CN110734532A - heat-resistant hydroxypropyl-terminated PDMS (polydimethylsiloxane) room-temperature rapid self-repairing elastomer and preparation method and application thereof - Google Patents
heat-resistant hydroxypropyl-terminated PDMS (polydimethylsiloxane) room-temperature rapid self-repairing elastomer and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides heat-resistant hydroxypropyl-terminated PDMS (polydimethylsiloxane) room-temperature quick self-repairing elastomers which are prepared from raw materials of hydroxypropyl-terminated polydimethylsiloxane, isocyanate and a chain extender, wherein the chain extender is dihydroxyl disulfide, the flexible heat-resistant material is endowed with a room-temperature quick self-repairing function, the material can quickly complete self-repairing at room temperature, the repairing efficiency is high, the thermal stability is good, the maintenance-free characteristic of the material can be realized, the reliability is effectively improved, the service life is prolonged, and the gap in the field is filled.
Description
Technical Field
The invention belongs to the field of intelligent high polymer materials, and particularly relates to heat-resistant hydroxypropyl-terminated PDMS (polydimethylsiloxane) room-temperature rapid self-repairing elastomers, 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 a thermal protection layer, whose cracking is a significant risk and a fatal threat to the safety of an aerospace vehicle, is still an ineffectively avoidable risk, and therefore maintaining the structural integrity of the thermal protection layer is of paramount importance. 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 novel materials capable of self-repairing when an object is damaged, and the self-repairing aims to prevent the crack from continuously expanding at the initial stage of crack formation, or can automatically close after the material is damaged, so that the initial structure and performance of the material are recovered, the application reliability of the material is improved, the application range is expanded, and the service life is prolonged.
The intrinsic self-repairing material does not need to be additionally provided with a 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.
For example, Wu X et al (Heat-trigged poly (siloxane-urethane) based on dispersed fibers substrates for self-healing application [ J ]. Journal of Applied Polymer science,2018,135(31):46532.) synthesize self-healing elastomers with reversible disulfide bonds by forming HDI diisocyanate and aminopropyl terminated PDMS into a prepolymer, 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, and cannot meet the requirement of aerospace heat-resistant materials.
For another example, in populus forest and the like (preparation and characterization of thermally reversible self-repairing polyurethane elastomers [ J ] material engineering, 2017,45 (8)), Hexamethylene Diisocyanate (HDI) trimer is used as a cross-linking agent, 4, 4-diaminodiphenyl disulfide (AFD) is used as a chain extender, and a reversible disulfide bond is introduced into a polyester polyurethane elastomer, wherein 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 of 60 ℃ and 24h of repairing time.
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 heat-resistant hydroxypropyl-terminated PDMS (polydimethylsiloxane) room-temperature fast self-repairing elastomers, and a preparation method and application thereof.
The invention provides heat-resistant hydroxypropyl-terminated PDMS (polydimethylsiloxane) room-temperature fast self-repairing elastomer which is prepared from raw materials of hydroxypropyl-terminated polydimethylsiloxane, isocyanate and a chain extender, wherein the molar ratio of the hydroxypropyl-terminated polydimethylsiloxane to the isocyanate to the chain extender is (1-10) to (20-35) to (10-25), and the chain extender is an aliphatic or aromatic dihydroxy disulfide containing a reversible disulfide bond.
, the mol ratio of the hydroxypropyl end capping polydimethylsiloxane, the isocyanate and the chain extender is 10 (21-31.5) to 10-20.
Further , the hydroxypropyl terminated polydimethylsiloxane, the isocyanate and the chain extender are in a molar ratio of 10:23.625: 12.5.
Further , the isocyanate is a diisocyanate, preferably isophorone diisocyanate, hexamethylene diisocyanate, 4 'dicyclohexylmethane diisocyanate or diphenylmethane diisocyanate, and/or the chain extender is 4,4' -dihydroxydiphenyl disulfide.
The invention also provides a preparation method of self-repairing elastomers, which 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) chain extension reaction: dissolving a chain extender into an organic solvent, adding the chain extender into the prepolymer, and reacting to obtain a reaction solution;
(3) and pouring the reaction solution into a mould, and curing to obtain the product.
In a step , the method further comprises,
in the step (1), the catalyst is dibutyltin dilaurate;
and/or, in the step (2), the organic solvent is dimethylacetamide or dimethylformamide.
In a step , the method further comprises,
in the step (2), the method for adding the organic solvent containing the chain extender into the prepolymer is dropwise adding;
and/or, in the step (2), the reaction solution is prepared into a reaction solution with a polymer concentration of 30% by using dimethylacetamide or dimethylformamide for chain extension reaction.
In a step , the method further comprises,
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 reaction is carried out for 2-4h at the temperature of 20-60 ℃;
and/or in the step (3), the solidification is carried out at 90 ℃ for 12 hours under vacuum, and residual solvent is removed;
preferably, in the step (1), the reaction is carried out at 80 ℃ by introducing argon and stirring for 3 h;
and/or in the step (2), the reaction is carried out at 60 ℃ for 2 h.
The invention also provides application of the self-repairing elastomer in preparation of the heat-resistant room-temperature self-repairing material.
, 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 product 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 aircraft outer coating.
The self-repairing elastomer has stable service performance, a service range of and long service life, can be applied to various systems such as elastomers, coating materials, encapsulating materials, adhesives and the like, and particularly applied to a high-temperature environment or an outer protective coating and a flexible workpiece material with heat-resisting and anti-burning requirements, such as an aircraft heat-resisting coating, and has the advantages of maintenance-free performance, high reliability and the like, and the application prospect is excellent.
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 by way of examples , but it should not be construed that the scope of the above subject matter is limited to the examples described below.
Drawings
FIG. 1 is an infrared spectrum of a self-healing elastomer of the present invention.
FIG. 2 is a Raman spectrum of a self-healing elastomer of the present invention.
FIG. 3 is a self-healing tensile stress strain curve of the self-healing elastomer of comparative example 1.
FIG. 4 is a self-healing tensile stress-strain curve of a self-healing elastomer of the present invention; a: PIH-10, b: PIH-12.5, c: PIH-15, d: PIH-20.
FIG. 5 is a graph of the tensile strength self-healing efficiency of the self-healing elastomers of the present invention.
FIG. 6 is an optical photograph of an incision repair with a self-healing elastomer of the present invention.
FIG. 7 is a graph of the thermal weight loss of a self-healing elastomer of the present invention; a: thermal degradation thermogravimetric curve, b: DTG curve.
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 a self-healing elastomer of the invention
(1) Synthesis of prepolymer: 10mmol of hydroxypropyl-terminated polydimethylsiloxane (HO-PDMS-OH, molecular weight 2000-4000) and 21mmol of isophorone diisocyanate (IPDI) are poured into a flask, 3000ppm of catalyst dibutyltin dilaurate (DBTDL) is added, argon is introduced at 80 ℃ for stirring for 3h, and the mixture is cooled to room temperature to obtain a prepolymer.
(2) Chain extension reaction: dissolving 10mmol of 4,4' -dihydroxy diphenyl disulfide (HPDS) serving as a chain extender into 2mL of dimethylacetamide, dropwise adding the chain extender into the prepolymer prepared in the step (1), reacting at 60 ℃ for 2 hours, and after the reaction is finished, adding dimethylacetamide to prepare a reaction solution with the polymer concentration of 30% obtained through a chain extension reaction.
(3) Pouring the reaction solution into a polytetrafluoroethylene mold, maintaining vacuum at 90 ℃ for 12h, and removing residual solvent to obtain an elastomer sheet (PDMS-IPDI-HPDS)10Abbreviated as PIH-10).
Example 2 preparation of a self-healing elastomer of the invention
(1) Synthesis of prepolymer: 10mmol of hydroxypropyl-terminated polydimethylsiloxane (HO-PDMS-OH, molecular weight 2000-4000) and 23.625mmol of isophorone diisocyanate (IPDI) are poured into a flask, 3000ppm of catalyst dibutyltin dilaurate (DBTDL) is added, argon is introduced at 80 ℃ for stirring for 3h, and the mixture is cooled to room temperature to obtain a prepolymer.
(2) Chain extension reaction: dissolving 12.5mmol of 4,4' -dihydroxy diphenyl disulfide (HPDS) serving as a chain extender into 2mL of dimethylacetamide, dropwise adding the chain extender into the prepolymer prepared in the step (1), reacting at 60 ℃ for 2 hours, and adding dimethylacetamide to prepare a reaction solution with the polymer concentration of 30% obtained through chain extension reaction by adding dimethylacetamide after the reaction is finished.
(3) Pouring the reaction solution into a polytetrafluoroethylene mold, maintaining vacuum at 90 ℃ for 12h, and removing residual solvent to obtain an elastomer sheet (PDMS-IPDI-HPDS)12.5Abbreviated as PIH-12.5).
Example 3 preparation of a self-healing elastomer of the invention
(1) Synthesis of prepolymer: 10mmol of hydroxypropyl-terminated polydimethylsiloxane (HO-PDMS-OH, molecular weight 2000-4000) and 26.25mmol of isophorone diisocyanate (IPDI) are poured into a flask, 3000ppm of catalyst dibutyltin dilaurate (DBTDL) is added, argon is introduced at 80 ℃ for stirring for 3h, and the mixture is cooled to room temperature to obtain a prepolymer.
(2) Chain extension reaction: dissolving 15mmol of 4,4' -dihydroxy diphenyl disulfide (HPDS) serving as a chain extender into 2mL of dimethylacetamide, dropwise adding the chain extender into the prepolymer prepared in the step (1), reacting at 60 ℃ for 2 hours, and after the reaction is finished, adding dimethylacetamide to prepare a reaction solution with the polymer concentration of 30% obtained through a chain extension reaction.
(3) Pouring the reaction solution into a polytetrafluoroethylene mold, maintaining vacuum at 90 ℃ for 12h, and removing residual solvent to obtain an elastomer sheet (PDMS-IPDI-HPDS)15Abbreviated as PIH-15).
Example 4 preparation of a self-healing elastomer of the invention
(1) Synthesis of prepolymer: 10mmol of hydroxypropyl-terminated polydimethylsiloxane (HO-PDMS-OH, molecular weight 2000-4000) and 31.5mmol of isophorone diisocyanate (IPDI) are poured into a flask, 3000ppm of catalyst dibutyltin dilaurate (DBTDL) is added, argon is introduced at 80 ℃ for stirring for 3h, and the mixture is cooled to room temperature to obtain a prepolymer.
(2) Chain extension reaction: dissolving 20mmol of 4,4' -dihydroxy diphenyl disulfide (HPDS) serving as a chain extender into 2mL of dimethylacetamide, dropwise adding the chain extender into the prepolymer prepared in the step (1), reacting at 60 ℃ for 2 hours, and after the reaction is finished, adding dimethylacetamide to prepare a reaction solution with the polymer concentration of 30% obtained through a chain extension reaction.
(3) Pouring the reaction solution into a polytetrafluoroethylene mold, maintaining vacuum at 90 ℃ for 12h, and removing residual solvent to obtain an elastomer sheet (PDMS-IPDI-HPDS)20Abbreviated as PIH-20).
Comparative example 1 preparation of self-healing elastomer
(1) Synthesis of prepolymer: 10mmol of hydroxypropyl-terminated polydimethylsiloxane (HO-PDMS-OH, molecular weight 2000-4000) and 21mmol of isophorone diisocyanate (IPDI) are poured into a flask, 3000ppm of catalyst dibutyltin dilaurate (DBTDL) is added, argon is introduced at 80 ℃ for stirring for 3h, and the mixture is cooled to room temperature to obtain a prepolymer.
(2) Chain extension reaction: dissolving 10mmol of Ethylene Glycol (EG) as a chain extender into 2mL of dimethylacetamide, dropwise adding the chain extender into the prepolymer prepared in the step (1), reacting for 2 hours at 60 ℃, and adding dimethylacetamide to prepare a reaction solution with the polymer concentration of 30% obtained through a chain extension reaction by adding the dimethylacetamide after the reaction is finished.
(3) Pouring the reaction solution into a polytetrafluoroethylene mold, keeping the vacuum at 90 ℃ for 12h, and removing the residual solvent to obtain an elastomer sheet (PDMS-IPDI-EG)10Abbreviated as PIE-10).
The advantageous effects of the present application are demonstrated by specific test examples below.
Test example 1 structural characterization of self-healing elastomer of the invention
Fourier Infrared characterization
1. Test method
Taking the self-repairing elastomers prepared in the embodiments 1 to 4, and respectively carrying out Fourier infrared spectrum detection. 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 peak positions of all groups in the infrared spectrum are shown in table 1, and the detection results of the infrared spectrum of the self-repairing elastomer prepared in the embodiments 1 to 4 are shown in fig. 1.
TABLE 1 position of the peak of each radical in the IR spectrum
IPDI upper-NCO at 2258cm-1There should be peaks, but in FIG. 1, after the self-repairing elastomers are prepared, the infrared spectrogram of four groups of self-repairing elastomers has a peak corresponding to-NCO (2258 cm)-1) All the IPDI in the four groups of self-repairing elastomers disappears, which shows that the IPDI in the four groups of self-repairing elastomers participates in synthesis and fully reacts; 1708cm on the infrared spectrum-1And 1532cm-1Two peaks, typical of a bimodal polyurethane, 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 double peak and the PDMS appear in the self-repairing elastomer at the same time, and the-NCO peak disappears, which indicates that the self-repairing elastomer is successfully prepared.
Second, Raman characterization
1. Test method
The self-repairing elastomers prepared in examples 1-4 were taken and subjected to raman spectroscopy. A Raman spectrum test is carried out by adopting a LABRAM-1B multichannel confocal display micro Raman spectrometer, and 532nm laser is selected for excitation.
2. Test results
The detection results of Raman spectra of the self-repairing elastomers prepared in examples 1-4 are shown in FIG. 2. 490cm in FIG. 2-1Raman vibration of main chain Si-O-Si; 527cm-1 shoulders appear, here the Raman response of S-S, 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 bonds was successfully introduced.
The infrared spectrum detection and the Raman spectrum detection both prove that the room-temperature self-repairing elastomer is successfully prepared.
Test example 2 detection of self-repairing Performance of self-repairing elastomer according to the present invention
1. Test method
The self-repairing elastomers prepared in the embodiments 1-4 and the self-repairing elastomer prepared in the comparative example 1 are taken to perform self-repairing tests under different repairing conditions, and the repaired self-repairing elastomer is subjected to a tensile test. The detection conditions of the self-repair test and the tensile test are as follows:
and (3) tensile test: tensile testing was carried out according to GB/T528-. 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.
And (2) self-repairing test, namely cutting a sample from the middle by using a clean sharp blade, then placing the cut surface of the crushed sample at , placing the cut surface in an oven at 25 ℃ for self-repairing, observing the cut appearance of the damaged sample after the self-repairing by using a KEYENCE VHX-1000C type three-dimensional super-depth-of-field microscope produced in Japan, and calculating the self-repairing efficiency by using the following formula:
2. test results
The self-repairing performance results of the self-repairing elastomer are shown in FIGS. 3-6. FIG. 3 is a PIE-10 self-healing stress-strain curve of comparative example 1; in FIG. 4, a-d are self-repairing stress-strain curves of PIH-10, PIH-12.5, PIH-15 and PIH-20 of examples 1-4, respectively; FIG. 5 shows the self-repairing efficiencies of PIH-10, PIH-12.5, PIH-15, and PIH-20 of examples 1-4; FIG. 6 is a graph of the cut after PIH-10, PIH-12.5, PIH-15, and PIH-20 self-repairing.
From the figures 3-5, it can be known that although the PIE-10 does not contain a disulfide bond with a self-repairing function, the PIE-10 is subjected to chain extension by adopting ethylene glycol, and the molecular weight of PDMS at a soft segment is 3000 larger, so that the molecular chain is lack of rigid and hard segments for fixation, the PIE-10 is made to be very soft, the molecular chain mobility is very strong, and the material fracture is self-repaired through the movement of the molecular chain after being cut off, the PIH-10 sample is too soft and sticky, the tensile strength is about 0.1MPa, the elongation at break is more than 1000%, the self-repairing is very fast, but the maximum elongation at break is within 50%, with the tensile process, the tensile stress of the material is gradually reduced, the material is drawn into a thin cellophane shape, the lost material achieves the due mechanical strength, and is not suitable for being used as a material, the PIH-12.5, the PIH-15 and the PIH-20 have good mechanical strength, and fixed effects, the PIH-10 can be performed at room temperature, wherein the PIH-12.5 has the best tensile strength, the 3 h-self-repairing efficiency is very good, the PIH-20 has the very good self-repairing efficiency, the very good, the PIH-repairing efficiency is close to the 3548-repairing efficiency, and the PIH-repairing is very good, the PIH-repairing efficiency is very good, the very good, and the PIH-repairing is very short, the PIH-repairing efficiency is very short, the.
From FIG. 6, it can be seen that the PIH-10 is repaired at room temperature for 3h after being completely cut off, and only marks are left on the surface, which is also identical with the self-repairing stress-strain curve of the material, and has a self-repairing efficiency of more than 90%, but the PIH-10 is too soft, has too low strength, and has no practical value although the cut mark is easy to repair, when the PIH-12.5 is repaired at 25 ℃ for 3h, although the surface still has a scar caused by splicing, the surface becomes shallow and narrow obviously compared with the initial one, and the tensile strength repairing efficiency is 92%, which indicates that the interior of the material should have better repairing, and the surface marks basically disappear after being repaired for 24h, while the PIH-15 and the PIH-20 have the strong hard segment component and the molecular chain movement capability is reduced, so that the cut mark only becomes shallow and narrow in after being repaired at room temperature for 48h, and cannot be completely repaired, and the tensile performance repairing efficiency is about 50%.
Test results show that the self-repairing elastomers have good self-repairing capability. The PIH-12.5 has excellent self-repairing capability and high mechanical strength, and meets the requirements of practical application.
Test example 3 thermal weight loss of self-repairing elastomer of the present invention
1. Test method
The thermal stability of the samples (the room temperature self-repairing elastomers prepared in examples 1-4 and the self-repairing elastomers prepared in comparative example 1) in nitrogen flow (60 mLmin) is tested by recording thermogravimetry by a TG STA 449C type thermogravimeter produced by Germany NETZSCH company-1) At the rate of 10K min-1Heating rate 5-10 mg of the sample was heated from 40 ℃ to 800 ℃.
2. Test results
The thermal degradation thermogravimetric curve and the DTG curve of each group of room temperature self-repairing elastomers are shown in FIG. 7 (in FIG. 7, a is a thermal degradation thermogravimetric curve, and b is a DTG curve); the thermal stability parameters under nitrogen for each set of room temperature self-healing elastomers are shown in table 2.
TABLE 2 thermal stability parameters under nitrogen for different materials
As can be seen from Table 2 and FIG. 7, the initial decomposition temperature of the self-healing elastomer PIE-10 without HPDS is much lower than that of the room temperature self-healing elastomer (PIH series) with HPDS. Under the condition of maintaining the rapid room temperature self-repairing performance of the PIH series, the initial decomposition temperature is still at a higher level in the polyurethane elastomer, and the thermal stability is good. In each group of self-repairing elastomers of the PIH series, T is increased along with the content of HPDS5％The initial decomposition temperature of the PIH-12.5 shows a trend of increasing and then decreasing, the st maximum weight loss rate temperature is gradually decreased along with the increase of the content of the HPDS, wherein the PIH-12.5 st st maximum weight loss temperature is 324 ℃, the difference with the PIH-10 is not large, the HPDS content is continuously increased, the decomposition temperature is decreased, the thermal stability is reduced, and therefore, the thermal stability of the PIH-12.5 is optimal.
In conclusion, the self-repairing elastomer has stable service performance, a service range of and long service life, can be applied to various elastomers, coating materials, encapsulating materials, adhesives and other systems, is particularly applied to a high-temperature environment or an outer protective coating and a flexible workpiece material with heat-resisting and anti-burning requirements, such as an aircraft heat-resisting coating, and has the advantages of maintenance-free performance, high reliability and the like, and the application prospect is excellent.
Claims (10)
- The heat-resistant hydroxypropyl-terminated PDMS room-temperature fast self-repairing elastomer is characterized by being prepared from hydroxypropyl-terminated polydimethylsiloxane, isocyanate and a chain extender, wherein the molar ratio of the hydroxypropyl-terminated polydimethylsiloxane to the isocyanate to the chain extender is (1-10) to (20-35) to (10-25), and the chain extender is an aliphatic or aromatic dihydroxy disulfide containing a reversible disulfide bond.
- 2. The self-healing elastomer of claim 1, wherein: the molar ratio of the hydroxypropyl-terminated polydimethylsiloxane to the isocyanate to the chain extender is 10 (21-31.5) to 10-20.
- 3. The self-healing elastomer of claim 2, wherein: the molar ratio of the hydroxypropyl-terminated polydimethylsiloxane, the isocyanate and the chain extender is 10:23.625: 12.5.
- 4. The self-repairing elastomer according to any one of claims 1-3- , wherein the isocyanate is a diisocyanate, preferably isophorone diisocyanate, hexamethylene diisocyanate, 4 '-dicyclohexylmethane diisocyanate or diphenylmethane diisocyanate, and/or the chain extender is 4,4' -dihydroxydiphenyl disulfide.
- 5, A method for preparing the self-repairing elastomer of any of claims 1-4, which is characterized in that the method 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) chain extension reaction: dissolving a chain extender into an organic solvent, adding the chain extender into the prepolymer, and reacting to obtain a reaction solution;(3) 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 (2), the organic solvent is dimethylacetamide or dimethylformamide.
- 7. The method of claim 5, wherein:in the step (2), the method for adding the organic solvent containing the chain extender into the prepolymer is dropwise adding;and/or, in the step (2), the reaction solution is prepared into a reaction solution with a polymer concentration of 30% by using dimethylacetamide or dimethylformamide for chain extension reaction.
- 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 reaction is carried out for 2-4h at the temperature of 20-60 ℃;and/or in the step (3), the solidification is carried out at 90 ℃ for 12 hours under vacuum, and residual solvent is removed;preferably, in the step (1), the reaction is carried out at 80 ℃ by introducing argon and stirring for 3 h;and/or in the step (2), the reaction is carried out at 60 ℃ for 2 h.
- 9. Use of the self-healing elastomer of any one of claims 1 to 4 to in the preparation of a heat-resistant room temperature self-healing 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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|---|---|---|---|---|
| CN111388355A (en) * | 2020-04-06 | 2020-07-10 | 华中科技大学同济医学院附属协和医院 | Skin protective agent for preventing pathogen contact and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082862A (en) * | 2017-05-18 | 2017-08-22 | 中国科学院深圳先进技术研究院 | Selfreparing organic silicon modified polyurethane elastomer and preparation method thereof |
| CN108003317A (en) * | 2017-12-22 | 2018-05-08 | 四川大学 | A kind of silicone elastomer and its preparation method and application |
| CN108659188A (en) * | 2018-06-01 | 2018-10-16 | 南京理工大学 | A kind of polyureas selfreparing thermoplastic elastomer (TPE) and preparation method thereof |
| CN109942773A (en) * | 2019-03-18 | 2019-06-28 | 四川大学 | A kind of selfreparing polyurethane and preparation method thereof of the key of thiourethane containing dynamic |
| KR20190083551A (en) * | 2018-01-04 | 2019-07-12 | 한국과학기술연구원 | Self healing elastomer, self healing complex and self healing film |
| CN110105534A (en) * | 2019-04-30 | 2019-08-09 | 郑州大学 | A kind of transparent high-intensity and high-tenacity room temperature selfreparing thermoplastic polyurethane urea elastomer and preparation method |
-
2019
- 2019-09-19 CN CN201910884651.4A patent/CN110734532A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082862A (en) * | 2017-05-18 | 2017-08-22 | 中国科学院深圳先进技术研究院 | Selfreparing organic silicon modified polyurethane elastomer and preparation method thereof |
| CN108003317A (en) * | 2017-12-22 | 2018-05-08 | 四川大学 | A kind of silicone elastomer and its preparation method and application |
| KR20190083551A (en) * | 2018-01-04 | 2019-07-12 | 한국과학기술연구원 | Self healing elastomer, self healing complex and self healing film |
| CN108659188A (en) * | 2018-06-01 | 2018-10-16 | 南京理工大学 | A kind of polyureas selfreparing thermoplastic elastomer (TPE) and preparation method thereof |
| CN109942773A (en) * | 2019-03-18 | 2019-06-28 | 四川大学 | A kind of selfreparing polyurethane and preparation method thereof of the key of thiourethane containing dynamic |
| CN110105534A (en) * | 2019-04-30 | 2019-08-09 | 郑州大学 | A kind of transparent high-intensity and high-tenacity room temperature selfreparing thermoplastic polyurethane urea elastomer and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| ALAITZ REKONDO等: ""Catalyst-free room-temperature self-healing elastomers based on aromatic disulfide metathesis"", 《MATERIALS HORIZONS》 * |
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