CN111135999A - Engineering application method of microcapsule sealant based on urea-formaldehyde resin - Google Patents
Engineering application method of microcapsule sealant based on urea-formaldehyde resin Download PDFInfo
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- CN111135999A CN111135999A CN201911317479.0A CN201911317479A CN111135999A CN 111135999 A CN111135999 A CN 111135999A CN 201911317479 A CN201911317479 A CN 201911317479A CN 111135999 A CN111135999 A CN 111135999A
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- microcapsule
- sealant
- urea
- formaldehyde resin
- engineering application
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- 239000000565 sealant Substances 0.000 title claims abstract description 99
- 239000003094 microcapsule Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229920001807 Urea-formaldehyde Polymers 0.000 title claims abstract description 20
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 title claims abstract description 19
- 239000000853 adhesive Substances 0.000 claims abstract description 28
- 230000001070 adhesive effect Effects 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 238000012360 testing method Methods 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 9
- 238000004073 vulcanization Methods 0.000 claims description 47
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 229910021538 borax Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000004328 sodium tetraborate Substances 0.000 description 11
- 230000008859 change Effects 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 239000002775 capsule Substances 0.000 description 9
- 230000001066 destructive effect Effects 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 239000008393 encapsulating agent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 241001391944 Commicarpus scandens Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 241000587161 Gomphocarpus Species 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QDNBHWFDWXWFTG-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1.OC1=CC=CC(O)=C1 QDNBHWFDWXWFTG-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent 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
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
-
- 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
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2518/00—Other type of polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention belongs to the technical field of novel materials, and discloses an engineering application method of a microcapsule sealant based on urea-formaldehyde resin, which comprises the following steps: s1, mixing the dried microcapsule particles with a curing agent according to the mass ratio of 100: 17; s2, adding an adhesive into the mixture obtained in the step S1, and uniformly mixing; s3, pre-coating the mixture obtained in the step S2 on the surface of a test piece, and drying; s4, solidifying the surface of the pre-coated test piece for a preset time at normal temperature to finish pre-coating, realizing the engineering application of the microcapsule sealant based on the urea-formaldehyde resin, and greatly improving the production and assembly efficiency of the equipment.
Description
Technical Field
The invention belongs to the technical field of novel materials, and particularly relates to an engineering application method of a microcapsule sealant based on urea-formaldehyde resin.
Background
The microcapsule sealant sealing technology is a brand new sealing technology. The active substance (capsule core substance) is coated by a polymer film-forming material through a certain process to form micro particles. The sealant in the microcapsule is slowly released in the using process, so that the sealing efficiency is effectively prolonged, and the service life of the sealant is prolonged by 50% compared with that of the traditional sealant. The microcapsule preparation technology has the main advantages that the microcapsule has a special core/shell structure, the capsule has the function of effectively isolating capsule core objects from the external environment, so that the capsule core can be prevented from being influenced by external temperature, oxygen, humidity, ultraviolet rays and other environmental factors, and the capsule wall can be released after being damaged under the influence of pressurization, temperature rise or other external factors, thereby improving the environmental stability and the construction performance of active substances; or the capsule core can diffuse outwards through the capsule wall under the condition of not damaging the capsule wall so as to achieve the purpose of controlled release. The application research of the microcapsule sealant can solve the sealing problem of large strain structures at the bottoms of equipment such as seaplanes, ships and the like; by applying the high corrosion resistance design of the microcapsule sealant, the corrosion resistance of the equipment connecting structure can be effectively improved; the precoating performance of the microcapsule sealant is utilized, so that the production and assembly efficiency of equipment is greatly improved; simultaneously, the production and assembly cost of the equipment can be effectively reduced.
The sealing of equipment such as domestic airplanes and the like mainly adopts a wet assembly mode of spraying primer and dipping sealant, so that the problems of cracking of a sealing layer after structural deformation, complex sealing process and the like exist, and the corrosion problem caused by sealing failure generally exists in airplanes. At present, the application of the microcapsule sealant on an airplane is not available in China, and most of the microcapsule sealants stay in a laboratory stage.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a process application method of a microcapsule sealant based on urea-formaldehyde resin, which obtains the optimal pre-coating process of the microcapsule sealant by researching the influence of different mixing ratios of sealant particles, curing time, drying temperature and the like on the destructive moment, the disassembly moment and the corrosion protection performance of the sealant, realizes the engineering application of the microcapsule sealant based on urea-formaldehyde resin, and greatly improves the production and assembly efficiency of equipment.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for the engineered application of a urea-formaldehyde resin based microcapsule sealant, the method comprising:
s1, mixing the dried microcapsule particles with a curing agent according to the mass ratio of 100: 17;
s2, adding an adhesive into the mixture obtained in the step S1, and uniformly mixing;
s3, pre-coating the mixture obtained in the step S2 on the surface of a test piece, and drying;
and S4, curing the surface of the pre-coated test piece for a preset time at normal temperature to finish the pre-coating.
The technical scheme of the invention has the characteristics and further improvements that:
(1) in S1, the curing agent is a vulcanizing agent.
(2) In S2, the adhesive is polyvinyl formal.
(3) The synthesis process conditions of the polyvinyl formal are as follows:
the polyvinyl formal is obtained by condensation with 6mol/L hydrochloric acid and 10% polyvinyl alcohol-1799 (PVA-1799) which is completely dissolved at 95 ℃.
(4) The polyvinyl formal synthesis process comprises the following components in percentage by mass:
m (H2O), m (PVA-1799) and m (formaldehyde) 10:1: 0.7.
(5) In S3, the drying temperature is 25 ℃.
(6) In S4, the preset time is 18 hours.
(7) After S1 and before S2, the method further comprises:
sodium thiosulfate was added to the mixture obtained in S1 to accelerate the vulcanization process.
The invention is based on the best preparation process parameters of the microcapsule sealant taking the urea-formaldehyde polymer as the capsule wall material, and obtains the best pre-coating process of the microcapsule sealant by researching the influence of different mixing ratios, curing time, drying temperature and the like of the sealant particles on the destructive moment, the disassembly moment and the corrosion protection performance of the sealant, thereby solving the difficult problem of engineering application of the microcapsule sealant based on the urea-formaldehyde resin and greatly improving the assembly efficiency of equipment.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The microcapsule sealant engineering application method based on the urea-formaldehyde resin provided by the invention comprises the following steps: the influence of the mixing ratio of the composite particles and other components of the sealant on the microcapsule sealant, the influence of the coating and curing time on the performance of the microcapsule sealant, the influence of the drying temperature on the microcapsule sealant and the pre-coating exemplary application of the microcapsule sealant.
1. Effect of the mixing ratio of the composite particles with other components of the sealant on the microcapsule sealant
(1) Adjustment of alkalinity of mixed sealant curing agent and microcapsule
Selecting low-pollution and volatile ethyl acetate as a solvent, mixing the prepared microcapsule particles with other components of the sealant, in the process, because the alkalinity of sodium sulfide and sodium hydroxide is too strong and is not suitable for being added in a vulcanization reaction, mixing a certain amount of alkaline substances to recover the damaged weakly alkaline vulcanization condition, then, placing a test sample at room temperature, observing the change condition generated on the surface of the mixture, and further screening out a suitable additive. As shown in table 1.
TABLE 1 vulcanization Effect of sealants with different additives
| Numbering | Step (ii) of | Phenomenon after drying (50 ℃ C.) |
| 1 | 2d 10% hexamethylenetetramine (pH 8) | Is brittle and inelastic |
| 2 | 2d 10% sodium carbonate (pH 7-8) | It is brittle, inelastic, and whitish |
| 3 | 2d 10% sodium bicarbonate (pH 8) | Easy to break and has elasticity |
| 4 | 2d 10% sodium thiosulfate (pH 7) | Is not easy to break and has elasticity |
| 5 | 2d 10% sodium sulfite (pH 9) | Easy breakage and poor elasticity |
| 6 | 2d 10% sodium nitrite (pH 7) | Easy to break and has elasticity |
| 7 | 2d 10% sodium bisulfite (pH 5-6) | Is fragile, has large color change and no elasticity, and has no vulcanization reaction |
The test results show that in the case of sodium thiosulfate as an additive, the sample after vulcanization does not easily break and has a certain elasticity, so that a certain amount of sodium thiosulfate is added during the pre-coating process to promote the vulcanization process.
(2) Effect of film selection on sealant application
After the prepared microcapsule and the curing agent thereof are determined to be subjected to vulcanization reaction, a proper adhesive is selected to connect the sealant and the screwed and riveted test piece, so as to ensure that the microcapsule sealant can be fixed on the surface of the test piece and cannot easily fall off after pre-coating (see tables 2 and 3).
Table 2 conditions after curing of the different adhesives
| Numbering | Step (ii) of | Post cure phenomena of adhesive (50 ℃ C.) |
| 1 | E-44 epoxy resin | Transparent and brittle, and can not form a tearable film |
| 2 | PVA-borax (2%) solidification | Transparent and hard, no tearable film can be formed |
| 3 | 107 adhesive | Transparent and capable of forming a tearable film |
| 4 | Resorcinol-phenol-formaldehyde adhesive | Reddish brown is harder and dries slowly |
TABLE 3 curing and vulcanization of different adhesives and rubbers after mixing, coating and drying
| Numbering | Step (ii) of | Post-baking phenomena of adhesive + sealant (50 ℃ C.) |
| 1 | E-44 epoxy resin | Hard non-tearing rubber film |
| 2 | PVA-borax (2%) solidification | Hard non-tearing rubber film |
| 3 | 107 adhesive | Rubber hardened tearable film |
According to the test results, although the epoxy resin film and the PVA-borax (2%) cured film are hard films which cannot be torn off, the epoxy resin film needs a longer time to be cured, and the PVA-borax (2%) cured film has the characteristic of short curing time, and can be torn off in a sheet mode under the action of a certain force after the 107 glue film is cured, and the PVA-borax (2%) cured film is also a suitable material for pre-coating adhesive.
According to the PVA-borax (2%) curing principle, the polyvinyl alcohol with high polymerization degree and high viscosity is selected to be more in line with the coating requirement, so that the best conditions for curing are selected by selecting the polyvinyl alcohol-124 (PVA-124) and 2% borax solution at different temperatures. See table 4.
TABLE 4 post-cure phenomena under different curing conditions
The experimental result shows that in the experiment of borax curing polyvinyl alcohol-124, a hard film can be obtained through curing within the temperature range of 25-45 ℃, when the concentration of polyvinyl alcohol is low, the film is very thin, the phenomenon of delamination can occur after curing, the strength is not enough to be used as an adhesive of a microcapsule sealant, the thickness of the film is increased along with the increase of the concentration of polyvinyl alcohol, the strength is correspondingly improved, and the phenomenon of delamination also disappears. When the polyvinyl alcohol content reaches 5%, the cured rigid film may have bubbles and wrinkles, and small particles of polyvinyl alcohol that have not been completely swollen may be present, and the film may not be very uniform. And when the concentration of the polyvinyl alcohol is kept unchanged, comparing the influence of the temperature on the curing effect. The formed hard film has uneven thickness and non-smoothness of wrinkles. All the influencing factors are combined, and the polyvinyl alcohol with the concentration of 3 percent is selected, and the film is cured at normal temperature to form a film more suitably.
Putting 3% of PVA-124 into a mixture of microcapsules and a curing agent which are mixed according to a certain proportion to ensure that the mixture has better fluidity, uniformly coating the mixture on the surface of an M10 bolt, immediately soaking the bolt into a 2% borax solution for curing for 10 seconds, taking out the bolt, and assembling the bolt and a matched nut after water is volatilized. The small portion of the bolt contacted with the control nut rusted after the drying, and in addition, during the process of assembling the nut, the microcapsules already fixed on the bolt had a lump-shedding phenomenon as the nut was screwed in, which indicates that the PVA-borax cured film had poor adhesion to the metal, and although the curing time of the film was short, this method was not feasible in the actual pre-coating process.
The polyvinyl formal adhesive used as the adhesive is preferably synthesized by condensing 6mol/L hydrochloric acid with 10% of completely dissolved polyvinyl alcohol-1799 (PVA-1799) at a temperature of about 95 ℃. Wherein m (H2O), m (PVA-1799) and m (formaldehyde) are 10:1:0.7, the viscosity of the prepared adhesive is relatively suitable. The adhesive has the characteristics of strong adhesive force, stability in storage, low cost and the like, and is different from a PVA-borax curing film in that a 107 adhesive has certain tensile property after being completely cured, the characteristic can be beneficial to improving the tensile property after pre-coating, a proper amount of 107 adhesive is put into a mixture of microcapsules and a curing agent which are mixed in proportion, the mixture is uniformly coated on a bolt and dried to form a film, and the bolt and a matched nut are assembled after 18 hours. Preliminary tests showed that the microencapsulated sealant adhered to the bolt did not fall off during the assembly process, indicating that the 107 adhesive had a strong adhesive force. Therefore, in the experiment of assembling the sealant and the bolt, polyvinyl formal glue is selected as the adhesive of the sealant.
2. Effect of coating cure time on microcapsule encapsulant Performance
Mixing the dried microcapsule particles with a curing agent according to the following steps of: the vulcanizing agent is proportioned according to the mass ratio of 100:17, then a proper amount of polyvinyl formal is added as an adhesive, the mixture is uniformly mixed and coated on the surface of the bolt in a small amount of times, and the same amount of sealant coated on the bolt every time is ensured as much as possible in the coating process. And (3) placing the coated bolt test piece for curing at normal temperature for 4h, 8h, 16h and 18h, screwing a matched nut into the bolt, and performing an experiment and recording the change of the moment along with the increase of the vulcanization time. Table 5 shows the change in breaking torque and removal torque at different vulcanization times after 4h of curing ((3 sets of tests).
TABLE 5 destructive torque and disassembly torque values at different vulcanization times after 4h of curing
| Time of day | Mean-Tba | S-DTba | MeanT1 | MeanT2 | MeanT3 | Mean-T | S-DT |
| 2.5 | 2.94333 | 1.26057 | 2.335 | 3.7975 | 1.3125 | 2.48167 | 1.24898 |
| 5 | 4.65333 | 2.74748 | 2.995 | 5.1275 | 2.4725 | 3.53167 | 1.40651 |
| 10 | 3.32333 | 0.69974 | 2.7975 | 3.9925 | 2.17 | 2.98667 | 0.92586 |
| 15 | 2.73333 | 0.40464 | 2.365 | 1.775 | 1.9025 | 2.01417 | 0.31045 |
| 20 | 3.96333 | 0.57422 | 3.16 | 2.4075 | 4.965 | 3.51083 | 1.31435 |
| 25 | 3.65667 | 1.12394 | 1.955 | 4.2425 | 5.3625 | 3.85333 | 1.73676 |
From the above test data, it can be seen that, under the condition that the curing time is 4h, along with the increase of the vulcanization time, the sealant breaking moment and the sealant dismantling moment fluctuate greatly in the early stage of curing and then gradually tend to be stable, and the maximum breaking moment and the dismantling moment thereof appear on the 5 th day of the vulcanization reaction and respectively reach 7.8N.m and 5.13 N.m. Significantly higher than the uncoated maximum torque of the sealant (5.86N.m and 4.44N.m)
TABLE 6 destructive torque and disassembly torque values at different vulcanization times under 8h of cure
| Time of day | Mean-Tba | S-DTba | MeanT1 | MeanT2 | MeanT3 | Mean-T | S-DT |
| 2.5 | 2.37333 | 0.64748 | 1.86 | 2.18 | 2.32 | 2.12 | 0.2358 |
| 5 | 3.24 | 1.03116 | 3.28 | 1.785 | 2.6325 | 2.56583 | 0.74973 |
| 10 | 4.22667 | 0.86002 | 3.985 | 3.48 | 1.9725 | 3.14583 | 1.04704 |
| 15 | 2.58 | 0.57559 | 2.595 | 1.92 | 2.725 | 2.41333 | 0.43216 |
| 20 | 3.94 | 1.59433 | 3.445 | 2.5325 | 4.5475 | 3.50833 | 1.00899 |
| 25 | 4.86333 | 2.12015 | 2.9225 | 7.125 | 3.0025 | 4.35 | 2.40355 |
It can be seen from the test data that, under the condition that the curing time is 8h (see table 6), along with the increase of the vulcanization time, the destructive torque and the disassembly torque of the sealant are increased firstly and then reduced, and then increased again, the destructive torque and the disassembly torque of the sealant have large value fluctuation, and the maximum destructive torque and the disassembly torque respectively reach 7.3N.m and 7.13N.m on the 25 th day of the vulcanization reaction and are obviously higher than the maximum torque of the uncoated sealant.
TABLE 7 destructive torque and disassembly torque values at different vulcanization times for 16h of cure
| Time of day | Mean-Tba | S-DTba | MeanT1 | MeanT2 | MeanT3 | Mean-T | S-DT |
| 2.5 | 4.60333 | 2.46435 | 2.98 | 1.7325 | 4.9575 | 3.22333 | 1.62621 |
| 5 | 4.46 | 2.22603 | 2.4025 | 1.845 | 4.9225 | 3.05667 | 1.63973 |
| 10 | 4.15333 | 3.43788 | 1.94 | 5.5625 | 1.7725 | 3.09167 | 2.14144 |
| 15 | 2.18667 | 0.46544 | 1.195 | 1.6225 | 1.59 | 1.46917 | 0.23799 |
| 20 | 3.80333 | 0.29263 | 2.98 | 3.73 | 2.9775 | 3.22917 | 0.43374 |
| 25 | 2.74333 | 0.57744 | 1.9575 | 2.275 | 1.8125 | 2.015 | 0.23655 |
It can be seen from the test data that in the case of a curing time of 16h (see table 7), the breaking torque and the removal torque of the sealant tended to decrease gradually as the vulcanization time increased, and the maximum breaking torque and the removal torque reached maximum values at 10 days after the vulcanization reaction, which were 5.43n.m and 5.56 n.m, respectively, and were equivalent to the uncoated sealant torque values.
TABLE 8 destructive torque and removal torque values at different curing times for 18h
| Time of day | Mean-Tba | S-DTba | MeanT1 | MeanT2 | MeanT3 | Mean-T | S-DT |
| 2.5 | 4.67667 | 2.0651 | 3.1725 | 2.415 | 5.8025 | 3.79667 | 1.77791 |
| 5 | 6.95 | 3.64045 | 6.9675 | 7.75 | 2.775 | 5.83083 | 2.67519 |
| 10 | 4.85333 | 2.81347 | 3.2675 | 6.7 | 2.6525 | 4.20667 | 2.18108 |
| 15 | 7.39667 | 6.68297 | 3.39 | 2.43 | 11.225 | 5.68167 | 4.8246 |
| 20 | 6.41667 | 1.64342 | 5.1075 | 4.87 | 2.85 | 4.27583 | 1.2405 |
| 25 | 9.62333 | 7.21399 | 4.56 | 14.55 | 2.935 | 7.34833 | 6.28953 |
From the above test data, it can be seen that the breaking torque and the removal torque of the sealant gradually increase with the increase of the vulcanization time under the condition of the curing time of 18h (see table 8), and the maximum breaking torque and the removal torque values reached maximum values at 25 days of the vulcanization reaction, which are 17.9n.m and 14.55n.m, respectively, and are significantly higher than the uncoated sealant values. Compared with other mechanical data under different curing time, under the condition that the curing time is 18h, the moment is ideal, and the regularity is good.
Comparing the torque test data of the microcapsule sealant under different curing times, it can be seen that the torque variation condition of the sealant has great difference under different curing times. In general, under the conditions of 8h and 18h of curing time, the change rule of the sealant breaking moment and the disassembling moment is consistent and gradually increased along with the increase of the vulcanization time. Under the conditions that the curing time is 4h and 16h, the regularity of the torque change is poor, even the torque is reduced, and meanwhile, the torque value is small. The data from the parallel experiments differed slightly. Comprehensive analysis shows that under the condition that the curing time is 18 hours, the vulcanizing effect of the sealant is good, and the torque experimental result after the vulcanizing reaction is regular and ideal. Comparing the torque data for the uncoated encapsulant and the microcapsule encapsulant, it can be seen that the breaking torque and the removal torque (17.9n.m and 14.55n.m) of the microcapsule encapsulant reached 305% and 328% of the uncoated encapsulant (5.86n.m and 4.44n.m), respectively, when the torque was stable.
And comprehensively considering the optimal vulcanization time of the microcapsule sealant and the corresponding maximum breaking moment and disassembly moment, and finally determining that the curing time of the microcapsule sealant is 18h under the normal temperature condition.
3. Effect of drying temperature on microcapsule sealants
Mixing the dried microcapsule particles with a curing agent according to the following microcapsule sealant: mixing vulcanizing agents according to the mass ratio of 100:17, adding a proper amount of polyvinyl formal as an adhesive (pH is 8-9), uniformly mixing, coating the mixture on the surface of a bolt by a small amount of multiple times, and carefully adjusting the amount of a sealant coated on the bolt in the coating process to keep the coating amount of each bolt basically the same as much as possible. After the nut is screwed into the bolt test piece coated with the bolt, the assembled test piece is respectively placed in an oven at 15 ℃, 25 ℃ and 35 ℃ for vulcanization. Then, a torque measurement test was carried out, and the change in torque with the increase in vulcanization time was recorded. In order to ensure the reliability and the repeatability of experimental data, each vulcanization temperature point is simultaneously detected by 3 parallel samples, and the result is the average value of the results of the 3 parallel samples.
At 10 days, 5.15N.m and 4.41N.m were reached, respectively. At a vulcanization temperature of 35 ℃, the breaking moment and the disassembling moment of the sealant show a gradual increase trend along with the increase of the vulcanization time, and when the vulcanization reaction is carried out for 25 days, the maximum breaking moment and the disassembling moment reach maximum values of 17.9N.m and 14.55N.m respectively. Compared with 15 ℃ and 35 ℃ vulcanization temperatures, the torque of the sealant under 25 ℃ vulcanization conditions is obviously increased in the same vulcanization time, which shows that the vulcanization process of the sealant is accelerated along with the increase of the vulcanization reaction temperature, the adhesive strength of the vulcanized sealant is increased, and therefore, the torque of the sealant is increased in the same vulcanization time compared with that at other vulcanization temperatures.
Comparing the test results of the breaking moment and the disassembling moment of the microcapsule sealant at different vulcanization temperatures of 15 ℃, 25 ℃ and 35 ℃, it can be found that the change rule of the sealant moment has great difference at different vulcanization temperatures. In general, under the vulcanization conditions of 15 ℃ and 25 ℃, the change rules of the sealant breaking moment and the disassembly moment are consistent, and the trend of the sealant breaking moment and the disassembly moment gradually increases along with the prolongation of the vulcanization time. And when the vulcanization temperature is 35 ℃, the change regularity of the moment is poor, and the moment value is small. There is a large difference between the parallel test torque data values, which may be caused by differences in the flow of the sealant after assembly. The above experimental results are comprehensively analyzed, and the overall view is that when the vulcanization temperature is 25 ℃, the vulcanization effect of the assembled microcapsule sealant is ideal, the vulcanization reaction is complete, and the torque value is large. Compared with the torque measurement results of the uncoated sealant, it can be found that when the torque is substantially stable, the maximum breaking torque and the disassembly torque (17.9n.m and 14.55n.m) of the microcapsule sealant are 305% and 328% of the maximum torque (5.86n.m and 4.44n.m) of the uncoated sealant, respectively, indicating that the torque performance of the sealant is significantly improved after the sealant is microencapsulated, and the vulcanization temperature of the microcapsule sealant is 25 ℃.
4. Exemplary application of microcapsule sealant Pre-coating
The application process of the microcapsule sealant comprises the following steps:
mixing the microcapsule sealant with a vulcanizing agent according to a mass ratio of 100: 17;
uniformly coating the mixed sealant on a screw, a rivet rod or a nail head part by using a brush;
and after pre-coating, curing the mixture for 18 hours at normal temperature to form a film, and finishing the pre-coating.
The invention determines the engineering application implementation method based on the urea-formaldehyde resin microcapsule sealant by a building block type test means of elements, components and large parts, solves the corrosion prevention and sealing problem of large deformation structures such as ship bottoms and the like under the action of force, breaks through the implementation technology based on the urea-formaldehyde resin microcapsule sealant, and greatly reduces the sealing assembly efficiency of equipment deformation structures such as airplanes and the like and the corrosion problem caused by the action of force.
The engineering application implementation process based on the urea-formaldehyde resin microcapsule sealant can directly guide the microcapsule sealant to be applied to the connection and assembly of the equipment deformation structure. The technology has wide application prospect, is particularly suitable for equipment and equipment deformation structures applied to severe environments such as marine atmosphere or industrial pollution, and can effectively improve the corrosion resistance of an equipment connecting structure by applying the high corrosion resistance design of the microcapsule sealant; the precoating performance of the microcapsule sealant is utilized, so that the production and assembly efficiency of equipment is greatly improved; simultaneously, the production and assembly cost of the equipment can be effectively reduced.
Claims (8)
1. A method for the engineered application of a urea-formaldehyde resin based microcapsule sealant, the method comprising:
s1, mixing the microcapsule particles with a curing agent according to the mass ratio of 100: 17;
s2, adding an adhesive into the mixture obtained in the step S1, and uniformly mixing;
s3, pre-coating the mixture obtained in the step S2 on the surface of a test piece, and drying;
and S4, curing the surface of the pre-coated test piece for a preset time at normal temperature to finish the pre-coating.
2. The method for engineering application of a microcapsule sealant based on urea-formaldehyde resin as claimed in claim 1, wherein in S1, the curing agent is a vulcanizing agent.
3. The method for engineering application of a microcapsule sealant based on urea-formaldehyde resin as claimed in claim 1, wherein in S2, the adhesive is polyvinyl formal.
4. The method for applying the microcapsule sealant based on the urea-formaldehyde resin as claimed in claim 3, wherein the process conditions for synthesizing the polyvinyl formal are as follows:
the polyvinyl formal is obtained by condensation with 6mol/L hydrochloric acid and 10% polyvinyl alcohol-1799 (PVA-1799) which is completely dissolved at 95 ℃.
5. The engineering application method of the microcapsule sealant based on the urea-formaldehyde resin as claimed in claim 4, wherein the mass ratio of each component in the polyvinyl formal synthesis process is:
m (H2O), m (PVA-1799) and m (formaldehyde) 10:1: 0.7.
6. The method for engineering application of a microcapsule sealant based on urea-formaldehyde resin as claimed in claim 1, wherein the drying temperature in S3 is 25 ℃.
7. The method for engineering application of a microcapsule sealant according to claim 1, wherein the predetermined time period in S4 is 18 hours.
8. The method of claim 1, wherein after S1 and before S2, the method further comprises:
sodium thiosulfate was added to the mixture obtained in S1 to accelerate the vulcanization process.
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| US5594052A (en) * | 1995-09-11 | 1997-01-14 | The Goodyear Tire & Rubber Company | Sulfur vulcanizable rubber containing sodium thiosulfate pentahydrate |
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| CN104087391A (en) * | 2014-07-29 | 2014-10-08 | 泰州市嘉迪新材料有限公司 | Urea formaldehyde resin microcapsule lubrication oil, lubrication oil coating material and preparation method of lubrication oil |
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| US5594052A (en) * | 1995-09-11 | 1997-01-14 | The Goodyear Tire & Rubber Company | Sulfur vulcanizable rubber containing sodium thiosulfate pentahydrate |
| JP2001233902A (en) * | 1999-12-13 | 2001-08-28 | Nippon Shokubai Co Ltd | Preparation of porous cross-linked polymer |
| CN104087391A (en) * | 2014-07-29 | 2014-10-08 | 泰州市嘉迪新材料有限公司 | Urea formaldehyde resin microcapsule lubrication oil, lubrication oil coating material and preparation method of lubrication oil |
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