Manufacturing method of vulcanization capsule with wide temperature range and high adaptability and vulcanization capsule

Abstract

The application relates to the field of vulcanization capsules, in particular to a manufacturing method of a wide-temperature-range high-adaptability vulcanization capsule and the vulcanization capsule, which specifically comprises the following steps: cleaning a capsule body; pre-activating the surface of the cleaned capsule body to form a hydroxyl-modified layer covalently bonded with the body on the surface layer of the capsule body; performing two-step silane gradient grafting modification on the pre-activated capsule body; coating a conductive primer layer, an anchor layer and a gradient transition adhesive layer on the surface of the hydroxyl-activated layer in sequence and solidifying; preparing a protective layer containing perfluoroalkyl-modified thermotropic liquid crystal polyurethane and spraying the protective layer on the surface of the solidified gradient transition adhesive layer; performing ladder temperature curing on the sprayed protective layer to obtain a wide-temperature-range vulcanization capsule; the thermal expansion coefficient of the gradient transition adhesive layer continuously decreases from the side close to the capsule body to the side far from the capsule body; and the service life of the vulcanization capsule under wide-temperature-range repeated alternating working conditions is improved.

Description

Technical Field

[0001] This application relates to the field of vulcanized capsules, and more particularly to a method for manufacturing a vulcanized capsule with wide temperature range and high adaptability, and the vulcanized capsule itself. Background Technology

[0002] The vulcanizing bladder needs to be inserted into the inner cavity of the tire blank to be vulcanized, and a high-temperature, high-pressure medium is introduced to achieve tire shaping and vulcanization, directly determining the tire's molding precision and vulcanization quality. During production, the vulcanizing bladder must withstand high-temperature, high-pressure vulcanization conditions of 140-200℃ for extended periods, as well as alternating stress from periodic inflation and deflation.

[0003] One of the more mainstream methods for vulcanized capsules is to refer to a vulcanized capsule and its preparation method disclosed in announcement number CN112092428B. This method involves compounding modified polysulfide rubber with liquid polysulfide rubber and then combining it with a thermotropic liquid crystal polymer to prepare a polymer composition containing high and low double glass transition temperatures. A protective colloid is prepared by compounding it with sheet-like thermally conductive composite filler and then coating it onto the surface of the capsule body and curing it to form a protective layer.

[0004] However, in actual production, there are extreme temperature differences in different production scenarios in different regions. For example, the storage environment of -20℃ in workshops in cold regions during winter is switched instantly with the high temperature vulcanization of 200℃. Thermotropic liquid crystal polymers are prone to crystal orientation embrittlement at low temperatures and have a high crack initiation rate under extreme thermal shock.

[0005] In addition, the thermal expansion coefficients of the rubber body and the polysulfide-polyurethane protective layer are quite different. Under repeated alternating operating conditions in a wide temperature range, periodic shear stress and internal stress accumulation will occur at the interface, causing the protective layer to fall off prematurely and the capsule to fail.

[0006] Moreover, in tire vulcanization conditions, high-temperature and high-pressure steam, superheated water, and multiple media such as amine accelerators, vulcanization aids, and plasticizers released from tire rubber compounds will synergistically erode the vulcanizing capsule. Small molecules continuously penetrate to the interface between the protective layer and the rubber body, causing interface swelling and a sharp drop in adhesion. All these factors combined result in a shorter service life for the vulcanizing capsule under repeated alternating operating conditions in a wide temperature range. Summary of the Invention

[0007] In order to improve the service life of vulcanizing capsules under repeated alternating operating conditions in a wide temperature range, this application provides a method for manufacturing a vulcanizing capsule with high adaptability in a wide temperature range and a vulcanizing capsule.

[0008] Firstly, the manufacturing method of a wide-temperature-range, highly adaptable vulcanized capsule provided in this application adopts the following technical solution.

[0009] A method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule specifically includes the following steps.

[0010] S1. Clean the capsule body;

[0011] S2. Pre-activate the cleaned capsule surface to form a hydroxylated modified layer covalently bonded to the capsule surface.

[0012] S3. The pre-activated capsule body is modified by a two-step silane gradient grafting method. First, a covalently bonded fluorine-containing barrier layer is formed on the hydroxylation modification layer, and then a covalently bonded hydroxyl activation layer is formed on the fluorine-containing barrier layer.

[0013] S4. Coat the surface of the hydroxyl-activated layer with a conductive primer layer, an anchoring agent layer and a gradient transition adhesive layer in sequence and cure.

[0014] S5. Prepare a protective layer of thermotropic liquid crystal polyurethane containing perfluoroalkyl and spray it onto the surface of the cured gradient transition adhesive layer.

[0015] S6. The protective layer after spraying is cured by step temperature increase to obtain a wide temperature range vulcanized capsule.

[0016] The coefficient of thermal expansion of the gradient transition adhesive layer decreases continuously from the side closer to the capsule body to the side farther away from the body.

[0017] By adopting the above technical solution, the two-step silane gradient grafting modification solves the problems of instability and inability to form a uniform gradient structure in conventional one-pot silane systems. At the same time, it constructs an interface layer that combines resistance to media barrier and high activity of grafting, blocking the penetration of small molecule media into the interface during the sulfidation process and avoiding interface swelling failure.

[0018] The gradient transition adhesive layer with a continuously decreasing coefficient of thermal expansion eliminates the periodic shear stress caused by the difference in the coefficient of thermal expansion between the capsule body and the protective layer, and solves the problem of interface fatigue peeling under wide temperature range alternating working conditions.

[0019] The protective layer of thermotropic liquid crystal polyurethane containing perfluoroalkyl modified polyurethane solves the problems of low-temperature crystallization embrittlement and crack initiation under extreme thermal shock of conventional thermotropic liquid crystal polymers, and is suitable for wide temperature range rapid cooling and heating conditions in cold regions.

[0020] Optionally, the pre-activation of S2 specifically involves immersing the cleaned capsule body in a photografting solution containing a photoinitiator and hydroxyl monomer, removing it, draining it, subjecting it to UV full-surface irradiation, and then purifying and drying it.

[0021] By adopting the above technical solution and using the UV light grafting pre-activation method, the in-situ covalent grafting of hydroxyl monomers was achieved on the surface of saturated butyl rubber through the excitation effect of hydrogen-abstracting photoinitiators. The hydroxylated modified layer and the capsule body are chemically bonded rather than physically modified, which better avoids the risk of the modified layer falling off.

[0022] The process of immersion and full-surface UV irradiation is suitable for vulcanized capsules with different curvatures and specifications, and the full-surface modification has good uniformity and no blind spots.

[0023] Optionally, the photografting treatment solution comprises, by weight: 100 parts anhydrous ethanol, 1-3 parts benzophenone, and 4-6 parts hydroxyethyl acrylate.

[0024] By adopting the above technical solution, the precise formulation ratio achieves the optimal balance between photoinitiation efficiency and grafting effect. The amount of benzophenone can fully stimulate the saturated CH bonds of butyl rubber to generate alkyl free radicals, while avoiding side reactions caused by excessive amount and excessive cross-linking and embrittlement of the surface layer.

[0025] The amount of hydroxyethyl acrylate can be precisely controlled to control the density of surface hydroxyl groups, providing sufficient high-density reaction sites for subsequent silane grafting, while avoiding abrupt changes in the properties of the modified layer caused by excessive grafting.

[0026] Optionally, the gradient transition adhesive layer in S4 includes a transition bottom layer and a transition top layer, wherein the transition bottom layer is closer to the capsule body than the transition top layer.

[0027] The transition layer comprises, by weight, 100 parts of butyl rubber paste, 30-35 parts of hydroxyl-terminated polysulfide rubber paste, 6-7 parts of butyl rubber-g-polysulfide rubber graft compatibilizer, and 0.1-0.3 parts of catalyst.

[0028] The transition surface layer comprises, by weight: 25-35 parts of butyl rubber paste, 100 parts of hydroxyl-terminated polysulfide rubber paste, 6-7 parts of butyl rubber-g-polysulfide rubber graft compatibilizer, and 0.1-0.3 parts of catalyst.

[0029] By adopting the above technical solution and through layered formula design, the thermal expansion coefficients of the transition bottom layer and the transition surface layer are precisely controlled to form a continuous gradient from the capsule body to the protective layer, thereby eliminating interfacial shear stress under wide temperature range alternation.

[0030] Butyl rubber-g-polysulfide rubber graft compatibilizer is used to solve the problems of large polarity difference and easy phase separation between butyl rubber and polysulfide rubber, ensuring the uniformity and stability of the transition layer system, and without performance degradation caused by macroscopic phase separation.

[0031] Optionally, the anchoring agent layer in S4 is a single-terminated mercapto-single-terminated isocyanate-based polysulfide prepolymer coating.

[0032] By adopting the above technical solution, the bifunctional structure of the single-end mercapto-single-end isocyanate polysulfide prepolymer can achieve continuous covalent bonding of the conductive primer layer, anchoring agent layer and gradient transition adhesive layer. The mercapto at one end undergoes Michael addition click reaction with the active group of the primer, and the isocyanate group at the other end undergoes covalent reaction with the hydroxyl group of the transition layer, replacing physical adsorption bonding and improving interfacial adhesion.

[0033] The prepolymer's polysulfide main structure has excellent compatibility with the polysulfide system of the gradient transition adhesive layer and protective layer, eliminating abrupt changes in interfacial properties and further improving interfacial stability under wide temperature range alternation.

[0034] Furthermore, the prepolymer has mild reaction conditions and is not oxygen sensitive, and can complete the efficient click reaction at room temperature without the need for complex equipment or harsh operating conditions.

[0035] Optionally, the protective layer in S5 includes component A and component B; component A includes hydroxyl-terminated polysulfide rubber, polyether polyol, perfluoroalkyl modified thermotropic liquid crystal polyurethane, and modified core-shell thermally conductive filler; component B is a polyurethane prepolymer containing soft segment disulfide bonds.

[0036] By adopting the above technical solution, the introduction of perfluoroalkyl modified thermotropic liquid crystal polyurethane introduces fluorine-containing side chains into the molecular chain, which reduces the crystallinity of the liquid crystal unit, inhibits low-temperature crystallization orientation embrittlement, and makes the modulus of the protective layer fluctuate little in a wide temperature range, so as to withstand thermal shock and prevent crack initiation.

[0037] The modified core-shell thermally conductive filler forms a continuous thermally conductive path in the protective layer, which improves the thermal conductivity of the protective layer and accelerates the heat transfer efficiency of tire vulcanization. At the same time, the sheet-like structure forms a labyrinth-like barrier structure, which greatly reduces the permeability of oxygen, water vapor and vulcanization additives, and improves the airtightness and media resistance of the protective layer.

[0038] Hydroxyl-terminated polysulfide rubber provides the matrix with excellent elasticity, aging resistance and air tightness. The B component containing soft segment disulfide bonds forms an interpenetrating network crosslinking system with the A component, giving the protective layer dynamic self-healing properties. It can dissociate and release internal stress at high temperatures and quickly recombine at low temperatures, greatly extending the capsule's service life.

[0039] Optionally, the perfluoroalkyl-modified thermotropic liquid crystal polyurethane is prepared by reacting polytetrahydrofuran ether diol, perfluorobutyl ethyl hydroquinone, diisocyanate and chain extender.

[0040] By adopting the above technical solution, using perfluorobutylethyl hydroquinone as a modified monomer, fluorine-containing side chains are introduced into the liquid crystal polyurethane molecular chain, which reduces the crystallinity of the liquid crystal unit at the molecular structure level, solves the core problem of low-temperature crystallization embrittlement of conventional thermo-induced liquid crystal polymers, and significantly improves the water vapor resistance, amine additive resistance and aging resistance of liquid crystal polyurethane.

[0041] Polytetrahydrofuran ether diol is a soft segment that provides excellent low-temperature elasticity for liquid crystal polyurethane and has excellent compatibility with the polysulfide matrix of the protective layer, thus avoiding phase separation problems.

[0042] Optionally, the modified core-shell thermally conductive filler is a silane coupling agent modified sheet-like composite filler, which is prepared by hot pressing and pulverizing hexagonal boron nitride, boron nitride whiskers, α-alumina, mica sheets and talc powder.

[0043] By adopting the above technical solution, the composite system of hexagonal boron nitride, boron nitride whiskers and α-alumina can form a three-dimensional continuous heat conduction path in the protective layer, which can significantly improve the thermal conductivity of the protective layer, accelerate the heat transfer efficiency of tire vulcanization, and shorten the vulcanization cycle.

[0044] A sheet-like composite filler based on mica flakes and talc powder forms a labyrinthine barrier structure in the protective layer, which reduces the permeability of oxygen and water vapor, greatly improves the barrier performance and resistance to media erosion of the protective layer, and avoids interface failure caused by the penetration of vulcanizing auxiliaries.

[0045] The hot-pressed film re-pulverization process can precisely control the aspect ratio of the filler, achieve precise control of the thermal expansion coefficient of the protective layer, match it with the gradient transition adhesive layer, and further eliminate interfacial thermal stress under wide temperature range alternation.

[0046] Optionally, the stepwise temperature curing of S6 specifically includes the following steps:

[0047] S61, maintain a constant temperature of 45-55℃ for 10-20 minutes to achieve coating leveling;

[0048] S62, keep at 85-95℃ for 15-25 minutes to complete pre-crosslinking and release internal stress;

[0049] S63. Heat to 105-115℃ at a rate of 1-3℃ / min, hold at a constant temperature for 35-45min, and achieve orderly arrangement of liquid crystal cells;

[0050] S64. Heat to 120-130℃ at a rate of 0.5-1.5℃ / min, hold at that temperature for 25-35min to complete deep cross-linking and structural locking;

[0051] S65. Cool to room temperature at a rate of 1-3℃ / min to eliminate residual thermal stress.

[0052] By adopting the above technical solution, the phased step curing strictly follows the material curing logic of first leveling, then pre-crosslinking, then orderly arrangement of liquid crystals, and finally crosslinking and locking. The internal stress of the coating can be released in a controllable manner throughout the process, avoiding the problems of internal stress concentration, coating cracking and interface delamination caused by the rapid temperature rise of conventional one-step curing.

[0053] The first stage is low-temperature leveling, which ensures that the coating is fully leveled on the entire surface of the capsule, especially in the high curvature shoulder and inflection point areas, without defects such as sagging, pinholes and orange peel, and is suitable for capsules with different curvature specifications.

[0054] The second stage of pre-crosslinking forms a weakly crosslinked mobile network, while triggering dynamic exchange of disulfide bonds, completely releasing the leveling internal stress, avoiding the accumulation of internal stress during subsequent crosslinking, and realizing the graft copolymerization of filler and matrix, thus improving the stability of the system.

[0055] The third stage precisely controls the temperature within the stable liquid crystal state range, ensuring that the liquid crystal units in the weakly cross-linked network move fully and are arranged uniformly and orderly, forming a perfect nematic domain structure, achieving isotropic coating performance, and avoiding performance fluctuations caused by uneven orientation.

[0056] The fourth stage involves slow heating to achieve deep cross-linking, completely locking the ordered structure of the liquid crystal. At the same time, the cross-linking internal stress is released through the continuous dynamic exchange of disulfide bonds, ensuring uniform cross-linking and stable performance of the coating. Most of the disulfide bonds are retained, and the self-healing performance is not affected.

[0057] The fifth stage involves slow cooling to eliminate residual thermal stress and avoid interfacial delamination caused by thermal shrinkage differences between the coating and the substrate due to rapid cooling. As a result, the internal stress of the cured coating is significantly reduced, and its performance retention is excellent over a wide temperature range.

[0058] Secondly, the vulcanized capsule provided in this application adopts the following technical solution.

[0059] A vulcanized capsule is manufactured according to the above-described method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule.

[0060] In summary, this application includes at least the following beneficial effects:

[0061] By using UV light to graft and preactivate, a high-density covalently bonded hydroxylated modified layer is constructed on the surface of the saturated butyl rubber capsule, which solves the core problem of butyl rubber having no active reaction sites. Combined with a two-step silane gradient grafting modification, the interface resistance to media barrier and surface activation are achieved simultaneously, laying a fully covalently bonded high-adhesion interface foundation for subsequent coatings.

[0062] The gradient transition adhesive layer with a continuously decreasing coefficient of thermal expansion from the inside to the outside perfectly connects the difference in coefficient of thermal expansion between the capsule body and the protective layer, eliminating the interfacial shear stress and peeling risk under wide temperature range alternating conditions. Combined with the single-end mercapto-single-end isocyanate-based polysulfide prepolymer anchoring agent layer, it realizes the continuous connection of fully covalent bonds between the functional layers, further enhancing the long-term stability of the interfacial bonding.

[0063] By designing a protective layer formulation containing perfluoroalkyl-modified thermotropic liquid crystal polyurethane and modified core-shell thermally conductive filler, the industry pain point of low-temperature crystallization embrittlement of conventional thermotropic liquid crystal polymers was solved, achieving high stability of mechanical properties over a wide temperature range, while improving the thermal conductivity and dielectric barrier performance of the coating.

[0064] The stepped heating curing process with precise timing control enables stepwise regulation of the orderly arrangement and cross-linking of liquid crystal units, fully releasing the internal stress of the coating and ensuring the uniformity of coating thickness and structural stability of the high curvature capsule surface coating.

[0065] The resulting vulcanized capsule can withstand rapid cooling and heating shocks. Under long-term high-temperature and high-pressure vulcanization conditions, it exhibits no interfacial delamination, no low-temperature embrittlement cracking, and no failure due to media erosion. This significantly improves the capsule's cycle life and compatibility with multiple product specifications, while effectively ensuring the quality of tire vulcanization and reducing the overall cost of tire production. Attached Figure Description

[0066] Figure 1 This is a flowchart illustrating the steps of a method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule. Detailed Implementation

[0067] The present application will be further described in detail below with reference to the accompanying drawings.

[0068] This application discloses a method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule, referring to... Figure 1 Specifically, it includes the following steps.

[0069] S1. Clean the capsule body.

[0070] The capsule body can be a butyl rubber vulcanized capsule. Immerse the capsule body in anhydrous ethanol and ultrasonically clean for 15 minutes to remove residual release agent, oil, or dust from the surface. Remove the capsule body, rinse it three times with deionized water, and then dry it in an environment of 60°C and a vacuum degree of -0.09 MPa for 2 hours, followed by cooling to room temperature. S2 must be performed 30 minutes after S1.

[0071] S2. Pre-activate the cleaned capsule surface to form a hydroxylated modified layer covalently bonded to the capsule surface.

[0072] Pre-activation requires the use of a photografting solution, which, by weight, comprises: 100 parts anhydrous ethanol, 1-3 parts benzophenone, and 4-6 parts hydroxyethyl acrylate. Stir all components of the photografting solution until completely dissolved. Prepare and use immediately, and keep the solution within 1 hour of storage.

[0073] The capsule body treated with S1 is completely immersed in a 25°C photografting solution for 60 seconds, ensuring that the photoinitiator and monomer penetrate 50-100nm into the rubber surface. If necessary, a rotating fixture can be used to rotate the capsule body in the photografting solution. Then, the capsule is removed, excess solution is drained from the surface, and it is immediately placed in the UV light treatment chamber with the capsule body rotating. A medium-pressure mercury lamp with a wavelength of 365nm and a power of 80W / cm is turned on, and the entire surface is uniformly irradiated for 60 seconds.

[0074] Under UV irradiation, benzophenone is excited to abstract hydrogen, causing alkyl free radicals to be generated from the saturated CH bonds in the butyl rubber of the capsule body. Hydroxyethyl acrylate monomers are then grafted in situ, forming a covalently bonded hydroxylated modified layer at a depth of 50-100 nm on the surface of the capsule body.

[0075] After irradiation, immediately rinse the capsule surface three times with anhydrous ethanol to remove unreacted monomers and photoinitiators, then dry it in a vacuum environment of 60°C and -0.09 MPa for 15 minutes to complete pre-activation. After pre-activation, it must enter S3 within 20 minutes to avoid the decay of surface hydroxyl activity.

[0076] S3. The pre-activated capsule body is modified by a two-step silane gradient grafting method. First, a covalently bonded fluorine-containing barrier layer is formed on the hydroxylation modification layer, and then a covalently bonded hydroxyl activation layer is formed on the fluorine-containing barrier layer. The fluorine-containing barrier layer is a 50-100 nm thick medium-resistant barrier layer, and the hydroxyl activation layer is a 10-20 nm thick highly active hydroxyl layer.

[0077] Step 1: Fluorosilane deep barrier grafting.

[0078] First, prepare a fluorosilane treatment solution, comprising, by weight: 95 parts anhydrous ethanol, 3 parts deionized water, 0.2 parts glacial acetic acid, 2 parts perfluorohexylethyltrimethoxysilane, and 0.05 parts dibutyltin dilaurate. Stir all components of the fluorosilane treatment solution thoroughly, adjust the pH to 5.0-5.5, pre-hydrolyze at 25°C for 15 minutes, and use immediately after preparation.

[0079] The S2-treated capsule body was immersed in a fluorosilane treatment solution and kept rotating at 25°C for 120 seconds. Utilizing the small molecular size and fast diffusion rate of fluorosilane, it diffused into the deep rubber layer of the capsule body (50-100 nm), undergoing dehydration condensation with UV-grafted hydroxyl groups to form a Si-OC covalently bonded fluorinated barrier layer. The capsule was then removed, and its entire surface was rinsed three times with anhydrous ethanol to terminate the reaction. It was then dried in a 40°C oven for 5 minutes to remove residual solvent without affecting the activity of unreacted hydroxyl groups on the surface.

[0080] Step 2: Activation and grafting of hydroxysilane surface layer.

[0081] First, prepare a hydroxysilane treatment solution, comprising, by weight: 95 parts anhydrous ethanol, 4 parts deionized water, 0.2 parts glacial acetic acid, 3 parts KH550, and 0.05 parts dibutyltin dilaurate. Stir all components of the hydroxysilane treatment solution thoroughly, adjust the pH to 5.0-5.5, pre-hydrolyze at 25°C for 10 minutes, and use immediately after preparation.

[0082] After the first step of treatment, the capsule body was immersed in a hydroxyl silane treatment solution and kept rotating at 25°C for 60 seconds. KH550 only underwent a condensation reaction with the remaining hydroxyl groups in the outermost 10-20 nm of the capsule body, forming a high-density outermost layer of amino and hydroxyl active sites, making the capsule surface hydrophilic. The capsule body was then removed and immediately rinsed three times with anhydrous ethanol to terminate the reaction. It was then dried at 60°C and -0.09 MPa for 20 minutes to complete the gradient grafting modification. After modification, it must proceed to step S4 within 30 minutes.

[0083] S4. Coat the surface of the hydroxyl-activated layer with a conductive primer layer, an anchoring agent layer and a gradient transition adhesive layer in sequence and cure.

[0084] First, a conductive primer was prepared, comprising, by weight: 100 parts of hydrolysis-resistant polyether-based waterborne polyurethane, 2 parts of hydroxyl-modified multi-walled carbon nanotubes, 3 parts of KH570, 0.5 parts of carbodiimide hydrolysis stabilizer, 200 parts of deionized water, and 0.3 parts of BYK-066N. The components of the conductive primer were dispersed at high speed for 40 minutes, then ultrasonically dispersed for 20 minutes, and finally defoamed under vacuum for 10 minutes to obtain a conductive primer working solution with a solid content of 30%.

[0085] After S3 treatment, the capsule body was rotated at a constant speed, and conductive primer was evenly sprayed onto the entire surface of the capsule using an air spraying method, controlling the dry film thickness to be 5μm. After spraying, it was placed in an 80℃ oven for 15 minutes to complete curing. After hydrolysis, KH570 in the conductive primer undergoes dehydration condensation with the hydroxyl groups on the capsule surface to form stable Si-O-Si covalent bonds, resulting in high interfacial adhesion. High-density methacryloyloxy active groups are generated in situ on the conductive primer surface, eliminating emulsifier migration issues.

[0086] After the conductive primer has cured, the entire surface of the capsule body is cleaned with oxygen plasma at a power of 50W and a vacuum of 20Pa for 30 seconds to remove trace amounts of residual organic contaminants and further increase the density of active groups. Within 10 minutes after the treatment is completed, the anchoring agent layer is prepared and coated.

[0087] The anchoring agent coating solution comprises, by weight, 100 parts of a single-thiol-single-isocyanate-based polysulfide prepolymer, 230 parts of a uniform solvent, and 0.5 parts of a triethylamine catalyst. The components of the anchoring agent coating solution are stirred thoroughly and prepared immediately. The uniform solvent in this application is a 1:1 mixture of toluene and ethyl acetate. The preparation method of the single-thiol-single-isocyanate-based polysulfide prepolymer is as follows.

[0088] The first step involved weighing 100 parts of hydroxyl-terminated polysulfide rubber (Mn=1000, hydroxyl value=112±2mgKOH / g) and dehydrating it for 2 hours at 75℃ under a vacuum of -0.095MPa. Then, under nitrogen protection, the mixture was cooled to room temperature, and 8.7 parts of TDI-80 and 0.1 parts of dibutyltin dilaurate were added. The temperature was then raised to 75℃ and maintained for 2 hours. Finally, di-n-butylamine titration was performed to determine the -NCO content to the theoretical value (3.2%), confirming the formation of a polysulfide semi-terminated prepolymer with single-terminated -NCO and single-terminated -OH groups.

[0089] In the second step, under nitrogen protection, the reaction system from the first step was cooled to 50°C, and 3.9 parts of 2-mercaptoethanol were added. The reaction was maintained at this temperature for 3 hours. Taking advantage of the fact that the reaction rate of -NCO and -OH at 50°C is more than 100 times that of -SH, polysulfide prepolymers with single-ended -SH and single-ended -OH were directionally generated. Then, titration was performed to check if the -NCO content had decreased to 0, and iodometric analysis confirmed that the -SH value deviated from the theoretical value within ±0.1%, thus confirming the formation of the target product.

[0090] In the third step, under nitrogen protection, 7.9 parts of TDI-80 and 0.05 parts of dibutyltin dilaurate were added to the reaction system from the second step, and the reaction was maintained at 50°C for 2 hours. -NCO reacts only with -OH and not with -SH, generating the target single-terminated mercapto-single-terminated isocyanate-based polysulfide prepolymer. Titration analysis showed that the -NCO content deviated from the theoretical value (3.2%) within ±0.1%, and the -SH value retention rate was 100%. The mixture was then cooled to room temperature, sealed, and stored under nitrogen for later use.

[0091] After plasma cleaning, the capsules are rotated at a constant speed, and the anchoring agent coating solution is sprayed on, controlling the dry film thickness to 5-10 μm. After spraying, the capsules are left to stand at 25°C for 15 minutes to complete the Michael addition click reaction between the -SH group at the anchoring agent end and the methacryloyloxy group on the KH570 surface of the conductive primer. The -NCO group at the other end of the anchoring agent layer is exposed to the outside, for covalent bonding with the hydroxyl groups of the subsequent gradient transition adhesive layer.

[0092] The gradient transition layer includes a transition bottom layer and a transition top layer. The transition bottom layer is closer to the capsule body than the transition top layer. The coefficient of thermal expansion of the gradient transition layer decreases continuously from the side closer to the capsule body to the side farther away from the capsule body.

[0093] The transitional underlayer adhesive is prepared, comprising, by weight: 100 parts butyl rubber adhesive, 30-35 parts hydroxyl-terminated polysulfide rubber adhesive, 6-7 parts butyl rubber-g-polysulfide rubber graft compatibilizer, and 0.1-0.3 parts dibutyltin dilaurate. Both the butyl rubber adhesive and the hydroxyl-terminated polysulfide rubber adhesive have a solid content of 30% and use the same solvent.

[0094] The gradient transition adhesive is evenly sprayed onto the surface of the anchoring agent layer, controlling the dry film thickness to 8-10 μm. After spraying, it is kept at 80℃ for 10 minutes to pre-cur until it is surface dry and not sticky, thus completing the covalent bonding with the anchoring agent layer.

[0095] The transition surface adhesive is prepared by weight as follows: 25-35 parts of butyl rubber adhesive, 100 parts of hydroxyl-terminated polysulfide rubber adhesive, 6-7 parts of butyl rubber-g-polysulfide rubber graft compatibilizer, and 0.1-0.3 parts of dibutyltin dilaurate.

[0096] Spray a transition topcoat onto the pre-cured transition substrate, controlling the dry film thickness to 8-10 μm, and the total thickness of the gradient transition adhesive layer to 15-20 μm. After spraying, keep it at 100℃ for 15 min to complete curing, forming a continuous thermal expansion gradient interface without phase separation or stress concentration.

[0097] S5. Prepare a protective layer of thermotropic liquid crystal polyurethane containing perfluoroalkyl and spray it onto the surface of the cured gradient transition adhesive layer.

[0098] The protective layer comprises component A, component B, and initiator mother liquor. Component A is prepared first, comprising, by weight: 100 parts hydroxyl-terminated polysulfide rubber, 25-35 parts polyether polyol, 10-20 parts perfluoroalkyl-modified thermotropic liquid crystal polyurethane, and 35-45 parts modified core-shell thermally conductive filler. Component A is further divided into A1 base material and A2 catalyst mother liquor.

[0099] Preparation of A1 base material:

[0100] First, the perfluorobutyl ethyl modified thermotropic liquid crystal polyurethane prepolymer was synthesized.

[0101] First, 110 parts of polytetrahydrofuran ether glycol with a molecular weight of 2000, 12 parts of perfluorobutylethyl hydroquinone, and 32 parts of MDI were measured and reacted at 80°C for 2 hours under nitrogen protection. Then, 6 parts of 1,4-butanediol and 8 parts of PDMS glycol with a number average molecular weight of 1000 were added, and the reaction was continued at 80°C for 3 hours. The -NCO content was measured to be 0, and the product was cooled and discharged to obtain the target liquid crystal polyurethane, which was then sealed and stored for later use.

[0102] Then, the modified core-shell thermally conductive filler is prepared.

[0103] Measure 15 parts of hexagonal boron nitride, 35 parts of boron nitride whiskers, and 50 parts of α-alumina, and mix them evenly to obtain a first mixture. Add deionized water at a weight ratio of the first mixture to deionized water of 40:60, stir and disperse for 30 minutes to obtain a mixture with a solid content of 40%.

[0104] Take 50 parts of mica flakes and 50 parts of talc powder, mix them, add deionized water, and stir to disperse to obtain a slurry with a solid content of 60%.

[0105] First, the slurry is evenly coated onto a filter cloth to form a 40μm thick wet film. Then, a mixed liquid is sprayed onto the surface at a rate of 10g / m², resulting in the first layer. A second layer of slurry of the same thickness is then coated, followed by another spray of the same amount of mixed liquid, resulting in the second layer. The first and second layers are hot-pressed at 150℃ and 5MPa for 5 minutes to obtain a composite membrane with a thickness of 40-45μm. The composite membrane is dried at 120℃ for 4 hours and then placed in a liquid nitrogen cryogenic pulverizer, where it is pulverized and graded at -196℃ to obtain sheet-like fillers with an aspect ratio of (15-20):1.

[0106] Next, take 100 parts by weight of sheet-like packing material, 200 parts by weight of anhydrous ethanol, 20 parts by weight of deionized water, and 4 parts by weight of KH570. Add glacial acetic acid to adjust the pH to 5.5, and stir the reaction at 60℃ for 4 hours. High-density vinyl double bonds are grafted onto the packing surface through siloxane bonds. After the reaction is complete, filter out the sheet-like packing material, wash it three times with anhydrous ethanol, and dry it in a vacuum environment of 120℃ and -0.095MPa for 4 hours to obtain the modified core-shell thermally conductive packing material, which is then sealed and stored for later use.

[0107] Then, the preparation of the A1 base material began. First, 100 parts of hydroxyl-terminated polysulfide rubber and 30 parts of DL-2000 polyether polyol were measured, stirred, and dehydrated for 2 hours at 75°C and a vacuum of -0.095 MPa. Then, under nitrogen protection, 15 parts of perfluorobutyl ethyl modified thermotropic liquid crystal polyurethane were added, heated to 130°C, and stirred for 20 minutes until completely dissolved, then cooled to 75°C. Next, 40 parts of modified core-shell thermally conductive filler, 0.5 parts of hydroxyl-modified multi-walled carbon nanotubes, 2 parts of flake conductive mica powder, 8 parts of BYK-410 rheology modifier, and 0.5 parts of BYK-066N defoamer were added, stirred and dispersed at 3000 r / min for 60 minutes, and then defoamed under a vacuum of -0.095 MPa for 30 minutes. Then, the temperature was lowered to below 25°C, and 0.25 parts of delayed acetylacetone chelated organic bismuth catalyst were added. The mixture was stirred for 5 minutes, sealed, and stored under nitrogen to obtain the A1 base material.

[0108] Preparation of A2 catalyst mother liquor:

[0109] Six parts of the delayed acetylacetone chelated organobismuth catalyst and 94 parts of the uniform solvent were measured and stirred evenly to obtain a mother liquor of A2 catalyst with a solid content of 6%, which was sealed and stored for later use.

[0110] Initiator mother liquor preparation:

[0111] Measure 10 parts of BPO and 90 parts of ethyl acetate, stir well, seal and store in a cool environment below 10°C for later use.

[0112] Preparation of component B:

[0113] 100 parts of poly(1,4-butanediol adipate) diol with a number average molecular weight of 2000 and 15 parts of dimethylolpropionic acid were weighed and dehydrated at 120°C and -0.098 MPa vacuum for 3 hours to obtain a second mixture. The mixture was then cooled to 75°C, and 45 parts of MDI were added under nitrogen protection. The mixture was stirred for 2 hours, and the -NCO content was measured to the theoretical value to obtain a second prepolymer. The mixture was then cooled to 55°C, and 0.1 parts of a delayed-type acetylacetone chelating organobismuth catalyst, 8 parts of a soft-segment disulfide chain extender HEDS, 0.2 parts of a DBU dynamic catalyst, 0.15 parts of a TBP synergistic catalyst, and 0.5 parts of a composite antioxidant (antioxidant 1010:antioxidant 168 = 1:1) were added. The mixture was stirred for 1.5 hours, and the -NCO content was measured to the theoretical value. The mixture was then cooled to room temperature, sealed, and stored under nitrogen to obtain component B.

[0114] Protective coating application:

[0115] The colloid for spraying was prepared on-site by measuring 80 parts of A1 base material, 0.6 parts of A2 catalyst mother liquor, 5.6 parts of initiator mother liquor, and 20 parts of component B. The mixture was stirred for 5 minutes and then degassed under a vacuum of -0.095 MPa for 10 minutes to obtain the protective colloid for spraying. Electrostatic spraying was then initiated, controlling the dry film thickness to be stable at 200 μm, with the overall surface thickness deviation controlled within ±4%.

[0116] S6. The protective layer after spraying is cured by step temperature increase to obtain a wide temperature range vulcanized capsule.

[0117] Immediately after spraying, transfer the capsule body for heating and curing, following the steps below.

[0118] S61, constant temperature holding at 45-55℃ for 10-20 minutes, to achieve full leveling of the entire coating surface (including the high curvature shoulder), eliminate thickness deviation, and prevent cross-linking reaction.

[0119] S62, constant temperature holding at 85-95℃ for 15-25 min, decapsulates the delayed organobismuth catalyst, specifically catalyzing the hydroxyl-NCO reaction to form a weakly cross-linked mobile network. Simultaneously, the DBU and TBP composite catalyst rapidly and dynamically exchanges disulfide bonds in the soft segment backbone, releasing leveling internal stress. BPO stably decomposes to release free radicals, triggering the graft copolymerization of vinyl double bonds on the filler surface with the matrix.

[0120] S63. Heat to 105-115℃ at a rate of 1-3℃ / min, and hold at that temperature for 35-45min. The liquid crystal units in the weakly cross-linked network move fully, complete the uniform and orderly arrangement, and form a perfect nematic domain structure.

[0121] S64, heated to 120-130℃ at a rate of 0.5-1.5℃ / min, and held at that temperature for 25-35min, allows the organic bismuth catalyst to dominate deep crosslinking, completely locking the ordered liquid crystal structure. Simultaneously, the soft-segment disulfide bonds continuously and dynamically exchange to release crosslinking internal stress, while the composite antioxidant inhibits thermal decomposition.

[0122] S65. Cool to room temperature at a rate of 1-3℃ / min to eliminate residual thermal stress.

[0123] After curing, the capsule body is removed, and the edges are trimmed to remove burrs and excess coating. Simultaneously, a rubber thickness gauge is used to measure the coating thickness across the entire surface; a thickness deviation within ±4% is considered acceptable. Then, an airtightness tester is used, holding the product at 1.5 MPa for 30 minutes; a pressure drop within 0.02 MPa is considered acceptable. Further accelerated aging verification is performed, aging at 180℃ and 2.5 MPa saturated steam for 72 hours; no delamination or blistering at the interface is considered acceptable. The qualified product is then stored in a dry, cool place in a sealed container to obtain the final wide-temperature-range, highly adaptable vulcanized capsule.

[0124] This application also discloses a vulcanized capsule manufactured according to the above-described method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule.

[0125] The following detailed description uses specific embodiments and comparative examples.

[0126] Example 1:

[0127] The manufacturing method of a wide-temperature-range, highly adaptable vulcanized capsule, as described above, mainly involves determining the weight proportions of the following components and the parameters for S6 stepwise temperature-increase curing.

[0128] The photografting treatment solution comprises, by weight: 100 parts anhydrous ethanol, 1 part benzophenone, and 4 parts hydroxyethyl acrylate.

[0129] The transition layer comprises, by weight, 100 parts of butyl rubber paste, 30 parts of hydroxyl-terminated polysulfide rubber paste, 6 parts of butyl rubber-g-polysulfide rubber graft compatibilizer, and 0.1 parts of catalyst.

[0130] The transition surface layer comprises, by weight: 25 parts butyl rubber paste, 100 parts hydroxyl-terminated polysulfide rubber paste, 6 parts butyl rubber-g-polysulfide rubber graft compatibilizer, and 0.1 parts catalyst.

[0131] The S6 step temperature curing process specifically includes the following steps:

[0132] S61, keep warm at 45℃ for 10 minutes;

[0133] S62, keep warm at 85℃ for 15 minutes;

[0134] S63. Heat to 105℃ at a rate of 1℃ / min and hold at that temperature for 35min.

[0135] S64. Heat to 120℃ at a rate of 0.5℃ / min and hold at that temperature for 25 minutes.

[0136] S65, cool to room temperature at a rate of 1℃ / min.

[0137] Example 2:

[0138] The difference from Example 1 is that the photografting treatment solution comprises, by weight, 100 parts of anhydrous ethanol, 3 parts of benzophenone, and 6 parts of hydroxyethyl acrylate.

[0139] The transition layer comprises, by weight, 100 parts of butyl rubber paste, 35 parts of hydroxyl-terminated polysulfide rubber paste, 7 parts of butyl rubber-g-polysulfide rubber graft compatibilizer, and 0.3 parts of catalyst.

[0140] The transition surface layer comprises, by weight: 35 parts butyl rubber paste, 100 parts hydroxyl-terminated polysulfide rubber paste, 7 parts butyl rubber-g-polysulfide rubber graft compatibilizer, and 0.3 parts catalyst.

[0141] The S6 step temperature curing process specifically includes the following steps:

[0142] S61, keep warm at 55℃ for 20 minutes;

[0143] S62, 95℃ constant temperature for 25 minutes;

[0144] S63. Heat to 115℃ at a rate of 3℃ / min and hold at that temperature for 45min.

[0145] S64. Heat to 130℃ at a rate of 1.5℃ / min and hold at that temperature for 35 minutes.

[0146] S65, cool to room temperature at a rate of 3℃ / min.

[0147] Comparative Example 1:

[0148] The difference from Example 1 is that S2 is not performed; that is, S3 is performed after S1 is completed.

[0149] Comparative Example 2:

[0150] The difference from Example 1 is that in S3, the two-step silane gradient grafting modification is changed to a one-step silane gradient grafting modification. That is, only the preparation and corresponding modification of the fluorosilane treatment solution are carried out, and the preparation and corresponding modification of the hydroxysilane treatment solution are not carried out. Furthermore, the fluorosilane treatment solution includes, by weight, 95 parts of anhydrous ethanol, 7 parts of deionized water, 0.4 parts of glacial acetic acid, 2 parts of perfluorohexylethyltrimethoxysilane, 3 parts of KH550, and 0.1 parts of dibutyltin dilaurate.

[0151] Comparative Example 3:

[0152] The difference from Example 1 is that the gradient transition adhesive layer of S4 is removed, that is, S5 is performed after the anchoring agent layer related treatment of S4 is completed.

[0153] Comparative Example 4:

[0154] The difference from Example 1 is that the anchoring agent coating liquid of S4 comprises, by weight: 100 parts of hydroxyl-terminated liquid polysulfide rubber and 230 parts of uniform solvent.

[0155] Comparative Example 5:

[0156] The difference from Example 1 is that in S5, the perfluorobutyl ethyl modified thermotropic liquid crystal polyurethane prepolymer is replaced with a conventional thermotropic liquid crystal polyurethane prepolymer, that is, the perfluorobutyl ethyl hydroquinone in the synthesis process of the thermotropic liquid crystal polyurethane prepolymer is replaced with hydroquinone.

[0157] Comparative Example 6:

[0158] The difference from Example 1 is that the staged temperature rise curing in S6 is changed to one-step constant temperature curing, that is, after the protective layer is sprayed, it is cured at 120°C for 2 hours.

[0159] The following indicators were tested on the vulcanized capsules obtained in the above embodiments and comparative examples.

[0160] Initial interface adhesion test:

[0161] Three test points were selected on both the straight section and the high-curvature area of ​​the shoulder of the vulcanized capsule. A six-blade cross-cutting device was used with a 1mm spacing between the cuts. 3M 600 standard test tape was attached and peeled off vertically at a uniform speed. The coating peeling was observed and rated from 0 to 5 (0 for no coating peeling, 1 for less than 5% of the coating peeling area, 2 for 5-15% of the coating peeling area, 3 for 15-35% of the coating peeling area, 4 for 35-65% of the coating peeling area, and 5 for more than 65% of the coating peeling area). The worst rating of the six test points was taken as the final result.

[0162] Interfacial adhesion test after damp heat aging:

[0163] The sample was placed in a saturated steam autoclave at 180℃ and 2.5MPa and aged at constant temperature and pressure for 72 hours. After being removed, it was placed at room temperature for 2 hours. The initial interface adhesion test was performed as described above, and the change in adhesion level was recorded.

[0164] Crack initiation rate test after rapid cooling and heating thermal shock:

[0165] The sample was placed at -20℃ for 2 hours and then rapidly transferred to a 200℃ oven for 30 minutes within 30 seconds. This constituted one complete impact cycle, which was repeated 10 times. After each cycle, the entire surface of the capsule was scanned using a stereomicroscope. The area covered by cracks longer than 50 μm was counted, and the crack initiation rate was calculated as (total crack area / total observed capsule area) × 100%. The maximum crack length was recorded simultaneously.

[0166] Wide-temperature-range energy storage modulus fluctuation amplitude test:

[0167] A standard sample (30mm×5mm×2mm) was cut from the sample surface. A dynamic thermomechanical analyzer was used in three-point bending mode, with a test frequency of 1Hz, a heating rate of 3℃ / min, and a test temperature range of -40-200℃. The storage modulus was recorded throughout the test. The modulus fluctuation range is calculated as follows: (maximum storage modulus in the test temperature range - minimum storage modulus in the test temperature range) / storage modulus at room temperature of 25℃ × 100%.

[0168] Interface peeling rate test after 500 vulcanization cycles:

[0169] After 500 vulcanization cycles, the entire surface of the capsule was scanned using a stereomicroscope. The total area of ​​delamination and bubbling at the interface between the coating and the body was counted, and the interface peeling rate was calculated as: total delamination and bubbling area / total surface area of ​​the capsule × 100%.

[0170] Mass swelling rate test for resistance to media:

[0171] Cut a standard specimen (20mm × 20mm × 2mm) from the sample surface and weigh its initial mass. Immerse the specimen in a vulcanizing medium mixture (accelerator CZ: plasticizer DOP = 1:1) at 180℃ and soak for 72 hours. After removal, quickly blot the surface liquid with filter paper and immediately weigh the swollen mass. Calculate the mass swelling rate = (swollen mass - initial mass) / initial mass × 100%. The lower the value, the better the resistance to medium erosion.

[0172] The specific experimental results are shown in Table 1.

[0173] Table 1:

[0174]

[0175] After removing S2 in Comparative Example 1, the saturated butyl rubber had no active reaction sites, and silane could not be covalently grafted. The initial adhesion dropped sharply and completely failed after aging. This verifies that the pre-activation to form a covalently bonded hydroxylated modified layer is a key step to achieve stable bonding at the interface.

[0176] In Comparative Example 2, after the silane gradient grafting modification was replaced with a one-step silane system, the silane system became unstable due to premature cross-linking and could not form a gradient structure combining the barrier layer and the activation layer. The resistance to media and the interfacial stability decreased significantly, which verified the core role of the stepwise grafting process in resisting media erosion and activating interfacial activity.

[0177] In Comparative Example 3, after removing the gradient transition adhesive layer of S4, the difference in thermal expansion coefficients between the capsule body and the protective layer could not be eliminated. Under wide temperature range alternation, the interfacial shear stress was concentrated, and the thermal shock crack initiation rate and the interfacial peeling rate after cycling were high, verifying that the gradient transition layer is the core means to solve the interfacial fatigue peeling problem.

[0178] In Comparative Example 4, after replacing the single-terminated mercapto-single-terminated isocyanate-based polysulfide prepolymer with conventional hydroxyl-terminated liquid polysulfide rubber, it was impossible to achieve continuous covalent bonding of all functional layers. The interfacial bonding force relied solely on physical adsorption, and the adhesion and cycle stability decreased significantly after aging. This verified the crucial role of the special anchoring agent in the long-term reliability of the interfacial bonding.

[0179] In Comparative Example 5, after replacing the perfluoroalkyl-modified thermotropic liquid crystal polyurethane with unmodified liquid crystal polyurethane, the problem of low-temperature crystallization embrittlement was fully manifested. After 10 thermal shocks, the crack initiation rate was 100%, and the modulus fluctuation over the wide temperature range exceeded 70%, directly verifying that perfluorination modification is the core key to solving low-temperature embrittlement and achieving stable performance over the wide temperature range.

[0180] In Comparative Example 6, after replacing the five-stage stepped temperature curing process with a one-step constant temperature curing process, the internal stress of the coating could not be released, the thickness uniformity was severely out of control, and thermal shock cracking and interface peeling problems were prominent. This verified the key role of the stepped curing process in the stability of the coating structure and the elimination of internal stress.

[0181] The above are all preferred embodiments of this application, and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the structure, shape and principle of this application should be covered within the scope of protection of this application.

Claims

1. A method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule, characterized in that: Specifically, the following steps are included: S1. Clean the capsule body; S2. Pre-activate the cleaned capsule surface to form a hydroxylated modified layer covalently bonded to the capsule surface. S3. The pre-activated capsule body is modified by a two-step silane gradient grafting method. First, a covalently bonded fluorine-containing barrier layer is formed on the hydroxylation modification layer, and then a covalently bonded hydroxyl activation layer is formed on the fluorine-containing barrier layer. S4. Coat the surface of the hydroxyl-activated layer with a conductive primer layer, an anchoring agent layer and a gradient transition adhesive layer in sequence and cure. S5. Prepare a protective layer of thermotropic liquid crystal polyurethane containing perfluoroalkyl and spray it onto the surface of the cured gradient transition adhesive layer. S6. The protective layer after spraying is cured by step temperature increase to obtain a wide temperature range vulcanized capsule. The coefficient of thermal expansion of the gradient transition adhesive layer decreases continuously from the side closer to the capsule body to the side farther away from the body.

2. The method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule according to claim 1, characterized in that: The pre-activation of S2 specifically involves immersing the cleaned capsule body in a photografting solution containing a photoinitiator and hydroxyl monomer, removing it, draining it, subjecting it to UV full-surface irradiation, and then purifying and drying it.

3. The method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule according to claim 2, characterized in that: The photografting treatment solution comprises, by weight: 100 parts anhydrous ethanol, 1-3 parts benzophenone, and 4-6 parts hydroxyethyl acrylate.

4. The method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule according to claim 1, characterized in that: The gradient transition layer in S4 includes a transition bottom layer and a transition top layer, with the transition bottom layer being closer to the capsule body than the transition top layer. The transition layer comprises, by weight, 100 parts of butyl rubber paste, 30-35 parts of hydroxyl-terminated polysulfide rubber paste, 6-7 parts of butyl rubber-g-polysulfide rubber graft compatibilizer, and 0.1-0.3 parts of catalyst. The transition surface layer comprises, by weight: 25-35 parts of butyl rubber paste, 100 parts of hydroxyl-terminated polysulfide rubber paste, 6-7 parts of butyl rubber-g-polysulfide rubber graft compatibilizer, and 0.1-0.3 parts of catalyst.

5. The method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule according to claim 1, characterized in that: The anchoring agent layer in S4 is a single-terminal mercapto-single-terminal isocyanate-based polysulfide prepolymer coating.

6. The method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule according to claim 1, characterized in that: The protective layer in S5 includes component A and component B; component A includes hydroxyl-terminated polysulfide rubber, polyether polyol, perfluoroalkyl modified thermotropic liquid crystal polyurethane and modified core-shell thermally conductive filler; component B is a polyurethane prepolymer containing soft segment disulfide bonds.

7. The method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule according to claim 6, characterized in that: The perfluoroalkyl-modified thermotropic liquid crystal polyurethane is prepared by reacting polytetrahydrofuran ether diol, perfluorobutylethyl hydroquinone, diisocyanate and chain extender.

8. The method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule according to claim 6, characterized in that: The modified core-shell thermally conductive filler is a silane coupling agent modified sheet-like composite filler, which is prepared by hot pressing and pulverizing hexagonal boron nitride, boron nitride whiskers, α-alumina, mica sheets and talc powder.

9. The method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule according to claim 1, characterized in that: The step-by-step temperature curing of S6 specifically includes the following steps: S61, maintain a constant temperature of 45-55℃ for 10-20 minutes to achieve coating leveling; S62, keep at 85-95℃ for 15-25 minutes to complete pre-crosslinking and release internal stress; S63. Heat to 105-115℃ at a rate of 1-3℃ / min, hold at a constant temperature for 35-45min, and achieve orderly arrangement of liquid crystal cells; S64. Heat to 120-130℃ at a rate of 0.5-1.5℃ / min, hold at that temperature for 25-35min to complete deep cross-linking and structural locking; S65. Cool to room temperature at a rate of 1-3℃ / min to eliminate residual thermal stress.

10. A vulcanized capsule, characterized in that: The method for manufacturing a wide-temperature-range, highly adaptable vulcanized capsule according to any one of claims 1-9 is used.

Images