alpha-ethyl cyanoacrylate under the protection of dry nitrogen, adding premix under the protection of dry nitrogen flow, and stirring at 120rpm for 30min to obtain the waterproof quick-drying adhesive.
Example 3
The waterproof quick-drying adhesive is prepared by the embodiment, and the specific implementation process is as follows:
1) Preparation of waterproof toughening agent
1.1, taking trifluoroacetaldehyde hydrate, triethylamine and dioxane as mixed materials, adding 180rpm for mechanical stirring, heating the raw materials to 85 ℃, adding epichlorohydrin into a reaction system for 3 times, wherein the intermittent time of each addition is 25min, continuing constant-temperature reflux reaction after the addition is completed, controlling the total addition reaction time of epichlorohydrin to be 1.8h, after the reaction is completed, dissolving sodium hydroxide into deionized water at room temperature to prepare saturated solution, adding sodium hydroxide into the reaction system, continuously heating to 100 ℃ for constant-temperature rotary evaporation, removing low-boiling-point substances such as dioxane and moisture, and filtering the reaction solution to prepare an intermediate 1, wherein in the above reaction, the dosage ratio of trifluoroacetaldehyde hydrate, epichlorohydrin, triethylamine, sodium hydroxide and dioxane is 0.1mol:0.24mol:4mL:7g:120mL.
1.2, taking amino silicone oil, N-diisopropylethylamine and tetrahydrofuran, mixing and feeding, mechanically stirring at 540rpm, heating in a water bath, controlling the temperature to be constant at 40 ℃, slowly adding the intermediate 1 within 25min, keeping constant temperature stirring for reaction after adding, controlling the total adding reaction time of the intermediate 1 to be 50min, and removing tetrahydrofuran by reduced pressure rotary evaporation after the reaction is finished to obtain an intermediate 2, wherein in the reaction, the molar ratio of the amino content of the amino silicone oil to the intermediate 1 is 1:1, N-diisopropylethylamine was 1.6% by weight of the aminosilicone and intermediate 1, and tetrahydrofuran was 1.3 times the volume of the aminosilicone.
1.3, taking intermediate 2 and butanone for mixing and feeding, adopting ice water bath to control the temperature to be constant at 0-5 ℃, assisting in 28kHz ultrasonic vibration, slowly dropwise adding allyl chloride in 30min, removing ultrasonic vibration after adding, applying 360rpm mechanical stirring, controlling the total adding reaction time of the allyl chloride to be 2.5h, and removing butanone by rotary evaporation after the reaction is finished, and simultaneously removing excessive allyl chloride to obtain the waterproof toughening agent, wherein in the reaction, the dosage ratio of the intermediate 2, the allyl chloride and the butanone is 100g:12mL:180mL.
2) Preparation of waterproof quick-drying adhesive
2.1, 185 parts of waterproof toughening agent, 0.42 part of polymerization inhibitor, 0.06 part of stabilizer, 70 parts of thickener, 0.16 part of thixotropic agent and 45 parts of dispersing agent are calculated, and all the raw materials are added into a stirrer and stirred and mixed for 1h at 240rpm to obtain premix;
2.2, feeding the alpha-ethyl cyanoacrylate under the protection of dry nitrogen, adding premix under the protection of dry nitrogen flow, and stirring at 120rpm for 30min to obtain the waterproof quick-drying adhesive.
Example 4
The waterproof quick-drying adhesive is prepared by the embodiment, and the specific implementation process is as follows:
1) Preparation of waterproof toughening agent
1.1, taking trifluoroacetaldehyde hydrate, triethylamine and dioxane as mixed materials, adding 120rpm mechanical stirring to heat the raw materials to 85 ℃, adding epichlorohydrin into a reaction system for 4 times, wherein the intermittent time of each addition is 20min, continuing constant-temperature reflux reaction after the addition is completed, controlling the total addition reaction time of epichlorohydrin to be 1.8h, after the reaction is completed, dissolving sodium hydroxide into deionized water at room temperature to prepare saturated solution, adding sodium hydroxide into the reaction system, continuing to heat to 100 ℃ for constant-temperature rotary evaporation, removing low-boiling-point substances such as dioxane and moisture, and filtering the reaction solution to prepare an intermediate 1, wherein in the above reaction, the dosage ratio of trifluoroacetaldehyde hydrate, epichlorohydrin, triethylamine, sodium hydroxide and dioxane is 0.1mol:0.24mol:4mL:8g:130mL.
1.2, taking amino silicone oil, N-diisopropylethylamine and tetrahydrofuran, mixing and feeding, mechanically stirring at 540rpm, heating in a water bath, controlling the temperature to be constant at 40 ℃, slowly adding the intermediate 1 within 25min, keeping constant temperature stirring for reaction after adding, controlling the total adding reaction time of the intermediate 1 to be 55min, and removing tetrahydrofuran by reduced pressure rotary evaporation after the reaction is finished to obtain an intermediate 2, wherein in the reaction, the molar ratio of the amino content of the amino silicone oil to the intermediate 1 is 1:1, N-diisopropylethylamine was 1.5% by weight of the aminosilicone and intermediate 1, and tetrahydrofuran was 1.4 times the volume of the aminosilicone.
1.3, taking intermediate 2 and butanone for mixing and feeding, adopting ice water bath to control the temperature to be constant at 0-5 ℃, assisting 33kHz ultrasonic vibration, slowly dropwise adding allyl chloride in 30min, removing ultrasonic vibration after adding, applying 360rpm mechanical stirring, controlling the total adding reaction time of the allyl chloride to be 2.2h, and removing butanone by rotary evaporation after the reaction is finished, and simultaneously removing excessive allyl chloride to obtain the waterproof toughening agent, wherein the dosage ratio of the intermediate 2, the allyl chloride and the butanone is 100g in the reaction: 12mL:180mL.
2) Preparation of waterproof quick-drying adhesive
2.1, taking 170 parts of waterproof toughening agent, 0.4 part of polymerization inhibitor, 0.07 part of stabilizer, 70 parts of thickener, 0.14 part of thixotropic agent and 45 parts of dispersing agent, adding the raw materials into a stirrer, and stirring and mixing for 1h at 240rpm to obtain premix;
2.2, feeding the alpha-ethyl cyanoacrylate under the protection of dry nitrogen, adding premix under the protection of dry nitrogen flow, and stirring at 120rpm for 30min to obtain the waterproof quick-drying adhesive.
Comparative example
The comparative example is a commercially available toughened cyanoacrylate quick-drying adhesive, and the specific model is le tai 480.
The following performance tests were performed with the adhesives prepared in examples 1-4 and the instant adhesives provided in the comparative examples:
viscosity test: with reference to GB/T2794-2022 standard, the test temperature is 25+/-0.5 ℃;
curing time test: referring to GB/T7124-2008 standard, the test temperature is 25+/-0.5 ℃ and the humidity is 60+/-5%;
tensile shear strength test: referring to QB/T2568-2002 standard, taking a PVC plate as an adhesion sample, setting the curing conditions as follows: the temperature is 25 ℃, the humidity is 80 percent, and the time is 24 hours;
the specific test results are shown in table 1:
table 1 results of the bond strength test for examples and comparative examples
As can be seen from the data in Table 1, the viscosity of the adhesive prepared in the examples is 147-165 mPa.s, the adhesive is moderate in viscosity and easier to coat and construct compared with the comparative examples, the curing time is 97-112s, the adhesive is similar to and slightly higher than the comparative examples, a longer curing period is required in practical application, the tensile shear strength is 25.4-27.1MPa, and the adhesive strength is slightly higher than the comparative examples.
Based on the above test data, to verify the water resistance of the above adhesive, referring to the tensile shear strength test method, after the sample is bonded and solidified, the sample is immersed in hot water at 60 ℃, immersed for 24 hours at constant temperature, taken out, dried by a hot air blower, cooled to room temperature, subjected to tensile shear strength test again, and measured for strength retention in water environment, and specific test data are shown in table 2:
table 2 results of the waterproof property test of examples and comparative examples
As can be seen from the data in Table 2, the adhesive prepared in the examples has a tensile shear strength in water of 23.7-24.7MPa and a strength retention of 89.6-93.3%, and exhibits excellent water resistance as compared with the comparative examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (8)
1. The waterproof quick-drying adhesive is characterized by comprising the following components in parts by weight: 1000 parts of alpha-ethyl cyanoacrylate, 140-220 parts of waterproof toughening agent, 0.35-0.5 part of polymerization inhibitor, 0.05-0.07 part of stabilizer, 60-70 parts of thickener, 0.12-0.17 part of thixotropic agent and 40-50 parts of dispersing agent;
the waterproof toughening agent is prepared by the following method:
step A1: mixing trifluoroacetaldehyde hydrate, triethylamine and dioxane, stirring and heating to 80-90 ℃, intermittently adding epichlorohydrin for reflux reaction, controlling the total adding reaction time to be 1.5-2h, adding sodium hydroxide solution for mixing, removing low-boiling substances by rotary evaporation at 100 ℃, and filtering to obtain filtrate to obtain an intermediate 1;
step A2: mixing amino silicone oil, N-diisopropylethylamine and tetrahydrofuran, stirring, keeping the temperature at 35-45 ℃ in a water bath, slowly adding the intermediate 1, controlling the total adding reaction time to be 40-60min, and removing the tetrahydrofuran by reduced pressure rotary evaporation after the reaction is finished to obtain an intermediate 2;
step A3: mixing the intermediate 2 with butanone, keeping the temperature in an ice water bath at 0-5 ℃, adding ultrasonic vibration, slowly dropwise adding allyl chloride, stirring for reaction after dropwise adding, controlling the total adding reaction time to be 2-3h, and removing the butanone after the reaction is finished by rotary evaporation to obtain the waterproof toughening agent.
2. The waterproof quick-drying adhesive according to claim 1, wherein the usage ratio of trifluoroacetaldehyde hydrate, epichlorohydrin, triethylamine, sodium hydroxide and dioxane is 0.1mol:0.23-0.25mol:3-4mL:6-9g:100-150mL.
3. The waterproof quick-drying adhesive according to claim 2, wherein the molar ratio of the amino content of the amino silicone oil to the intermediate 1 is 1:1, N-diisopropylethylamine is 1.4-1.8wt% of amino silicone oil and intermediate 1, and tetrahydrofuran is 1.2-1.5 times the volume of the amino silicone oil.
4. The waterproof quick-drying adhesive according to claim 3, wherein the dosage ratio of the intermediate 2, allyl chloride and butanone is 100g:10-14mL:150-200mL.
5. A method for preparing the waterproof quick-drying adhesive according to any one of claims 1 to 4, which is characterized by comprising the following specific operations: and (3) premixing the waterproof toughening agent, the polymerization inhibitor, the stabilizer, the thickener, the thixotropic agent and the dispersing agent uniformly, and then adding the premix into the ethyl alpha-cyanoacrylate for uniform mixing under the protection of dry nitrogen flow to obtain the waterproof quick-drying adhesive.
6. The method for preparing a water-proof quick-drying adhesive according to claim 5, wherein the stabilizer is p-toluenesulfonic acid.
7. The method for preparing a water-repellent quick-drying adhesive according to claim 5, wherein the thixotropic agent is fumed silica.
8. The method for preparing a waterproof quick-drying adhesive according to claim 5, wherein the dispersing agent is acetone.
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