CN116023630B - Preparation method of amine pressure-sensitive microcapsule curing agent - Google Patents
Preparation method of amine pressure-sensitive microcapsule curing agent Download PDFInfo
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- CN116023630B CN116023630B CN202211359761.7A CN202211359761A CN116023630B CN 116023630 B CN116023630 B CN 116023630B CN 202211359761 A CN202211359761 A CN 202211359761A CN 116023630 B CN116023630 B CN 116023630B
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- pressure
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 91
- 150000001412 amines Chemical class 0.000 title claims abstract description 86
- 239000003094 microcapsule Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011259 mixed solution Substances 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 24
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 6
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 18
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 10
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 10
- 229920000053 polysorbate 80 Polymers 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000011257 shell material Substances 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000011162 core material Substances 0.000 description 4
- XZUAPPXGIFNDRA-UHFFFAOYSA-N ethane-1,2-diamine;hydrate Chemical compound O.NCCN XZUAPPXGIFNDRA-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Manufacturing Of Micro-Capsules (AREA)
Abstract
The application provides a preparation method of an amine pressure-sensitive microcapsule curing agent, which comprises the following steps: (1) Dissolving an amine curing agent in deionized water to obtain a mixed solution A1; (2) Adding an emulsifying agent into cyclohexane to be uniformly dispersed to obtain a dispersion liquid A2; (3) Adding A1 into A2, and uniformly stirring at low speed to obtain mixed solution A3; (4) Mixing silicate and a silane coupling agent and then dissolving the mixture in cyclohexane to obtain a mixed solution A4; (5) Dropwise adding A4 into A3 under a heating condition to react for a period of time to obtain a mixed solution A5 containing amine pressure-sensitive microcapsule curing agents; (6) And (5) filtering A5, washing and drying the residual solid to obtain the amine pressure-sensitive microcapsule curing agent. The amine curing agent prepared by the application has high coating rate and good mechanical property; the curing time can be accurately regulated and controlled, the complete curing time is shortened to be within 24 hours, and the curing effect is improved; the preparation process is environment-friendly, simple, low in cost and beneficial to large-scale production.
Description
Technical Field
The application belongs to the technical field of self-repairing materials, and particularly relates to a preparation method of an amine pressure-sensitive microcapsule curing agent.
Background
The amine curing agent has the characteristics of low cost, easy availability, high reaction activity, variable performance and the like, and is most used in the market. However, the use of the polymer has a problem that the curing time is difficult to control because of its high reactivity. Microcapsule technology is to coat solid, liquid and gas with film-forming materials to form particles, and the prepared particles are called microcapsules. The microcapsule consists of two parts, wall material and capsule core. The capsule core is a substance coated in the microcapsule, and can be composed of one or more substances, the wall material is a coating film outside the microcapsule, and the amine curing agent is coated in the microcapsule to form solid powder, so that the solid powder can be conveniently stored and transported, and the curing time of the solid powder can be well controlled.
However, at present, the preparation process of the microcapsule curing agent is relatively sensitive to raw materials and reaction conditions, so that the amine microcapsule curing agent industrially used at home is relatively less, and meanwhile, the problems of low coating rate of the amine curing agent, complicated preparation process, special reaction reagent, non-environment-friendly organic reagent in the preparation process, poor experimental repeatability, high preparation cost and the like exist. And some of the amine microcapsule curing agents are mainly made of materials with lower heat resistance and poorer mechanical properties, so that the microcapsule curing agents are easy to crack, decompose or volatilize in advance, and the curing reaction is caused to occur in advance.
In view of the above technical problems, researchers have made much research. According to the tetraethyl orthosilicate coated epoxy resin microcapsule and the preparation method thereof disclosed in the CN103331134B application, the wall material coated epoxy resin is formed by hydrolysis polycondensation reaction of the tetraethyl orthosilicate under an acidic condition, so that the environment-friendly microcapsule with excellent heat stability, storage stability, no toxicity and no harm is obtained. However, the shell material prepared by the method has high brittleness and poor mechanical property, and the core material is spontaneously coated by the oil-in-water system, so that the coating effect is poor. In addition, as CN103285795A urea resin prepolymer or formaldehyde resin prepolymer is microcapsule wall material coated modified amine curing agent, but the preparation process is complex and the raw material price is high, and formaldehyde is used in the preparation process, so that the environment protection is not facilitated.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a preparation method of an amine pressure-sensitive microcapsule curing agent, which is characterized in that a silane coupling agent is used for connecting silicate and an amine curing agent to obtain a shell material with excellent mechanical properties and sacrifice a part of amine curing agent to obtain a higher coating rate of the amine curing agent. Specifically, the application is realized by the following technical scheme:
the application provides a preparation method of an amine pressure-sensitive microcapsule curing agent, which comprises the following steps:
(1) Dissolving an amine curing agent in deionized water to obtain a mixed solution A1;
(2) Adding an emulsifying agent into cyclohexane to be uniformly dispersed to obtain a dispersion liquid A2;
(3) Adding A1 into A2, and uniformly stirring at low speed to obtain mixed solution A3;
(4) Mixing silicate and a silane coupling agent and then dissolving the mixture in cyclohexane to obtain a mixed solution A4;
(5) Dropwise adding A4 into A3 under a heating condition to react for a period of time to obtain a mixed solution A5 containing amine pressure-sensitive microcapsule curing agents;
(6) And (5) filtering A5, washing and drying the residual solid to obtain the amine pressure-sensitive microcapsule curing agent.
The amine curing agent in the step (1) is one or more selected from ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
The cyclohexane in the step (2) can be replaced by n-hexane.
The emulsifier in the step (2) is one or more selected from nonionic emulsifiers, and the HLB value of the emulsifier is 5-6.
The silicate in the step (4) is selected from one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate.
The silane coupling agent in the step (4) is one or more selected from KH560, KH550, KH570 and KH 580.
The reagent washed in the step (6) is a nonpolar reagent and is selected from one or more of cyclohexane, n-hexane, acetone, toluene and xylene.
The mass ratio of the water added in the step (1) to the amine curing agent is 1: 1-5, and the dissolution temperature is 20-50 ℃.
The mass concentration of the emulsifier in the step (2) is 1-10%, the dispersion temperature is 20-50 ℃, and the mass ratio of the added amount of the emulsifier to the amine curing agent in the step (1) and the silicate in the step (4) is that the amine curing agent: emulsifying agent: silicate=3 to 7:1:2 to 5.
The mass ratio of silicate to silane coupling agent in the step (4) is 1-8:1.
The dripping time in the step (5) is 0.5-2 h, the reaction temperature is 40-60 ℃, and the reaction time is 1-3 h.
The drying temperature in the step (6) is 40-60 ℃ and the drying time is 1-3 h.
The amine pressure-sensitive microcapsule curing agent prepared according to the method takes silicon dioxide as a shell material and takes the amine curing agent as a core material.
The curing time of the amine pressure-sensitive microcapsule curing agent is 10 min-2 h.
The stirring speed and stirring time in the step (3) can influence the particle size, low-speed stirring is selected, and when the stirring speed is 300-1200 rpm, the stirring time is 10-20 min, and the particle size of the microcapsule curing agent can be controlled to be 4-16 um correspondingly; preferably, the stirring speed is 500 to 800rpm.
The amine pressure-sensitive microcapsule curing agent is irregularly spherical.
The coating rate of the amine curing agent in the amine pressure-sensitive microcapsule curing agent is 85% -94%.
The amine pressure-sensitive microcapsule curing agent is applied to the field of paint or coating.
The silicate is subjected to hydrolysis reaction in water under the alkaline condition provided by an amine curing agent to generate silicon hydroxyl when contacting with an aqueous solution of the amine curing agent. Epoxy groups on the silane coupling agent react with amine groups on the amine curing agent, and methoxy groups in the silane coupling agent also react on the surface of the aqueous solution of the amine curing agent in a hydrolysis manner to generate silicon hydroxyl groups. The silicon hydroxyl generated by the hydrolysis of the silane coupling agent and the silicon hydroxyl generated by the hydrolysis of the silicate are subjected to crosslinking condensation, and the silicon hydroxyl generated by the hydrolysis of the silicate is subjected to polycondensation reaction to crosslink the silicon hydroxyl to form the shell material. Compared with the prior art, the application has the following beneficial effects:
1. the silicate, the silane coupling agent and the amine curing agent are added, the silane coupling agent can be simultaneously connected with the shell material formed by the silicate and the amine curing agent, the coating rate of the amine curing agent in a system can be improved, and the cross-linking density of the microcapsule shell material is enhanced through the cross-linking of the silicate, the silane coupling agent and the amine curing agent, and the mechanical property of the microcapsule shell material is greatly improved;
2. according to the application, the amine curing agent is coated by adopting a microcapsule technology, and the prepared amine pressure-sensitive microcapsule curing agent can realize accurate regulation and control of the curing time of the material, so that the complete curing time is shortened to be within 24 hours, and the curing efficiency is greatly improved;
3. the amine pressure-sensitive microcapsule curing agent disclosed by the application is free from adding formaldehyde and other harmful substances in the preparation process, does not need to be additionally modified to enhance the mechanical properties of the microcapsule curing agent, is environment-friendly in preparation process, simple in preparation process, low in preparation cost and higher in storage stability, and is beneficial to large-scale production.
Detailed Description
The present application will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present application, but are not intended to limit the application in any way. It should be noted that variations and modifications can be made by those skilled in the art without departing from the spirit of the application, which falls within the scope of the application.
Example 1
(1) Dissolving 40g of ethylenediamine in 20g of deionized water to obtain an ethylenediamine aqueous solution;
(2) Uniformly dispersing 1g of Tween 80 and 5g of span 80 in 280ml of cyclohexane at 40 ℃ to obtain an emulsifier dispersion;
(3) Adding the ethylenediamine aqueous solution in the step (1) into the dispersion liquid in the step (2), and stirring at 600rpm for 10min;
(4) Mixing 30g of ethyl orthosilicate and 7.5g of KH560, dissolving in 120ml of cyclohexane, and stirring at 400rpm for 15min;
(5) Dripping the solution obtained in the step (4) into the solution obtained in the step (3) for 1h, and reacting for 2h at 50 ℃ to obtain a mixed solution containing amine pressure-sensitive microcapsule curing agents;
(6) And (3) carrying out suction filtration on the mixed solution in the step (5), washing with cyclohexane for 5 times, and drying at 60 ℃ for 2 hours to obtain the amine pressure-sensitive microcapsule curing agent.
Example 2
(1) Dissolving 40g of ethylenediamine in 8g of deionized water to obtain an ethylenediamine aqueous solution;
(2) Uniformly dispersing 1g of Tween 80 and 5g of span 80 in 280ml of cyclohexane at 40 ℃ to obtain an emulsifier dispersion;
(3) Adding the ethylenediamine aqueous solution in the step (1) into the dispersion liquid in the step (2), and stirring at 600rpm for 10min;
(4) Mixing 30g of ethyl orthosilicate and 7.5g of KH560, dissolving in 120ml of cyclohexane, and stirring at 400rpm for 15min;
(5) Dripping the solution obtained in the step (4) into the solution obtained in the step (3) for 1h, and reacting for 2h at 50 ℃ to obtain a mixed solution containing amine pressure-sensitive microcapsule curing agents;
(6) And (3) carrying out suction filtration on the mixed solution in the step (5), washing with cyclohexane for 5 times, and drying at 60 ℃ for 2 hours to obtain the amine pressure-sensitive microcapsule curing agent.
Example 3
(1) Dissolving 40g of ethylenediamine in 40g of deionized water to obtain an ethylenediamine aqueous solution;
(2) Uniformly dispersing 1g of Tween 80 and 5g of span 80 in 280ml of cyclohexane at 40 ℃ to obtain an emulsifier dispersion;
(3) Adding the ethylenediamine aqueous solution in the step (1) into the dispersion liquid in the step (2), and stirring at 600rpm for 10min;
(4) Mixing 30g of ethyl orthosilicate and 7.5g of KH560, dissolving in 120ml of cyclohexane, and stirring at 400rpm for 15min;
(5) Dripping the solution obtained in the step (4) into the solution obtained in the step (3) for 1h, and reacting for 2h at 50 ℃ to obtain a mixed solution containing amine pressure-sensitive microcapsule curing agents;
(6) And (3) carrying out suction filtration on the mixed solution in the step (5), washing with cyclohexane for 5 times, and drying at 60 ℃ for 2 hours to obtain the amine pressure-sensitive microcapsule curing agent.
Example 4
(1) Dissolving 40g of ethylenediamine in 40g of deionized water to obtain an ethylenediamine aqueous solution;
(2) Uniformly dispersing 2g of Tween 80 and 10g of span 80 in 280ml of cyclohexane at 40 ℃ to obtain an emulsifier dispersion;
(3) Adding the ethylenediamine aqueous solution in the step (1) into the dispersion liquid in the step (2), and stirring at 600rpm for 10min;
(4) Mixing 30g of ethyl orthosilicate and 7.5g of KH560, dissolving in 120ml of cyclohexane, and stirring at 400rpm for 15min;
(5) Dripping the solution obtained in the step (4) into the solution obtained in the step (3) for 1h, and reacting for 2h at 50 ℃ to obtain a mixed solution containing amine pressure-sensitive microcapsule curing agents;
(6) And (3) carrying out suction filtration on the mixed solution in the step (5), washing with cyclohexane for 5 times, and drying at 60 ℃ for 2 hours to obtain the amine pressure-sensitive microcapsule curing agent.
Example 5
(1) Dissolving 40g of ethylenediamine in 40g of deionized water to obtain an ethylenediamine aqueous solution;
(2) Uniformly dispersing 2g of Tween 80 and 10g of span 80 in 280ml of cyclohexane at 40 ℃ to obtain an emulsifier dispersion;
(3) Adding the ethylenediamine aqueous solution in the step (1) into the dispersion liquid in the step (2), and stirring at 600rpm for 10min;
(4) Mixing 30g of ethyl orthosilicate and 3.8g of KH560, dissolving in 120ml of cyclohexane, and stirring at 400rpm for 15min;
(5) Dripping the solution obtained in the step (4) into the solution obtained in the step (3) for 1h, and reacting for 2h at 50 ℃ to obtain a mixed solution containing amine pressure-sensitive microcapsule curing agents;
(6) And (3) carrying out suction filtration on the mixed solution in the step (5), washing with cyclohexane for 5 times, and drying at 60 ℃ for 2 hours to obtain the amine pressure-sensitive microcapsule curing agent.
Example 6
(1) Dissolving 40g of ethylenediamine in 40g of deionized water to obtain an ethylenediamine aqueous solution;
(2) Uniformly dispersing 2g of Tween 80 and 10g of span 80 in 280ml of cyclohexane at 40 ℃ to obtain an emulsifier dispersion;
(3) Adding the ethylenediamine aqueous solution in the step (1) into the dispersion liquid in the step (2), and stirring at 600rpm for 10min;
(4) Mixing 30g of ethyl orthosilicate and 30g of KH560, dissolving in 120ml of cyclohexane, and stirring at 400rpm for 15min;
(5) Dripping the solution obtained in the step (4) into the solution obtained in the step (3) for 1h, and reacting for 2h at 50 ℃ to obtain a mixed solution containing amine pressure-sensitive microcapsule curing agents;
(6) And (3) carrying out suction filtration on the mixed solution in the step (5), washing with cyclohexane for 5 times, and drying at 60 ℃ for 2 hours to obtain the amine pressure-sensitive microcapsule curing agent.
Example 7
(1) Dissolving 40g of tetraethylenepentamine in 20g of deionized water to obtain an ethylenediamine water solution;
(2) Uniformly dispersing 1g of Tween 80 and 5g of span 80 in 280ml of cyclohexane at 40 ℃ to obtain an emulsifier dispersion;
(3) Adding the ethylenediamine aqueous solution in the step (1) into the dispersion liquid in the step (2), and stirring at 600rpm for 10min;
(4) Mixing 30g of ethyl orthosilicate and 7.5g of KH560, dissolving in 120ml of cyclohexane, and stirring at 400rpm for 15min;
(5) Dripping the solution obtained in the step (4) into the solution obtained in the step (3) for 1h, and reacting for 2h at 50 ℃ to obtain a mixed solution containing amine pressure-sensitive microcapsule curing agents;
(6) And (3) carrying out suction filtration on the mixed solution in the step (5), washing with cyclohexane for 5 times, and drying at 60 ℃ for 2 hours to obtain the amine pressure-sensitive microcapsule curing agent.
Example 8
(1) Dissolving 40g of tetraethylenepentamine in 20g of deionized water to obtain an ethylenediamine water solution;
(2) Uniformly dispersing 1g of Tween 80 and 5g of span 80 in 280ml of cyclohexane at 40 ℃ to obtain an emulsifier dispersion;
(3) Adding the ethylenediamine aqueous solution in the step (1) into the dispersion liquid in the step (2), and stirring at 600rpm for 10min;
(4) Mixing 30g of ethyl orthosilicate and 7.5g of KH570, dissolving in 120ml of cyclohexane, and stirring at 400rpm for 15min;
(5) Dripping the solution obtained in the step (4) into the solution obtained in the step (3) for 1h, and reacting for 2h at 50 ℃ to obtain a mixed solution containing amine pressure-sensitive microcapsule curing agents;
(6) And (3) carrying out suction filtration on the mixed solution in the step (5), washing with cyclohexane for 5 times, and drying at 60 ℃ for 2 hours to obtain the amine pressure-sensitive microcapsule curing agent.
Example 9
(1) Dissolving 40g of tetraethylenepentamine in 20g of deionized water to obtain an ethylenediamine water solution;
(2) Uniformly dispersing 1g of Tween 80 and 5g of span 80 in 280ml of cyclohexane at 40 ℃ to obtain an emulsifier dispersion;
(3) Adding the ethylenediamine aqueous solution in the step (1) into the dispersion liquid in the step (2), and stirring for 20min at 300 rpm;
(4) Mixing 30g of ethyl orthosilicate and 7.5g of KH570, dissolving in 120ml of cyclohexane, and stirring at 400rpm for 15min;
(5) Dripping the solution obtained in the step (4) into the solution obtained in the step (3) for 1h, and reacting for 2h at 50 ℃ to obtain a mixed solution containing amine pressure-sensitive microcapsule curing agents;
(6) And (3) carrying out suction filtration on the mixed solution in the step (5), washing with cyclohexane for 5 times, and drying at 60 ℃ for 2 hours to obtain the amine pressure-sensitive microcapsule curing agent.
Example 10
(1) Dissolving 40g of tetraethylenepentamine in 20g of deionized water to obtain an ethylenediamine water solution;
(2) Uniformly dispersing 1g of Tween 80 and 5g of span 80 in 280ml of cyclohexane at 40 ℃ to obtain an emulsifier dispersion;
(3) Adding the ethylenediamine aqueous solution in the step (1) into the dispersion liquid in the step (2), and stirring for 10min at 1200 rpm;
(4) Mixing 30g of ethyl orthosilicate and 7.5g of KH570, dissolving in 120ml of cyclohexane, and stirring at 400rpm for 15min;
(5) Dripping the solution obtained in the step (4) into the solution obtained in the step (3) for 1h, and reacting for 2h at 50 ℃ to obtain a mixed solution containing amine pressure-sensitive microcapsule curing agents;
(6) And (3) carrying out suction filtration on the mixed solution in the step (5), washing with cyclohexane for 5 times, and drying at 60 ℃ for 2 hours to obtain the amine pressure-sensitive microcapsule curing agent.
Test results
The test results of the table show that the prepared amine pressure-sensitive microcapsule curing agent has higher coating rate, and the amine pressure-sensitive microcapsule curing agent prepared by the method has better mechanical property.
In addition, the amine-based pressure-sensitive microcapsule curing agent prepared in example 2 and isocyanate were mixed and reacted for 24 hours without pressing. After 24 hours, the isocyanate was found to be uncured. The amine pressure-sensitive microcapsule curing agent prepared by the application has good stability performance such as storage construction and good coating effect. And isocyanate was mixed with the amine-based pressure-sensitive microcapsule curing agent prepared in example 2, and the mixture was pressed to exude the curing agent in the microcapsules. The results showed that the mixture was completely cured 10min after pressing. The result shows that the amine pressure-sensitive microcapsule curing agent prepared by the application has shorter and controllable curing time.
Claims (8)
1. The preparation method of the amine pressure-sensitive microcapsule curing agent is characterized by comprising the following steps of:
(1) Dissolving an amine curing agent in deionized water to obtain a mixed solution A1;
(2) Adding an emulsifying agent into cyclohexane to be uniformly dispersed to obtain a dispersion liquid A2;
(3) Adding A1 into A2, and uniformly stirring at low speed to obtain mixed solution A3;
(4) Mixing silicate and a silane coupling agent and then dissolving the mixture in cyclohexane to obtain a mixed solution A4;
(5) Dropwise adding A4 into A3 under a heating condition to react for a period of time to obtain a mixed solution A5 containing amine pressure-sensitive microcapsule curing agents;
(6) Filtering A5, washing and drying the residual solid to obtain an amine pressure-sensitive microcapsule curing agent;
the amine curing agent in the step (1) is one or more selected from ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine;
the silane coupling agent in the step (4) is one or more selected from KH550, KH560, KH570 and KH 580;
the mass ratio of the added amount of the emulsifier in the step (2) to the amine curing agent in the step (1) to the silicate in the step (4) is that the amine curing agent: emulsifying agent: silicate=3 to 7:1:2 to 5.
2. The method for preparing an amine-based pressure-sensitive microcapsule curing agent according to claim 1, wherein the emulsifier in (2) is one or more of nonionic emulsifiers, and the HLB value of the emulsifier is 5-6.
3. The method for preparing an amine-based pressure-sensitive microcapsule curing agent according to claim 1, wherein the silicate in (4) is one or more selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate.
4. The method for preparing the amine-based pressure-sensitive microcapsule curing agent according to claim 1, wherein the mass ratio of deionized water to the amine-based curing agent in (1) is 1: 1-5, and the dissolution temperature is 20-50 ℃.
5. The method for preparing an amine-based pressure-sensitive microcapsule curing agent according to claim 1, wherein the mass concentration of the emulsifier in the cyclohexane in the step (2) is 1% -10%, and the dispersing temperature is 20-50 ℃.
6. The method for preparing an amine-based pressure-sensitive microcapsule curing agent according to claim 1, wherein the mass ratio of silicate to silane coupling agent in the step (4) is 1-8:1.
7. The method for preparing an amine-based pressure-sensitive microcapsule curing agent according to claim 1, wherein the time for dropping in (5) is 0.5-2 hours, the reaction temperature is 40-60 ℃, and the reaction time is 1-3 hours.
8. An amine-based pressure-sensitive microcapsule curing agent prepared by the method according to any one of claims 1 to 7, wherein the coating rate of the amine-based pressure-sensitive microcapsule curing agent is 85 to 94 percent.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103735533A (en) * | 2013-12-20 | 2014-04-23 | 中国科学院上海硅酸盐研究所 | Organic and inorganic compound nano-capsule agent and preparation method thereof |
| CN108993331A (en) * | 2018-07-27 | 2018-12-14 | 青岛理工大学 | Internal-repairing external-fixing type self-repairing microcapsule with cellular structure and preparation method thereof |
| CN111500264A (en) * | 2020-05-26 | 2020-08-07 | 常州大学 | Preparation method of hexadecanol-silicon dioxide phase change nano microcapsule |
| CN111621285A (en) * | 2020-04-30 | 2020-09-04 | 江南大学 | Organic/inorganic double-shell photochromic microcapsule and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103735533A (en) * | 2013-12-20 | 2014-04-23 | 中国科学院上海硅酸盐研究所 | Organic and inorganic compound nano-capsule agent and preparation method thereof |
| CN108993331A (en) * | 2018-07-27 | 2018-12-14 | 青岛理工大学 | Internal-repairing external-fixing type self-repairing microcapsule with cellular structure and preparation method thereof |
| CN111621285A (en) * | 2020-04-30 | 2020-09-04 | 江南大学 | Organic/inorganic double-shell photochromic microcapsule and preparation method thereof |
| CN111500264A (en) * | 2020-05-26 | 2020-08-07 | 常州大学 | Preparation method of hexadecanol-silicon dioxide phase change nano microcapsule |
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