CN110563922A - Chemical crosslinking type high-performance room-temperature rapid self-repairing flexible material and preparation method and application thereof - Google Patents
Chemical crosslinking type high-performance room-temperature rapid self-repairing flexible material and preparation method and application thereof Download PDFInfo
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Abstract
the invention provides a chemical crosslinking type high-performance room-temperature rapid self-repairing flexible material which is prepared from raw materials of hydroxypropyl terminated polydimethylsiloxane, isocyanate, a crosslinking agent and a chain extender. The flexible material has room temperature self-repairing performance and heat-resistant performance, a cross-linked structure is introduced to improve the heat resistance and strength, meanwhile, the good room temperature self-repairing performance is still maintained, the repairing efficiency is high, the defects that the existing flexible heat-resistant material does not have the self-repairing characteristic and the common room temperature self-repairing material does not resist high temperature are effectively overcome, and the gap in the field is filled. The flexible material has stable use performance, wide use range and long service life, can be applied to systems such as various elastomers, coating materials, encapsulating materials, adhesives and the like, is particularly applied to an outer protective coating and a flexible workpiece material which are applied to a high-temperature environment or have heat-resistant and ablation-resistant requirements, such as an aircraft heat-resistant coating, and has the advantages of maintenance-free performance, high reliability and the like, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of intelligent high polymer materials, and particularly relates to a chemical crosslinking type high-performance room-temperature rapid self-repairing flexible material, and a preparation method and application thereof.
Background
The heat-proof material has irreplaceable key effects in the aerospace craft, the aerodynamic thermal environment is more and more severe along with the continuous improvement of the flight speed of the aerospace craft, and the effective outer heat-proof layer can provide enough protection for the aerospace craft when the aerospace craft is subjected to severe aerodynamic heating, so that the flight safety is ensured. However, the mere presence of thermal protection in the thermal protection layer is still an ineffectively avoidable risk, wherein cracking of the thermal protection layer is a significant risk and a fatal threat to the safety of aerospace vehicles, for example, the U.S. accident "columbia" is caused by cracking of the thermal protection layer due to accidental impacts, and therefore, maintaining the structural integrity of the thermal protection layer is crucial. At present, the heat-resistant coating with the flexible structure characteristic is more and more important, the flexible material is easier to generate microcracks because the flexible material is subjected to mechanical actions such as static or dynamic stretching, extruding, shearing, twisting and the like for a long time, the existence of the defects such as the cracks is a great potential safety hazard of the heat-proof structure, therefore, the flexible heat-proof material is modified, the integrity of the structure can be maintained, the automatic healing function of the cracks is realized, the self-repairing function of the heat-proof material is endowed, the service life is prolonged, and the maintenance cost is reduced, so that the heat-proof material has very important.
the self-repairing material is a novel material capable of self-repairing when an object is damaged. The self-repairing purpose is to prevent the crack from continuing to expand in the initial stage of crack formation, or automatically close the crack after the material is damaged, and recover the initial structure and performance of the material, so that the application reliability of the material is improved, the application range is expanded, and the service life is prolonged. The room temperature self-repairing material has convenience and mild type of repairing conditions, so that the room temperature self-repairing material has important value in practical application, especially in the aspects of self-maintenance of protective materials and the like. If the ablation heat-proof material has a self-repairing function through modification, the ablation heat-proof material can be automatically repaired when the material has cracks and local damage, so that the safety and the reliability of the aircraft are greatly improved, the service life is prolonged, and the development of the flexible ablation heat-proof self-repairing material has important significance for the development of a new generation of aerospace aircraft. However, most of the existing self-repairing materials are used in the fields with mild service temperature, such as artificial skin, sensors, medical materials, automobile coatings and the like, and the research on the field of heat-resistant materials is very few.
The current self-repairing materials are divided into an external self-repairing material and an intrinsic self-repairing material according to the repairing types. The externally-applied self-repairing material is characterized in that the self-repairing function is realized by introducing additional components such as microcapsules containing a repairing agent system, carbon nano tubes, micro vessels or glass fibers into a material matrix. The intrinsic self-repairing material does not need an additional repairing system, but the material contains special chemical bonds or other physical and chemical properties such as reversible covalent bonds, non-covalent bonds, molecular diffusion and the like to realize the self-repairing function. The method does not depend on a repairing agent, complex steps such as a repairing agent embedding technology in advance and the like are omitted, repeated repairing can be realized on the same damaged part for many times, the influence on the performance of a matrix is small, the design of the molecular structure of the material is the biggest challenge of the method, and the method becomes a research focus at present.
At present, most of intrinsic self-repairing materials belong to linear non-crosslinked polymers, and the intrinsic self-repairing materials are rare for chemical crosslinking room-temperature self-repairing materials with better heat resistance. For a crosslinked polymer system based on a dynamic reversible covalent bond, in order to maintain sufficient molecular chain fluidity and diffusion capability of the material to facilitate the self-repairing reaction under room temperature or mild conditions, the application universality of most of the self-repairing systems reported at present, which are gels or low-molecular-weight soft material systems, is greatly restricted. It is a challenge to achieve a balance between self-healing properties and high mechanical strength under mild conditions of high molecular weight. Therefore, the development of polymer materials which can be repaired under mild conditions and have excellent mechanical properties has wide market demands and application requirements.
for example, Wu X et al (Heat-trigged poly (siloxane-urethane) based on dispersed substrates for self-healing application [ J ]. Journal of Applied Polymer Science,2018,135(31):46532.) synthesize a self-healing elastomer with reversible disulfide bonds by forming HDI diisocyanate and aminopropyl terminated PDMS into a prepolymer by a two-step process followed by the addition of aliphatic disulfide as a chain extender. The elastomer can be repaired for 12 hours at the temperature of 60 ℃, and the repairing efficiency can reach 40 percent; repairing for 12h at 90 ℃, wherein the repairing time can be 90%; repairing for 3h at 120 ℃, wherein the repairing efficiency reaches 90-97%. But the self-repairing condition still needs heating, and the room temperature self-repairing can not be realized. Meanwhile, the document does not consider the heat resistance of the material, the material is still a linear polymer, the heat resistance is insufficient, and the requirement of a further aerospace heat-resistant material cannot be met.
for another example, Kim et al (Superior material gauge and Fast Self-heating at Room Temperature Engineered by transient Materials, J. Advanced Materials,2017,30 (1)) studied different kinds of diisocyanates and polyether diols, and added disulfide bonds to perform chain extension and Self-repair to prepare a polyurethane elastomer, wherein the isophorone diisocyanate/polyether diol system is 25 ℃, the 2h repair rate is 88.2%, and the tensile strength can reach 6.0MPa, but the material is an uncrosslinked thermoplastic material and is difficult to meet the requirement of high Temperature and heat resistance.
for another example, yankee et al (preparation and characterization of thermoreversible self-repairing polyurethane elastomers [ J ] materials engineering, 2017,45(8).) introduced reversible disulfide bonds into polyester polyurethane elastomers using Hexamethylene Diisocyanate (HDI) trimer as a cross-linking agent and 4, 4-diaminodiphenyl disulfide (AFD) as a chain extender. The tensile strength of the self-repairing polyurethane elastomer is 7.7MPa, and the self-repairing efficiency of the tensile strength is 97.4% under the conditions that the temperature is 60 ℃ and the repairing time is 24 hours. However, although the self-repairing polyurethane elastomer has a cross-linked structure, the self-repairing condition also requires heating, and room-temperature self-repairing is not realized. Meanwhile, the heat resistance of the material is not considered in the selection of the main raw materials, and the requirement of the aerospace heat-resistant material cannot be met.
According to the existing literature search, no research report on the room temperature rapid self-repairing of the flexible heat-resistant material is reported.
disclosure of Invention
The invention aims to provide a chemical crosslinking type high-performance room-temperature rapid self-repairing flexible material, and a preparation method and application thereof.
The invention provides a chemical crosslinking type room temperature rapid self-repairing flexible material, which is prepared by taking hydroxypropyl end-capped polydimethylsiloxane, isocyanate, a crosslinking agent and a chain extender as raw materials; wherein the molar ratio of the hydroxypropyl end-capped polydimethylsiloxane, the isocyanate, the cross-linking agent and the chain extender is (1-10): 5-15): 0.1-5): 5-15; the cross-linking agent is a polyisocyanate cross-linking agent; the chain extender is an aliphatic or aromatic diamino disulfide containing reversible disulfide bonds.
Furthermore, the mole ratio of the hydroxypropyl-terminated polydimethylsiloxane, the isocyanate, the cross-linking agent and the chain extender is 5:10.5 (0.34-3.41) to 5.5-10.1.
Further, the molar ratio of the hydroxypropyl-terminated polydimethylsiloxane, the isocyanate, the cross-linking agent and the chain extender is 5:10.5:3.41: 10.1.
Further, the isocyanate is a diisocyanate, preferably isophorone diisocyanate, hexamethylene diisocyanate, 4' dicyclohexylmethane diisocyanate or diphenylmethane diisocyanate; and/or the cross-linking agent is hexamethylene diisocyanate trimer; and/or the chain extender is 4,4' -diaminodiphenyl disulfide.
The invention also provides a preparation method of the self-repairing flexible material, which is characterized by comprising the following steps: it comprises the following steps:
(1) Synthesis of prepolymer: adding a catalytic amount of catalyst into hydroxypropyl-terminated polydimethylsiloxane and isocyanate, and reacting to obtain a prepolymer;
(2) And (3) crosslinking reaction: adding a cross-linking agent into the prepolymer for cross-linking reaction to obtain a reaction solution;
(3) Chain extension reaction: dissolving a chain extender in an organic solvent, adding the chain extender into a reaction solution after a crosslinking reaction, and reacting to obtain a reaction solution;
(4) And pouring the reaction solution into a mould, and curing to obtain the product.
Further, the air conditioner is provided with a fan,
In the step (1), the catalyst is dibutyltin dilaurate;
and/or, in the step (3), the organic solvent is dimethylacetamide or dimethylformamide.
Further, the air conditioner is provided with a fan,
In the step (3), the method for adding the organic solvent containing the chain extender into the prepolymer is dropwise adding.
Further, the air conditioner is provided with a fan,
In the step (1), argon is introduced into the mixture for stirring for 1 to 6 hours at the temperature of between 60 and 100 ℃;
And/or in the step (2), the crosslinking reaction is carried out for 0.5-5h at the temperature of 60-100 ℃;
And/or, in the step (3), the reaction is stirred for 10-60min at the rotating speed of 200-800 r/min and the temperature of 20-60 ℃;
And/or, in the step (4), the solidification is carried out at 90 ℃ for 12 hours under vacuum;
Preferably, in the step (1), the reaction is carried out at 60 ℃ by introducing argon and stirring for 1 h;
And/or in the step (2), the crosslinking reaction is stirred for 0.5h at the temperature of 60 ℃;
And/or in the step (3), the reaction is stirred for 10min at the rotating speed of 200 revolutions per minute and the temperature of 60 ℃.
The invention also provides application of the self-repairing flexible material in preparation of the heat-resistant room-temperature self-repairing material.
Further, the heat-resistant room temperature self-repairing material is an elastomer, a coating, a potting material or an adhesive; or the heat-resistant room temperature self-repairing material is an outer protective coating and a flexible workpiece material which are applied to a high-temperature environment or have heat-resistant and ablation-resistant requirements, and preferably, the heat-resistant room temperature self-repairing material is an outer coating of an aircraft.
The chemical crosslinking type high-performance room temperature quick self-repairing flexible material has room temperature self-repairing performance and heat resistance, can still keep good room temperature self-repairing performance while introducing a crosslinking structure to improve heat resistance and strength, can quickly complete self-repairing at room temperature, has high repairing efficiency and good heat stability, effectively overcomes the defects that the existing flexible heat-resistant material does not have self-repairing characteristics and the common room temperature self-repairing material does not resist high temperature, and fills the gap in the field. The flexible material has stable use performance, wide use range and long service life, can be applied to systems such as various elastomers, coating materials, encapsulating materials, adhesives and the like, is particularly applied to an outer protective coating and a flexible workpiece material which are applied to a high-temperature environment or have heat-resistant and ablation-resistant requirements, such as an aircraft heat-resistant coating, and has the advantages of maintenance-free performance, high reliability and the like, and has wide application prospect.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is an infrared spectrum of each group of chemically cross-linked high-performance room temperature fast self-repairing flexible materials.
FIG. 2 is a Raman spectrum of each group of chemically cross-linked high-performance room temperature fast self-repairing flexible materials.
FIG. 3 is a diagram of the tensile strength repair efficiency of various groups of chemically cross-linked high-performance room temperature fast self-repairing flexible materials.
FIG. 4 is a graph of the repair efficiency of the elongation at break of each group of chemically cross-linked high-performance room temperature fast self-repairing flexible materials.
FIG. 5 is a tensile stress-strain curve of a chemically crosslinked high-performance room-temperature fast self-repairing flexible material after 1% TH is self-repaired under different repairing conditions.
FIG. 6 is a tensile stress-strain curve of a chemically cross-linked high-performance room-temperature fast self-repairing flexible material after 3% TH is self-repaired under different repairing conditions.
FIG. 7 is a tensile stress-strain curve of a chemically crosslinked high-performance room-temperature fast self-repairing flexible material after 5% TH is self-repaired under different repairing conditions.
FIG. 8 is a tensile stress-strain curve of a chemically crosslinked high-performance room-temperature fast self-repairing flexible material after 7% TH is self-repaired under different repairing conditions.
FIG. 9 is a tensile stress-strain curve of a chemically cross-linked high-performance room temperature fast self-repairing flexible material after 10% TH is self-repaired under different repairing conditions.
FIG. 10 is a thermal degradation thermogravimetric curve of various groups of chemically crosslinked high-performance room temperature fast self-repairing flexible materials in nitrogen.
FIG. 11 is a thermal degradation DTG curve of various groups of chemically crosslinked high-performance room temperature fast self-repairing flexible materials in nitrogen.
FIG. 12 is a thermal degradation thermogravimetric curve of various groups of chemically crosslinked high-performance room temperature fast self-repairing flexible materials in air.
FIG. 13 is a thermal degradation DTG curve of various groups of chemically crosslinked high-performance room temperature fast self-repairing flexible materials in air.
FIG. 14 is a photo of a thermal deformation test of each group of chemically cross-linked high-performance room temperature fast self-repairing flexible materials.
Detailed Description
the raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.
PDMS in the present invention is an abbreviation for polydimethylsiloxane.
example 1 preparation of chemically crosslinked high-performance room temperature fast self-repairing flexible material
(1) Synthesis of prepolymer: 5mmol of hydroxypropyl-terminated polydimethylsiloxane (HO-PDMS)3000Average molecular weight of 3000 and molecular weight range of 2000-4000) and 10.5mmol of isophorone diisocyanate (IPDI) are poured into a flask, 2000ppm of catalyst dibutyltin dilaurate (DBTDL) is added, argon is introduced at 60 ℃ for stirring for 1h, and the mixture is cooled to room temperature to obtain a prepolymer.
(2) And (3) crosslinking reaction: to the prepolymer was added 1% of the prepolymer mass of a crosslinking agent hexamethylene diisocyanate trimer (tri-HDI), i.e., 0.34mmol of tri-HDI, and the mixture was stirred at 60 ℃ for 0.5h to obtain a reaction solution.
(3) Chain extension reaction: dissolving 5.5mmol of 4,4' -diaminodiphenyl disulfide (APDS) serving as a chain extender in 2mL of dimethylacetamide, dropwise adding the chain extender into a reaction solution after crosslinking reaction, stirring at the rotating speed of 200 rpm at 60 ℃ for 10min, immediately pouring the obtained reaction solution into a mold, and vacuumizing at 90 ℃ for 12h to obtain the chemical crosslinking type high-performance room-temperature rapid self-repairing flexible material (1% TH).
Example 2 preparation of chemically crosslinked high-performance room temperature fast self-repairing flexible material
(1) Synthesis of prepolymer: 5mmol of hydroxypropyl-terminated polydimethylsiloxane (HO-PDMS)3000Average molecular weight of 3000 and molecular weight range of 2000-4000) and 10.5mmol of isophorone diisocyanate (IPDI) are poured into a flask, 2000ppm of catalyst dibutyltin dilaurate (DBTDL) is added, argon is introduced at 60 ℃ for stirring for 1h, and the mixture is cooled to room temperature to obtain a prepolymer.
(2) And (3) crosslinking reaction: and adding 3% of prepolymer mass of a cross-linking agent tri-HDI, namely 1.01mmol of tri-HDI into the prepolymer, and stirring at 60 ℃ for 0.5h to obtain a reaction solution.
(3) Chain extension reaction: dissolving 6.5mmol of 4,4' -diaminodiphenyl disulfide (APDS) serving as a chain extender in 2mL of dimethylacetamide, dropwise adding the chain extender into a reaction solution after crosslinking reaction, stirring at the rotating speed of 200 rpm at 60 ℃ for 10min, immediately pouring the obtained reaction solution into a mold, and vacuumizing at 90 ℃ for 12h to obtain the chemical crosslinking type high-performance room-temperature rapid self-repairing flexible material (3% TH).
Example 3 preparation of chemically crosslinked high-performance room temperature fast self-repairing flexible material
(1) Synthesis of prepolymer: 5mmol of hydroxypropyl-terminated polydimethylsiloxane (HO-PDMS)3000Average molecular weight of 3000 and molecular weight range of 2000-4000) and 10.5mmol of isophorone diisocyanate (IPDI) are poured into a flask, 2000ppm of catalyst dibutyltin dilaurate (DBTDL) is added, argon is introduced at 60 ℃ for stirring for 1h, and the mixture is cooled to room temperature to obtain a prepolymer.
(2) And (3) crosslinking reaction: and adding a cross-linking agent tri-HDI with the mass of 5% of the prepolymer, namely 1.69mmol of tri-HDI into the prepolymer, and stirring at 60 ℃ for 0.5h to obtain a reaction solution.
(3) Chain extension reaction: dissolving 7.5mmol of 4,4' -diaminodiphenyl disulfide (APDS) serving as a chain extender in 2mL of dimethylacetamide, dropwise adding the chain extender into a reaction solution after crosslinking reaction, stirring at the rotating speed of 200 rpm at 60 ℃ for 10min, immediately pouring the obtained reaction solution into a mold, and vacuumizing at 90 ℃ for 12h to obtain the chemical crosslinking type high-performance room-temperature rapid self-repairing flexible material (5% TH).
Example 4 preparation of chemically crosslinked high-performance room temperature fast self-repairing flexible material
(1) Synthesis of prepolymer: 5mmol of hydroxypropyl-terminated polydimethylsiloxane (HO-PDMS)3000Average molecular weight of 3000 and molecular weight range of 2000-4000) and 10.5mmol of isophorone diisocyanate (IPDI) are poured into a flask, 2000ppm of catalyst dibutyltin dilaurate (DBTDL) is added, argon is introduced at 60 ℃ for stirring for 1h, and the mixture is cooled to room temperature to obtain a prepolymer.
(2) And (3) crosslinking reaction: and adding a crosslinking agent tri-HDI with the mass of 7% of the prepolymer, namely 2.36mmol of tri-HDI into the prepolymer, and stirring at 60 ℃ for 0.5h to obtain a reaction solution.
(3) Chain extension reaction: dissolving 8.5mmol of 4,4' -diaminodiphenyl disulfide (APDS) serving as a chain extender in 2mL of dimethylacetamide, dropwise adding the chain extender into a reaction solution after crosslinking reaction, stirring at the rotating speed of 200 rpm at 60 ℃ for 10min, immediately pouring the obtained reaction solution into a mold, and vacuumizing at 90 ℃ for 12h to obtain the chemical crosslinking type high-performance room-temperature rapid self-repairing flexible material (7% TH).
Example 5 preparation of chemically crosslinked high-performance room temperature fast self-repairing flexible material
(1) Synthesis of prepolymer: 5mmol of hydroxypropyl-terminated polydimethylsiloxane (HO-PDMS)3000Average molecular weight of 3000 and molecular weight range of 2000-4000) and 10.5mmol of isophorone diisocyanate (IPDI) are poured into a flask, 2000ppm of catalyst dibutyltin dilaurate (DBTDL) is added, argon is introduced at 60 ℃ for stirring for 1h, and the mixture is cooled to room temperature to obtain a prepolymer.
(2) And (3) crosslinking reaction: and adding a crosslinking agent tri-HDI with the mass of 10% of the prepolymer, namely 3.41mmol of tri-HDI into the prepolymer, and stirring at 60 ℃ for 0.5h to obtain a reaction solution.
(3) Chain extension reaction: dissolving 10.1mmol of 4,4' -diaminodiphenyl disulfide (APDS) serving as a chain extender in 2mL of dimethylacetamide, dropwise adding the chain extender into a reaction solution after crosslinking reaction, stirring at the rotating speed of 200 rpm at 60 ℃ for 10min, immediately pouring the obtained reaction solution into a mold, and vacuumizing at 90 ℃ for 12h to obtain the chemical crosslinking type high-performance room-temperature rapid self-repairing flexible material (10% TH).
The advantageous effects of the present invention are demonstrated by specific test examples below.
Test example 1 characterization of chemical crosslinking type high-performance room temperature rapid self-repairing flexible material
First, infrared characterization
1. Test method
Taking the self-repairing flexible material prepared in the embodiment 1-5, and carrying out Fourier infrared spectrum detection. A small piece of material was taken from each group and subjected to total reflection infrared testing. The measurement was carried out by means of a Nicolet IS50 type infrared spectrometer manufactured by Thermo corporation, USA, at 4cm-1Is scanned 16 times.
2. Test results
The infrared spectrogram of each group of chemical crosslinking type high-performance room temperature rapid self-repairing flexible materials is shown in figure 1, and the peak emergence positions of each group in the infrared spectrogram are shown in table 1.
TABLE 1 position of the peak of each radical in the IR spectrum
The IPDI raw material will be at 2258cm-1There is a peak which is characteristic of-NCO, however, it can be seen from FIG. 1 that none of the five curves in the graph is 2258cm-1A peak appears, which indicates that IPDI participates in the synthesis and fully reacts; 3350cm-1is N-H stretching vibration in-NHCOO-, and is the formation of hydrogen bond which plays an important role in self-repair. 1696cm appears on the infrared spectrum-1and 1543cm-1two peaks, typical of a polyurethane, two peaks, 1696cm-1Stretching vibration of carbonyl groups orderly forming hydrogen bonds; 1260cm-1And 788cm-1Typical vibration peak of C-Si-C on hydroxyl terminated PDMS; 1082cm-1and 1008cm-1is a stretching vibration peak of a hydroxyl-terminated PDMS main chain Si-O-Si; the vibration peaks in the urethane bimodal peak and the PDMS bimodal peak appear in the material at the same time, and the-NCO peak disappears, which indicates that the material is successfully prepared.
Second, Raman characterization
1. Test method
And (3) carrying out Raman spectrum detection on the chemically crosslinked high-performance room-temperature fast self-repairing flexible material prepared in the embodiment 1-5. Taking a small piece of material, performing Raman spectrum test by adopting an LABRAM-1B multichannel confocal display micro Raman spectrometer, and selecting 532nm laser for excitation.
2. test results
The Raman spectrogram of each group of chemical crosslinking type high-performance room temperature rapid self-repairing flexible materials is shown in figure 2. 488cm in FIG. 2-1raman vibration of Si-O-Si at the main chain, 527cm-1Where a shoulder, here the raman response of S-S, appears. 1086cm-1is the Raman vibration of S-S connected with a benzene ring structure. From the Raman spectrum, it can be seen that the chain extender containing disulfide bond is successfulAnd (4) introducing.
The infrared spectrum detection and the Raman spectrum detection both prove that the chemical crosslinking type high-performance room-temperature quick self-repairing flexible material is successfully prepared.
Test example 2 self-repair performance detection of chemically crosslinked high-performance room-temperature rapid self-repair flexible material
1. test method
And (3) taking the chemical crosslinking type high-performance room-temperature rapid self-repairing flexible material prepared in the embodiment 1-5, detecting the self-repairing performance under different repairing conditions, and detecting the mechanical property of the repaired self-repairing flexible material.
And (3) tensile test: tensile testing was carried out according to GB/T528-2009 using an Instron model 5567 tensile tester, manufactured by Instron corporation, USA, and the test specimens were cut into dumbbell shapes having dimensions of 35mm by 2mm by 20 mm. All samples were at 100mm min-1Is tested at strain rate. The tensile strength and ultimate elongation at break were obtained from the stress-strain curve.
Self-repairing test: samples were cut from the middle with a clean sharp blade. The cut surfaces of the broken sample were then put together and placed in an oven at 25 ℃ for self-healing. Calculating the self-healing efficiency by the following formula:
2. Test results
The repairing efficiency of each group of self-repairing flexible materials under different repairing conditions is shown in tables 2-3 and figures 3-4 (TS in figure 3 refers to tensile strength, EB in figure 4 refers to elongation at break); the mechanical properties of the groups of self-repairing flexible materials after repair under different repair conditions are shown in figures 5-9.
As can be seen from the table 2 and the figures 3 to 9, each group of self-repairing flexible materials has good self-repairing capability. After each group of self-repairing elastomers are completely cut off, the self-repairing elastomers can restore more than 60% of the initial tensile strength after being repaired for 12 hours at the room temperature of 25 ℃, and can restore more than 70% of the initial tensile strength after being repaired for 48 hours at the room temperature of 25 ℃. The 10% TH group has the optimal self-repairing performance, the repairing is carried out for 48 hours at the room temperature of 25 ℃, the tensile strength repairing efficiency reaches 100.3%, the initial strength before cutting is achieved, the breaking elongation repairing efficiency reaches 93.0%, and the repairing effect is obvious.
TABLE 2 repair efficiency of tensile strength of each group of self-repairing flexible materials at different temperatures
TABLE 3 repair efficiency of each group of self-repairing flexible materials at different temperatures for elongation at break
Test example 3 thermal weight loss test of chemically crosslinked high-performance room temperature rapid self-repairing flexible material
1. Test method
The self-repairing flexible material prepared in the embodiment 1-5 is taken for a thermal weight loss test. The thermal stability of the samples under nitrogen and air flow was tested using a TG STA 449C thermogravimeter manufactured by NETZSCH, Germany, at a flow rate of 60mL min-1at 10K min-1Heating rate 5-10mg of the sample was heated from 40 ℃ to 800 ℃.
2. Test results
Thermal degradation thermogravimetric curves and DTG curves of the self-repairing flexible materials in nitrogen are respectively shown in FIG. 10 and FIG. 11; the thermal stability parameters under nitrogen for each set of self-repairing polyurethane elastomers are shown in table 4.
TABLE 4 thermal stability parameters of self-repairing flexible materials of each group under nitrogen
thermal degradation thermogravimetric curves and DTG curves of the self-repairing flexible materials in air are respectively shown in FIG. 12 and FIG. 13; the thermal stability under air parameters of each set of self-healing flexible materials are shown in table 5.
TABLE 5 thermal stability parameters of self-repairing flexible materials in air
The test results show that: 1) initial decomposition temperature T of each group of self-repairing flexible materials under nitrogen5％The cross-linking agent content does not change obviously and is stabilized above 290 ℃; the first maximum weight loss rate temperature is the temperature at which the hard segment begins to decompose and is 315 ℃, which shows that each group of self-repairing flexible materials has good thermal stability. Wherein, the first maximum weight loss temperature of 10 percent TH with the best self-repairing performance and mechanical property is not reduced, which shows that the content of hard segment is increased, and the thermal stability of the elastomer is not deteriorated. The 800 ℃ heat residual weight of the 10% TH group was also at the highest value in the five groups of samples, with higher heat residual weights reflecting better heat stability at high temperatures, indicating the best heat stability at 10% TH. 2) The thermal weight loss test under the air atmosphere can indirectly reflect the thermal stability condition of the material in the air. It can be seen that the initial decomposition temperature T5％The cross-linking agent content is increased to cause small reduction, but the cross-linking agent content is still at a higher level in polyurethane at about 290 ℃, so that the self-repairing flexible materials of each group have good thermal stability. Compared with the nitrogen atmosphere, the self-repairing flexible materials of each group are remarkably improved in 800 ℃ heat residual weight in the air, even can reach about 13 percent and is far higher than the 800 ℃ heat residual weight in the nitrogen, which shows that the self-repairing flexible materials of the invention have good heat stability in the air, and the 10 percent TH 800 ℃ heat residual weight is at the highest level in all the components, which shows that the 10 percent TH has the best heat stability.
Test example 4 thermal deformation test of chemically crosslinked high-performance room temperature rapid self-repairing flexible material
1. Test method
Two pieces of the self-repairing polyurethane flexible material prepared in the embodiment 1-5 with the same size are placed into a 2ml glass bottle, the glass bottle is placed into a 100 ℃ blast oven, the glass bottle is placed for 10min, 20min and 30min respectively, and the thermal deformation condition of the material is observed.
2. test results
As can be seen from FIG. 14, the five groups of samples all maintained the original shape without significant deformation at 100-10 min; at 100-20 min, other components except 10% TH have been significantly deformed, especially 1% TH and 3% TH, which are less cross-linking agents, have been severely softened. 10% TH group was slightly deformed; the softening and deformation phenomena are more serious than 100-20 min at 100-30 min, only 10% of TH groups are not completely bent and softened, and the self-supporting capability is still certain. The resistance to thermal deformation of 10% TH is best in the five groups.
In conclusion, the chemical crosslinking type high-performance room temperature quick self-repairing flexible material has room temperature self-repairing performance and heat resistance, can still keep good room temperature self-repairing performance while introducing a crosslinking structure to improve heat resistance and strength, can quickly complete self-repairing at room temperature, has high repairing efficiency and good heat stability, effectively overcomes the defects that the existing flexible heat-resisting material does not have self-repairing characteristics and the common room temperature self-repairing material does not resist high temperature, and fills the gap in the field. The flexible material has stable use performance, wide use range and long service life, can be applied to systems such as various elastomers, coating materials, encapsulating materials, adhesives and the like, is particularly applied to an outer protective coating and a flexible workpiece material which are applied to a high-temperature environment or have heat-resistant and ablation-resistant requirements, such as an aircraft heat-resistant coating, and has the advantages of maintenance-free performance, high reliability and the like, and has wide application prospect.
Claims (10)
1. A chemical crosslinking type room temperature rapid self-repairing flexible material is characterized in that: the material is prepared from hydroxypropyl end-capped polydimethylsiloxane, isocyanate, a cross-linking agent and a chain extender; wherein the molar ratio of the hydroxypropyl end-capped polydimethylsiloxane, the isocyanate, the cross-linking agent and the chain extender is (1-10): 5-15): 0.1-5): 5-15; the cross-linking agent is a polyisocyanate cross-linking agent; the chain extender is an aliphatic or aromatic diamino disulfide containing reversible disulfide bonds.
2. The self-healing flexible material of claim 1, wherein: the mole ratio of the hydroxypropyl end-capped polydimethylsiloxane, the isocyanate, the cross-linking agent and the chain extender is 5:10.5 (0.34-3.41) to 5.5-10.1.
3. The self-healing flexible material of claim 2, wherein: the molar ratio of the hydroxypropyl-terminated polydimethylsiloxane, the isocyanate, the cross-linking agent and the chain extender is 5:10.5:3.41: 10.1.
4. The self-repairing flexible material as claimed in any one of claims 1 to 3, wherein: the isocyanate is diisocyanate, preferably isophorone diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate or diphenylmethane diisocyanate; and/or the cross-linking agent is hexamethylene diisocyanate trimer; and/or the chain extender is 4,4' -diaminodiphenyl disulfide.
5. A preparation method of the self-repairing flexible material as claimed in any one of claims 1 to 4, characterized in that: it comprises the following steps:
(1) Synthesis of prepolymer: adding a catalytic amount of catalyst into hydroxypropyl-terminated polydimethylsiloxane and isocyanate, and reacting to obtain a prepolymer;
(2) And (3) crosslinking reaction: adding a cross-linking agent into the prepolymer for cross-linking reaction to obtain a reaction solution;
(3) Chain extension reaction: dissolving a chain extender in an organic solvent, adding the chain extender into a reaction solution after a crosslinking reaction, and reacting to obtain a reaction solution;
(4) and pouring the reaction solution into a mould, and curing to obtain the product.
6. The method of claim 5, wherein:
In the step (1), the catalyst is dibutyltin dilaurate;
And/or, in the step (3), the organic solvent is dimethylacetamide or dimethylformamide.
7. The method of claim 5, wherein:
In the step (3), the method for adding the organic solvent containing the chain extender into the prepolymer is dropwise adding.
8. The method of claim 5, wherein:
In the step (1), argon is introduced into the mixture for stirring for 1 to 6 hours at the temperature of between 60 and 100 ℃;
and/or in the step (2), the crosslinking reaction is carried out for 0.5-5h at the temperature of 60-100 ℃;
And/or, in the step (3), the reaction is stirred for 10-60min at the rotating speed of 200-800 r/min and the temperature of 20-60 ℃;
and/or, in the step (4), the solidification is carried out at 90 ℃ for 12 hours under vacuum;
Preferably, in the step (1), the reaction is carried out at 60 ℃ by introducing argon and stirring for 1 h;
And/or in the step (2), the crosslinking reaction is stirred for 0.5h at the temperature of 60 ℃;
And/or in the step (3), the reaction is stirred for 10min at the rotating speed of 200 revolutions per minute and the temperature of 60 ℃.
9. Use of the self-repairing flexible material of any one of claims 1 to 4 in preparation of a heat-resistant room temperature self-repairing material.
10. Use according to claim 9, characterized in that: the heat-resistant room temperature self-repairing material is an elastomer, a coating, a potting material or an adhesive; or the heat-resistant room temperature self-repairing material is an outer protective coating and a flexible workpiece material which are applied to a high-temperature environment or have heat-resistant and ablation-resistant requirements, and preferably, the heat-resistant room temperature self-repairing material is an outer coating of an aircraft.
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