CN113308183A - Outer heat-proof coating of dual selfreparing - Google Patents
Outer heat-proof coating of dual selfreparing Download PDFInfo
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- CN113308183A CN113308183A CN202110723339.4A CN202110723339A CN113308183A CN 113308183 A CN113308183 A CN 113308183A CN 202110723339 A CN202110723339 A CN 202110723339A CN 113308183 A CN113308183 A CN 113308183A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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Abstract
The invention relates to the technical field of heat-proof coatings, in particular to a double-self-repairing outer heat-proof coating, which is characterized in that siloxane resin and a disulfide chain extender are adopted to react to obtain a resin matrix containing a disulfide structure, a disulfide bond replacement reaction is utilized to realize chemical repair of microcracks in the coating, thermal expansion microspheres are introduced, the shell is softened after the thermal expansion microspheres are heated, internal gas is heated to expand, and the cracks of the coating are filled, so that the physical repair of the cracks of the coating is realized. The repair rate of the coating is obviously improved by regulating and controlling the content of the expanded microspheres, the self-repair temperature and the self-repair time. Meanwhile, the process is regulated, so that the shell of the expanded microsphere is kept complete, the good mechanical property of the coating is ensured, the weight of the coating is reduced, and the heat insulation and heat protection effects are achieved.
Description
Technical Field
The invention belongs to the field of intelligent high polymer materials and the field of heat-proof coatings, and relates to a double self-repairing outer heat-proof coating.
Background
In the flying process of the aerospace craft, due to the pneumatic heating effect generated by friction with air, each part is easily subjected to high heat flow and long-time air flow scouring, the mechanical property of the shell of the aerospace craft is easily reduced, and the necessary outer protective material is an important guarantee for ensuring safe flying. The outer heat-proof coating can play a role in heat insulation and heat protection when the outer heat-proof coating faces violent pneumatic heating, and heat is prevented from being transmitted to the inside of the bullet (arrow).
The heat-proof coating in the current market takes phenolic resin, epoxy resin, siloxane and the like as matrix resin, and the heat conductivity of the coating is reduced by adding hollow glass microspheres, but the breakage rate of the hollow glass microspheres is high in the mechanical mixing process of the coating, and the heat expansion microspheres taking polymers as the matrix can not damage the integrity of the microspheres in the mixing process, and have good resilience to bear multiple times of cyclic pressurization/pressure relief without fracture. Meanwhile, by controlling the process parameters and utilizing the excellent foaming performance of the coating, the self-repairing of the defects in the coating is realized, so that the basic requirements on heat insulation and ablation resistance can be met, and meanwhile, the flight instability caused by local defects such as microcracks and the like is reduced through the self-repairing.
The thermal expansion microspheres are softened by the shell at a certain temperature, the internal gas is heated to expand, the microsphere volume is increased, the microcracks are filled, and physical self-repairing is realized. Meanwhile, due to the air tightness of the shell, the complete spherical structure after expansion ensures the good mechanical property of the coating. The outer pressure and the inner gas pressure of the microspheres are in delicate balance, the microspheres can be foamed, and the microspheres are still a complete closed body after foaming, so that the coating structure cannot be damaged, and the coating weight can be reduced.
The heat-expandable microspheres are mainly used in heat-insulating, sound-insulating and heat-preserving coatings at present, but are not reported in the field of self-repair.
Patent CN201911307875.5 discloses a styrene-acrylate coating, which is formed by adding thermal expansion microspheres, and the material has better elastic damping performance, excellent sound insulation performance and stronger resilience performance;
patent CN202010814830.3 provides a preparation method of a water-based sound-insulation shock-absorption heat-insulation coating, 1-20 parts of thermal expansion microspheres are adopted, and the obtained coating has high hardness, has the functions of sound absorption, damping shock absorption, water resistance, moisture resistance and the like, and is an important component for developing green buildings.
Patent CN201910143502.2 provides a thermal insulation coating for an automobile shell, which is prepared by preparing thermal expansion hollow microspheres, then preparing stearic acid modified nano yttrium cerate powder, then loading the nano yttrium cerate powder on the surfaces of the hollow microspheres through spray deposition to form core-shell thermal insulation filler, and further mixing the core-shell thermal insulation filler with a resin system to obtain the thermal insulation coating. The added 25-30 parts of the thermal expansion hollow microsphere core layer expands by heating to increase the air amount in the coating so as to play a thermal insulation effect.
Disclosure of Invention
It can be seen that although expanded microspheres are adopted in the external heat-proof coating in the prior art, the invention provides the external heat-proof self-repairing coating for the rocket and the preparation method thereof, in order to achieve the heat-insulating and heat-proof effects, siloxane containing disulfide bonds is used as matrix resin, disulfide replacement reaction is used as a chemical repairing means, heating expansion of the expanded microspheres is used as a physical repairing means, and the two means act together to further remarkably improve the self-repairing rate and efficiency of the coating.
In order to achieve the purpose, the invention relates to the following specific technical scheme:
the double self-repairing outer heat-proof coating is characterized in that expanded microspheres which expand after being heated and can fill cracks of the coating are added into a resin matrix with a double-sulfur structure.
A method for repairing a double self-repairing outer heat-proof coating comprises the steps of reacting siloxane resin with a disulfide chain extender to obtain a resin matrix containing a disulfide structure, utilizing disulfide bond replacement reaction to realize chemical repair of microcracks in the coating, introducing thermal expansion microspheres, heating the microspheres to soften the shell, heating internal gas to expand, and filling cracks in the coating, thereby realizing physical repair of the cracks in the coating.
Compared with the prior art, the invention has the following advantages:
1) the adopted thermal expansion microspheres are inhibited in the processing process, the shell is softened by heating in the later use process, the internal gas is heated to expand, the thermal expansion microspheres are properly expanded by strictly controlling the process conditions, the filling effect is realized on the microcracks of the coating, and the self-repairing is quickly realized. Meanwhile, due to the air tightness of the shell, the complete spherical structure after expansion endows the coating with good mechanical property, and the coating can bear multiple times of cyclic heating/cooling without cracking;
2) the small hollow glass microspheres and the thermal expansion microspheres are compounded and uniformly dispersed in siloxane matrix resin according to different proportion formulas, so that the coating density can be reduced, and a good heat insulation and heat protection effect can be achieved;
3) the self-repairing coating repairing mechanism not only realizes physical repair by heating expansion of the thermal expansion microspheres, but also introduces a disulfide replacement group into a siloxane resin matrix structure to jointly ensure the repairing effect of the coating.
Drawings
FIG. 1 is an IR spectrum of a self-healing coating (a) without microspheres; (b) after the microspheres are added.
FIG. 2 is a Raman spectrum of the coating.
FIG. 3 is a graph showing the effects before and after self-healing when 1% expanded microspheres are added, wherein (a) the sample is (b) cut and (c) the sample is repaired.
FIG. 4 is a graph showing the effects before and after self-healing when 3% expanded microspheres are added, after (a) cutting (b) as is and (c) repairing.
FIG. 5 is a comparison of microspheres before and after expansion, after expansion (a) as received (b) and after recovery from cooling (c).
FIG. 6 is a comparison of microspheres before and after over-expansion, after (a) reduction in temperature of the original sample (b).
Detailed Description
The invention is further explained below with reference to the drawings and the embodiments.
The double self-repairing outer heat-proof coating comprises siloxane, polyisocyanate, bis (2-hydroxyethyl) disulfide (HEDS), expanded microspheres, hollow microspheres and butyl acetate, and the mass ratio of the two components is respectively 100 parts: 5-35 parts of: 5-20 parts of: 10-60 parts of: 10-60 parts of: 50-150 parts. The preparation method comprises the following steps:
firstly, respectively putting expanded microsphere powder and hollow microsphere powder into an oven with the temperature of 80 ℃ for drying for more than 5 hours, and treating the dried microsphere powder with a coupling agent for later use;
further, the preparation method of the self-repairing external heat-proof coating comprises the following specific steps: dissolving organic silicon resin and polyisocyanate in ethyl acetate solvent, reacting for 0.5-5 h at low temperature, and continuing to react for 1-5 h at room temperature to obtain a-NCO-terminated prepolymer;
because the reaction activity of the organic silicon resin is high, the reaction activity can be reduced by adopting low temperature, but the organic silicon resin is incompatible with an isocyanate system, and therefore, the raw material proportion and the reaction process conditions need to be properly controlled, and the end-NCO prepolymer is finally prepared.
Furthermore, the siloxane is amino-terminated polysiloxane or hydroxyl-terminated polysiloxane, and the molecular weight is adjustable from 500 to 4000; the polyisocyanate comprises HDI trimer and IPDI trimer;
further, adding a disulfide chain extender into the terminal-NCO prepolymer, and reacting at 20-80 ℃ to obtain a resin matrix; preferably, the disulfide chain extender is bis (2-hydroxyethyl) disulfide (HEDS), diaminodiphenyl disulfide (AFD), or the like; the addition of the disulfide chain extender is accomplished by utilizing a disulfide group displacement reaction in order to prepare a matrix resin containing a self-healing function.
Further, adding the thermal expansion microspheres, the hollow glass microspheres and a proper amount of solvent treated by the coupling agent into the resin matrix, and uniformly mixing at a certain rotating speed to obtain a semi-finished product of the self-repairing outer heat-proof coating; the expanded microsphere is as follows: expancel 551DU 40, Expancel 031DU 40, Expancel 461DU 40, Expancel 053DU 40, but not limited to these, the particle size range is 6-16 μm; the hollow microspheres are K25, K37, S15 and S38 of 3M company, but are not limited to the above, and the particle size ranges from 50 to 100 micrometers.
Further, the semi-finished product of the coating is sieved by a 100-mesh sieve, and residual agglomeration or caking and the like on the sieve are removed to obtain the self-repairing outer heat-proof coating.
According to the invention, the expanded microspheres are added into the resin matrix containing the disulfide structure, when the expanded microspheres are heated, the thermoplastic shell of the outer layer becomes soft, the gas of the inner core can expand by volume when being heated, and finally the volume of the microspheres is rapidly increased, the diameter can be increased from 10m to 40m, and the volume is increased by about 20-60 times. The controllable expansion of the microspheres can be realized by effectively controlling the heating temperature and the heating time, the physical filling of microcracks is realized by utilizing the volume expansion of the microspheres, and the self-repairing function of the resin matrix is combined to realize quick self-repairing jointly.
The expansion temperature ranges of the expanded microspheres with different structures are different, taking Expancel 031DU 40 as an example, the initial expansion temperature is 80-95 ℃, and the maximum expansion temperature is 120-135 ℃. At 60 ℃, the microspheres do not start to expand, so the repair of the coating can be finished only by means of disulfide replacement reaction in the resin, the rate is slower, the repair is slightly accelerated at 80 ℃, and the repair rate is fastest at 120 ℃, which is shown in table 1. However, the heating temperature is not too high, which can cause the microspheres to crack, not only can repair the coating, but also can cause the pores on the surface of the coating, as shown in fig. 6, the microspheres in the figure expand excessively, which directly causes the pores on the surface of the coating, and the pores can not be recovered even if the temperature is reduced to normal temperature.
The self-repairing coating prepared by the invention has the advantages that the self-repairing speed of the coating is obviously increased under the heating condition, and the resin matrix in the coating also has the self-repairing function, so that the self-repairing efficiency and the self-repairing speed of the coating can be obviously improved due to the mutual cooperation of the self-repairing function and the self-repairing function. When the coating is cooled, the shell of the expanded microsphere is hardened again, the volume is fixed, the slightly expanded microsphere is heated again and can expand for the second time, and the coating provided by the invention has multiple repairing effects by combining the repairability of the resin matrix;
according to the double self-repairing outer heat-proof coating, the thermal expansion microspheres are properly expanded to serve as a physical repairing agent by strictly controlling the process conditions, and meanwhile, the disulfide bonds capable of realizing self-repairing through replacement reaction are introduced into the resin matrix, so that the double self-repairing outer heat-proof coating is obtained.
The preparation process of the double self-repairing outer heat-proof coating is described as follows:
example 1
Dissolving 100 parts of hydroxyl-terminated silicone resin with the molecular weight of 1000 and 20 parts of HDI trimer in 50 parts of ethyl acetate, reacting for 2 hours at 0 ℃, and continuing to react for 5 hours at room temperature to obtain a prepolymer of terminal-NCO; adding 8 parts of bis (2-hydroxyethyl) disulfide, reacting at 50 ℃ to obtain a resin matrix, adding 20 parts of coupling agent treated expanded microspheres, 30 parts of hollow glass microspheres, other fillers and a proper amount of solvent butyl acetate, uniformly mixing, sieving by a 100-mesh sieve, and filtering out agglomerated or caked parts to obtain the self-repairing outer heat-proof coating 1.
Example 2
Dissolving 100 parts of hydroxyl-terminated silicone resin with molecular weight of 2000 and 30 parts of HDI trimer in 40 parts of ethyl acetate, reacting for 1 hour in an ice-water bath, and continuing to react for 2.5 hours at room temperature to obtain a prepolymer of terminal-NCO; adding 10 parts of bis (2-hydroxyethyl) disulfide, reacting at 60 ℃ to obtain a resin matrix, adding 30 parts of expanded microspheres, 20 parts of hollow glass microspheres and a proper amount of butyl acetate, and filtering out agglomerated or caked parts by using a 100-mesh sieve to obtain the self-repairing outer heat-proof coating 2.
Example 3
Dissolving 100 parts of hydroxyl-terminated silicone resin with the molecular weight of 1000 and 12 parts of IPDI trimer in 50 parts of ethyl acetate, reacting at low temperature for 1.5h, and continuing to react at room temperature for 4h to obtain a prepolymer of terminal-NCO; adding 15 parts of diamino diphenyl disulfide, reacting at 40 ℃ to obtain a resin matrix, adding 50 parts of coupling agent treated expanded microspheres, 20 parts of hollow glass microspheres and a proper amount of butyl acetate, and filtering out agglomerated or caked parts by using a 100-mesh sieve to obtain the self-repairing outer heat-proof coating 3.
Example 4
Dissolving 100 parts of hydroxyl-terminated silicone resin with the molecular weight of 1000 and 20 parts of IPDI trimer in 50 parts of ethyl acetate, reacting at low temperature for 4 hours, and continuing to react at room temperature for 2 hours to obtain a prepolymer of terminal-NCO; adding 12 parts of diamino diphenyl disulfide, reacting at 40 ℃ to obtain a resin matrix, adding 20 parts of coupling agent treated expanded microspheres, 30 parts of hollow glass microspheres and a proper amount of butyl acetate, and filtering out agglomerated or caked parts by using a 100-mesh sieve to obtain the self-repairing outer heat-proof coating 4.
For coatings with an optimal rate of self-healingThe repair temperature is generally between the initial expansion of the microspheres and the maximum expansion temperature, TBegins to expand＜TRepairing temperature＜TMaximum expansion。
TABLE 1 table of content and self-repairing rate of expanded microspheres
TABLE 1
Claims (10)
1. The double self-repairing outer heat-proof coating is characterized in that the coating is formed by adding expanded microspheres which expand after being heated and can fill cracks of the coating into a resin matrix with a disulfide structure.
2. The dual self-healing outer thermal barrier coating of claim 1, wherein the expanded microspheres are: expancel 551DU 40, Expancel 031DU 40, Expancel 461DU 40, Expancel 053DU 40, particle size 6-16 μm.
3. The double self-repairing outer heat-proof coating is characterized by comprising siloxane, polyisocyanate, a disulfide chain extender, expanded microspheres, hollow microspheres and butyl acetate, wherein the mass ratio of the siloxane to the polyisocyanate to the disulfide chain extender is respectively 100 parts: 5-35 parts of: 5-20 parts of: 10-60 parts of: 10-60 parts of: 50-150 parts.
4. The double self-repairing outer heat-proof coating as claimed in claim 3, wherein the siloxane is amino-terminated polysiloxane or hydroxyl-terminated polysiloxane, and the molecular weight is adjustable from 500 to 4000.
5. The dual self-healing outer thermal protective coating of claim 3, wherein the polyisocyanate comprises HDI trimer or IPDI trimer.
6. The dual self-healing outer thermal barrier coating of claim 3, wherein the disulfide chain extender is one or more of 4,4 ' -dihydroxydiphenyl disulfide, bis (2-hydroxyethyl) disulfide, 4 ' -diaminodiphenyl disulfide, 2,2 ' -dithiodipropionic acid, and the like.
7. The dual self-healing outer thermal barrier coating of claim 3, wherein said expanded microspheres are: expancel 551DU 40, Expancel 031DU 40, Expancel 461DU 40, Expancel 053DU 40, particle size 6-16 μm.
8. The double self-repairing outer heat-proof coating as claimed in claim 3, wherein the hollow microspheres are K25, K37, S15 or S38 of 3M company, and have a particle size of 50-100 μ M.
9. A preparation method of a double self-repairing outer heat-proof coating is characterized in that organic silicon resin and polyisocyanate are dissolved in ethyl acetate solvent, the reaction is carried out for 0.5-5 h at low temperature, the reaction is carried out for 1-5 h at room temperature, and a-NCO-terminated prepolymer is obtained; adding a disulfide chain extender, reacting at 20-80 ℃ to obtain a resin matrix, then adding expanded microspheres, hollow glass microspheres and a solvent treated by a coupling agent, uniformly mixing to obtain a semi-finished product of the self-repairing outer heat-proof coating, sieving the semi-finished product of the coating with a 100-mesh sieve, and removing residual aggregates or agglomerates on the sieve to obtain the self-repairing outer heat-proof coating.
10. A repairing method of a double self-repairing outer heat-proof coating is characterized in that siloxane resin reacts with a disulfide chain extender to obtain a resin matrix containing a disulfide structure, chemical repairing of microcracks in the coating is achieved through disulfide bond replacement reaction, thermal expansion microspheres are introduced, the shell is softened after the thermal expansion microspheres are heated, internal gas is heated to expand, the coating cracks are filled, and therefore physical repairing of the coating cracks is achieved.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736348A (en) * | 2022-05-20 | 2022-07-12 | 广东电网有限责任公司 | Anti-microcrack coating and preparation method thereof |
| CN115637092A (en) * | 2022-09-30 | 2023-01-24 | 上海航天化工应用研究所 | Self-repairing heat-proof coating based on dynamic exchange chemistry and preparation method thereof |
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| CN103665419A (en) * | 2013-12-06 | 2014-03-26 | 四川达威科技股份有限公司 | Synthesis method and application method of low-medium temperature thermal expansion microspheres |
| CN110551269A (en) * | 2019-09-19 | 2019-12-10 | 四川大学 | Heat-resistant room-temperature rapid self-repairing elastomer and preparation method and application thereof |
| CN112852151A (en) * | 2021-01-11 | 2021-05-28 | 井冈山大学 | Design of multiple self-repairing structure for brittle material with high glass transition temperature |
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- 2021-06-28 CN CN202110723339.4A patent/CN113308183A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103665419A (en) * | 2013-12-06 | 2014-03-26 | 四川达威科技股份有限公司 | Synthesis method and application method of low-medium temperature thermal expansion microspheres |
| CN110551269A (en) * | 2019-09-19 | 2019-12-10 | 四川大学 | Heat-resistant room-temperature rapid self-repairing elastomer and preparation method and application thereof |
| CN112852151A (en) * | 2021-01-11 | 2021-05-28 | 井冈山大学 | Design of multiple self-repairing structure for brittle material with high glass transition temperature |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736348A (en) * | 2022-05-20 | 2022-07-12 | 广东电网有限责任公司 | Anti-microcrack coating and preparation method thereof |
| CN114736348B (en) * | 2022-05-20 | 2023-09-05 | 广东电网有限责任公司 | Microcrack-resistant coating and preparation method thereof |
| CN115637092A (en) * | 2022-09-30 | 2023-01-24 | 上海航天化工应用研究所 | Self-repairing heat-proof coating based on dynamic exchange chemistry and preparation method thereof |
| CN115637092B (en) * | 2022-09-30 | 2023-12-12 | 上海航天化工应用研究所 | Self-repairing heat-proof coating based on dynamic exchange chemistry and preparation method thereof |
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