CN108659462B - Self-repairing type remoldable multiple deformation thermosetting shape memory resin material - Google Patents
Self-repairing type remoldable multiple deformation thermosetting shape memory resin material Download PDFInfo
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Abstract
The invention discloses a self-repairing type remolding multi-deformation thermosetting shape memory resin material, which is mainly prepared by taking bismaleimide, aromatic diamine, epoxy resin, dicarboxylic anhydride and ester exchange accelerant as raw materials, carrying out chain extension reaction on the bismaleimide resin through the aromatic diamine to form linear oligomer, then adding the epoxy resin, the accelerant and the dicarboxylic anhydride, and carrying out certain thermosetting process treatment. The material prepared by the invention can be reshaped into a new shape, has good shape memory effect after being deformed and recovered for more than 5 times, has good self-repairing capability, and has fracture toughness repairing efficiency of more than 62 percent. Therefore, the prepared material has wide application potential in high-performance structure function integrated materials.
Description
The invention discloses a self-repairing type remoldable multi-deformation thermosetting shape memory resin material and a preparation method thereof, belonging to the product part, wherein the application date is 2016, 12 and 12, and the application number is 201611141129X.
Technical Field
The invention belongs to the technical field of shape memory functionalized high-performance resin matrixes, and relates to a shape-remodelable multi-deformation thermosetting shape memory resin system with self-repairing capability.
Background
Shape Memory Polymers (SMPs) are unique stimulus-responsive polymers that can be programmed to set in a temporary shape and return to their original, original shape under a specific external stimulus. SMPs as an intelligent material capable of self-deforming have the advantages of light weight, low cost, easiness in processing, easiness in shape change control, easiness in transition temperature adjustment and the like. As thermosetting SMPs, the thermosetting SMPs have more excellent mechanical properties, higher thermal transition temperature and better heat resistance and thermal stability than thermoplastic SMPs, and play an irreplaceable role in the aerospace fields of space self-expanding structural members, deformable aircrafts and the like. Therefore, the development of novel high-performance thermosetting SMPs with integrated structure and function has great research significance for widening the potential application of the SMPs.
However, it is common to use thermosetting SMPs that only memorize a temporary shape once and then revert to a permanent shape, i.e., a dual shape memory effect (accounting for the original shape). The double shape memory change takes network cross-linking points as a fixed phase, molecular chains among the cross-linking points as a reversible deformation phase, and the deformation is based on the chain conformation change of the reversible deformation phase. The application of the thermosetting SMPs in the emerging technical field is greatly limited due to the defects of simple shape change, deformation and non-programming and the like of the thermosetting SMPs, and the thermosetting SMPs deformed in thermal response have poor shape memory cycle stability and limited deformation cycle times in the repeated heat treatment process. While SMPs containing multiple temperature transitions or wide-range temperature transitions can memorize various shapes, the reconstruction or remodeling of the material shape cannot be realized only by the superposition of dual shape memory effects, and the recovery deformation of complex shapes in two-dimensional or three-dimensional space cannot be met. Moreover, when the SMPs are in service in a complex environment, microcracks and other damages are inevitably generated in the SMPs, so that the mechanical property of the material is greatly reduced, and the service life and the safety of the material are shortened. Therefore, it is of positive significance to prepare a shape-remodelable multiple-deformation thermosetting shape-memory resin system having a long service life and high safety.
Disclosure of Invention
The invention aims to provide a multiple-deformation thermosetting shape memory resin system with a crack self-repairing function and capable of reshaping and a preparation method thereof, aiming at the problems that the existing thermosetting shape memory resin can not be reshaped, can not effectively realize complex shape deformation, can generate microcrack damage in the use process and the like.
In order to achieve the aim, the invention adopts the technical scheme that the preparation method of the self-repairing type remoldable multiple deformation thermosetting shape memory resin material comprises the following steps: reacting bismaleimide with an amine compound to obtain an oligomer; then adding the oligomer into epoxy resin, and then adding an accelerator; then adding acid anhydride to obtain a prepolymerization system; the prepolymerization system is subjected to thermocuring to obtain the self-repairing type remolding multi-deformation thermosetting shape memory resin material.
In the technical scheme, the mass ratio of the bismaleimide to the amine compound to the epoxy resin to the anhydride to the accelerator is (5-25) to (4-18) to (75-120) to (12-18) to (4-8).
In the above technical solution, the bismaleimide includes bismaleimide diphenylmethane, bismaleimide diphenyl methyl ether; the amine compound is a diamine compound; the epoxy resin comprises bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated epoxy resin, novolac epoxy resin, organic silicon epoxy resin and flame-retardant epoxy resin; the promoter is a metal salt; the acid anhydride is a dibasic acid anhydride.
Preferably, the diamine is an aromatic diamine or an aliphatic diamine, such as diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, bis (4-amino-3-methylcyclohexyl) methane, diaminobiphenyl; the dibasic acid anhydride is aromatic dibasic acid anhydride or aliphatic dibasic acid anhydride, such as dibasic acid anhydride including phthalic anhydride, hexahydrophthalic anhydride, glutaric anhydride, adipic anhydride, dodecenyl succinic anhydride, methyl cyclohexene tetracid dianhydride, methyl nadic anhydride; the metal salts include metal salts of zinc, tin, magnesium, calcium, such as zinc acetylacetonate, zinc acetate, calcium acetate, magnesium acetate, dibutyltin dilaurate.
In the above technical solution, preferably, the bismaleimide and the amine compound are reacted in a solvent; the reaction condition of the bismaleimide and the amine compound in the solvent is that the bismaleimide and the amine compound react for 8-15 hours at the temperature of 55-110 ℃; after removal of the solvent, an oligomer is obtained. The solvent is a solvent capable of dispersing bismaleimide and amine compounds, such as ketone solvents and the like, and after the reaction, the solvent is dried or removed by rotary evaporation to obtain a solid, namely the oligomer; the bismaleimide and the amine compound can be subjected to melt reaction without a solvent, the reaction controllability is poor under the condition, the industrial production is not facilitated, and the bismaleimide and the amine compound are preferably subjected to reaction in the presence of the solvent.
In the technical scheme, the oligomer is added into the epoxy resin, mixed at 90-110 ℃, and then added with the accelerator; the temperature of the heat curing is 100-180 ℃, the time is 8-15 hours, and a step curing process is preferably adopted.
Preferably, after adding the anhydride, a prepolymerization system is obtained, and then the addition component is added, and then the thermal curing is carried out; the additive component comprises cyanate ester resin, phenolic resin, organic silicon resin and furan resin; the adding amount of the adding component is 5-10% of the mass of the prepolymerization system; by adding the additive components, the comprehensive performance of the material can be improved.
The invention further discloses the self-repairing type remoldable multi-deformation thermosetting shape memory resin material prepared by the preparation method of the self-repairing type remoldable multi-deformation thermosetting shape memory resin material. The method has the following technical effects:
(1) the shape of the material can be automatically reshaped into a new shape, for example, a formed plane straight strip-shaped sample is fixedly formed into a standing inverted U-shaped at a high temperature (180-200 ℃), and the inverted U-shaped sample can be automatically bent upwards into a standing U-shaped after being restored to be straight under a control temperature (about 20 ℃ above the glass transition temperature).
(2) The material has more deformation recovery cycles, for example, after 5 cycles of test, the material can show very stable shape memory performance, and the deformation fixation rate is close to 100 percent.
(3) The material has the function of automatically healing microcracks, and the healing efficiency of the microcracks reaches over 62 percent.
(4) The material has excellent heat resistance, and the glass transition temperature (DMA method) is 110-140 ℃.
The invention also discloses a preparation method of the self-repairing type remoldable multiple deformation thermosetting shape memory resin system, which comprises the following steps: reacting bismaleimide with an amine compound to obtain an oligomer; then adding the oligomer into epoxy resin, and then adding an accelerator; then adding acid anhydride to obtain a self-repairing type remolding multi-deformation thermosetting shape memory resin system; the mass ratio of the bismaleimide to the amine compound to the epoxy resin to the acid anhydride to the accelerator is (5-25) to (4-18) to (75-120) to (12-18) to (4-8).
Preferably, after adding the anhydride, a prepolymerization system is obtained, and then the addition component is added, and then the thermal curing is carried out; the additive component comprises cyanate ester resin, phenolic resin, organic silicon resin and furan resin; the adding amount of the adding component is 5-10% of the mass of the prepolymerization system; by adding the additive components, the comprehensive performance of the material can be improved.
The polymer cross-linked network of the invention has two fixed cross-linking points, namely the ester exchange bond generated by the epoxy functional group and the acid anhydride and the cross-linking point generated by the epoxy functional group and the amine after curing. In the present invention, when the glass transition temperature of the material is reached, the mobility of the chains is enhanced, and the reversible deformation phase between the crosslinking points is the basis of the shape memory. When the temperature is increased to the ester bond exchange reaction temperature (180-200 ℃), the dynamic ester bond rapid exchange reaches balance, the topological structure of a cross-linked network is changed, the internal stress is relaxed, the temporary shape can be permanently fixed, the reconstruction or remodeling of the material shape is realized, and similarly, when microcracks occur in the material, the microcracks can be repaired and crack surfaces can be bonded based on the rapid exchange of molecular chains containing the ester bonds.
Compared with the prior art, the invention has the following beneficial effects:
1. the self-repairing type remoldable multiple deformation thermosetting shape memory resin material disclosed by the invention can realize the reconstruction of a cross-linked network molecular structure and the like by utilizing the characteristic of a dynamic ester exchange bond, and a molecular chain can perform an exchange reaction to achieve dynamic balance under the condition of the existence of a catalyst and under the control of proper temperature, and the main technical advantages are that: according to the embodiment of the invention, the formed plane straight strip type sample is fixed and formed into a standing inverted U shape at the ester exchange temperature, and the inverted U shape is fixed into a positive U shape at the controlled temperature (above the glass transition temperature), and at the moment, when the positive U shape is processed above the glass transition temperature of the material, the positive U shape is restored to the straight shape and then can be automatically bent upwards to form the standing positive U shape; the material has more deformation recovery cycles, can show very stable shape memory performance after 5-time cycle test, and has a deformation fixation rate close to 100% and a recovery rate greater than 82% compared with the initial deformation; the material has the function of automatically healing microcracks, and the healing efficiency of the microcracks reaches over 62 percent.
2. Compared with the traditional shape memory thermosetting material, the self-repairing type remoldable multiple deformation thermosetting shape memory resin material disclosed by the invention can quickly realize the automatic molding of a three-dimensional structural member in a short time (within 20 seconds), can still keep good shape memory performance after more than 5 times of deformation-recovery, has good crack repairing capability, and improves the use stability of the material, and in addition, the material prepared by the invention has excellent heat resistance compared with the traditional thermosetting shape memory material, and the glass transition temperature (DMA method) is 110-140 ℃.
3. The preparation method of the self-repairing type remoldable multiple deformation thermosetting shape memory resin material disclosed by the invention has the advantages that the process is controllable, the raw material composition is reasonable, and particularly under the action of an additive, more excellent comprehensive performance can be obtained; the preparation process has no special requirements, and is beneficial to industrial application.
Drawings
FIG. 1 is a diagram of the transesterification reaction and crack repair mechanism;
FIG. 2 is a graph of the shape memory cycle of the material of example 1;
FIG. 3 is a graph of shape recovery remodeling at 180 ℃ versus time for the material of example 1;
FIG. 4 is a graph of the shape memory cycle of the material of example 2;
FIG. 5 is a graph of shape recovery remodeling at 160 ℃ versus time for the material of example 2;
FIG. 6 is a graph of the shape memory 5 cycles of the material of example 3;
FIG. 7 is a graph of shape recovery remodeling at 180 ℃ versus time for the material of example 3.
Detailed Description
Example 1
Dissolving 5g of bismaleimide diphenylmethane (BMI) and 4g of 4,4' -diaminodiphenyl sulfone in acetone in a cooling reflux device, reacting for 12 hours at the controlled temperature of 60 ℃ under stirring, removing the acetone solvent by rotary evaporation of the solution, and drying for 12 hours at 70 ℃ in vacuum to obtain bismaleimide/aromatic diamine oligomer powder. Adding the oligomer into 75g of epoxy resin (E-54), melting the oligomer into a transparent solution at 100 ℃, adding 4g of promoter zinc acetylacetonate, stirring for about 3 minutes, adding 12g of glutaric anhydride, quickly stirring and uniformly mixing, pouring the mixture into a flat plate mold, performing vacuum defoaming at 110 ℃, treating according to a curing process of 110 ℃/1h +140 ℃/8h +160 ℃/2h, and naturally cooling and taking out the cured material.
FIG. 1 is a diagram showing the mechanism of ester exchange reaction and crack repair, in the material of the present invention, the molecular chain can perform an exchange reaction to reach a dynamic balance in the presence of a catalyst and under a proper temperature control, and when micro cracks appear in the material, the micro cracks can be repaired and crack surfaces can be bonded based on the rapid exchange of the molecular chain containing ester bonds.
Figure 2 is a shape memory cycle curve (dynamic thermomechanical analysis (DMA) test) of the above materials. The glass transition temperature of the prepared material is 110 ℃, and a sample is firstly heated to be higher than 130 ℃; the sample is then stretched under the action of an external force for 2min and then cooled at a rate to room temperature, at which time the length of the sample is recordedε load(ii) a The external force was then removed, and the length of the sample was recordedε unload (ii) a The sample was then reheated above 130 ℃ to trigger shape recovery when the decrease in length of the sample was recordedε rec . Rate of shape fixation: (R f ) And shape recovery rate: (R r ) The following formula was used for the calculation:
in the embodiment, the initial deformation fixing rate is 95%, the initial deformation recovery rate is 76%, the maximum deformation is changed from 10.48% to 10.36% after 5 times of circulation, and the maximum deformation is maintained at 98.8% of the initial deformation; after 5 cycles, the deformation amount of the shape recovery is changed from 2.42 percent to 2.82 percent, the deformation amount is maintained at 83.5 percent, and good shape deformation and recovery cycle stability are reflected. The thermal decomposition temperature (thermogravimetric analysis (TGA)) for a 5% weight loss of the material is 386 ℃, the initial fracture Toughness (TGA)K ICorginal ) Comprises the following steps: 1.45MPa.m1/2Fracture toughness of fracture sample after fracture surface healing after treatment at 200 ℃ for 1h (K IChealed ) Comprises the following steps: 1.1MPa.m1/2Crack healing efficiency: (K IChealed /K ICorginal ) It was 76%.
FIG. 3 is a graph of shape-recovery remodeling-time at 180 ℃ for a sample of a flat bar shape after material molding, wherein the sample is fixed at an ester exchange temperature (180 ℃) into a standing inverted U shape, the inverted U shape is fixed at 150 ℃ into a regular U shape, and the shape is deformed and reshaped. As can be seen from the figure, when the standing U-shaped sample is processed at 180 ℃, the material can be automatically bent downwards to form the standing inverted U shape after being restored to the straight shape, and the material can be quickly restored to the reshaped shape within 13 seconds.
Example 2
Dissolving 13g of bismaleimide diphenylmethane (BMI) and 9g of 4,4' -diaminodiphenyl sulfone in acetone in a cooling reflux device, reacting for 12 hours at the controlled temperature of 70 ℃ under stirring, removing the acetone solvent by rotary evaporation of the solution, and drying for 12 hours at the temperature of 70 ℃ in vacuum to obtain bismaleimide/aromatic diamine oligomer powder. Adding the oligomer into 100g of epoxy resin (E-51), melting the oligomer into a transparent solution at 100 ℃, adding 6.7g of promoter zinc acetylacetonate, stirring for about 3 minutes, adding 15g of glutaric anhydride, quickly stirring and uniformly mixing, pouring the mixture into a flat plate mold, performing vacuum defoamation at 110 ℃, treating according to a curing process of 110 ℃/1h +140 ℃/8h +160 ℃/2h, and naturally cooling and taking out the cured material.
FIG. 4 is a shape memory cycle curve (DMA test) for the material of example 2. The glass transition temperature of the prepared material is 128 ℃, and a sample is firstly heated to be above 150 ℃; the sample is then stretched under the action of an external force for 2min and then cooled at a rate to room temperature, at which time the length of the sample is recordedε load(ii) a The external force is then removed, at which time the sample has a length ofε unload (ii) a The sample is then reheated to above 150 ℃ to trigger shape recovery when the length of the sample is reducedε rec . In this example, the initial shape fixation rate was 96%, the shape recovery rate was 79%, and the maximum deformation amount was changed from 10.84% to 10.67% after 5 cycles, and the maximum deformation was maintained at 98.4% of the initial deformation; after 5 cycles, the deformation amount of the shape recovery is changed from 2.36 percent to 2.75 percent, the deformation amount is maintained at 83.5 percent, and good shape deformation and recovery cycle stability are reflected. The thermal decomposition temperature (TGA method) for 5wt% weight loss of the material is 371 ℃, and the initial fracture toughness: (K ICorginal ) Comprises the following steps: 1.59MPa.m1/2Fracture toughness of fracture sample after fracture surface healing after treatment at 200 ℃ for 1h (K IChealed ) Comprises the following steps: 1.1MPa.m1/2Crack healing efficiency (K IChealed /K ICorginal ) The content was 69%.
FIG. 5 is a diagram showing the shape-recovery remodeling-time at 160 ℃ after the planar straight strip sample formed by the above materials is fixed and formed into a standing inverted U shape at the transesterification temperature (180 ℃), and the inverted U shape is fixed into a regular U shape at 150 ℃. It can be seen that the straight U-shaped sample can be automatically bent upward into a standing straight U-shape after being restored to a straight shape at 160 ℃, and the material can be quickly restored and reshaped within 19 seconds.
Example 3
Dissolving 25g of bismaleimide diphenyl methyl ether and 18g of 4,4' -diaminodiphenyl ether in acetone in a cooling reflux device, reacting for 12 hours at the temperature of 70 ℃ under the stirring condition, removing the acetone solvent by rotary evaporation of the solution, and drying for 12 hours at the temperature of 70 ℃ in vacuum to obtain bismaleimide/aromatic diamine oligomer powder. Adding the oligomer into 120g of phenolic epoxy resin (F-51), melting the oligomer into a transparent solution at 100 ℃, adding 8g of promoter zinc acetylacetonate, stirring for about 5 minutes, adding 18g of hexahydrophthalic anhydride, quickly stirring and uniformly mixing, pouring the mixture into a flat plate mold, carrying out vacuum defoaming at 110 ℃, treating according to a curing process of 110 ℃/1h +140 ℃/8h +160 ℃/2h, naturally cooling, and taking out the cured material.
Figure 6 is a shape memory cycle curve (DMA test) of the above material. The glass transition temperature of the prepared material is 130 ℃, and a sample is firstly heated to be above 150 ℃; the sample is then stretched under the action of an external force for 2min and then cooled at a rate to room temperature, at which time the length of the sample is recordedε load(ii) a The external force is then removed, at which time the sample has a length ofε unload (ii) a The sample is then reheated to above 150 ℃ to trigger shape recovery when the length of the sample is reducedε rec . In this example, the initial shape fixation rate was 92% and the shape recovery rate was 76%, and the maximum deformation was maintained after 5 cycles98.3% of the initial deformation; after 5 cycles, the maximum deformation amount is changed from 7.66% to 7.53%, the deformation amount of the shape recovery is changed from 1.72% to 2.03%, and the deformation amount is maintained at 82%, so that good shape deformation and recovery cycle stability are embodied. The thermal decomposition temperature (TGA method) for 5wt% weight loss of the material is 283 ℃, and the initial fracture toughness: (K ICorginal ) Comprises the following steps: 1.76MPa.m1/2Fracture toughness of fracture sample after fracture surface healing after treatment at 200 ℃ for 1h (K IChealed ) Comprises the following steps: 1.35MPa.m1/2Crack healing efficiency (K IChealed /K ICorginal ) The content was 77%.
FIG. 7 is a graph of the flat bar-shaped sample of example 3, which is fixed at the ester exchange temperature (180 ℃) to form a standing inverted U-shape, the inverted U-shape is fixed at 150 ℃ to form a regular U-shape, and the shape is deformed and restored at 180 ℃ to reform the shape, which is shown in the figure, when the standing regular U-shaped sample is processed at 180 ℃, the material is automatically bent downward to form the standing inverted U-shape after being restored to the straight shape, and the material can be rapidly restored and reshaped within 21 seconds.
Example 4
20g of bismaleimide diphenyl methyl ether and 15g of bis (4-amino-3-methylcyclohexyl) methane are subjected to a melt reaction for 4 hours under the stirring condition to obtain bismaleimide/diamine oligomer powder. Adding the oligomer into 100g of hydrogenated bisphenol A epoxy resin, melting the oligomer into a transparent solution at 110 ℃, adding 7g of accelerator zinc acetylacetonate, stirring for about 10 minutes, adding 13g of hexahydrophthalic anhydride, quickly stirring and uniformly mixing, pouring the mixture into a flat plate mold, performing vacuum defoamation at 90 ℃, treating according to the curing process of 100 ℃/1h +130 ℃/10h +150 ℃/4h, naturally cooling, taking out the cured material, wherein the crack healing efficiency is 62%, the glass transition temperature is 116 ℃, and after five cycles (a DMA method and the testing method are the same as in example 1), the maximum deformation is maintained at 98.9% of the initial deformation; after 5 cycles, the amount of deformation was maintained at 85%.
Example 5
Dissolving 25g of bismaleimide diphenyl methyl ether and 14g of 4,4' -diaminodiphenyl ether in acetone in a cooling reflux device, carrying out reflux reaction for 8 hours under the stirring condition, and drying the solution to remove the solvent to obtain bismaleimide/aromatic diamine oligomer powder. Adding the oligomer into 90g of phosphorus-containing epoxy resin, melting the oligomer into a transparent solution at 90 ℃, adding 5g of accelerant zinc acetylacetonate, adding 12g of methylcyclohexene tetracarboxylic dianhydride under stirring, quickly stirring and uniformly mixing, pouring the mixture into a flat plate mold, carrying out vacuum defoamation at 90 ℃ according to a curing process of 110 ℃/2h +140 ℃/5h +160 ℃/3h, naturally cooling, taking out the cured material, wherein the crack healing efficiency is 69%, the glass transition temperature is 135 ℃, and after five cycles (a DMA method and the test method are the same as those in example 1), the maximum deformation is 98.5% of the initial deformation; after 5 cycles, the deformation amount was maintained at 84%.
Example 6
Dissolving 20g of bismaleimide diphenyl methyl ether and 6g of diaminobiphenyl in acetone in a cooling reflux device, reacting at 55 ℃ for 15 hours under the stirring condition, and drying the solution to remove the solvent to obtain bismaleimide/diamine oligomer powder. Adding oligomer into 110g of organic silicon epoxy resin, melting the oligomer into a transparent solution at 90 ℃, adding 6g of accelerant zinc acetylacetonate, stirring for about 20 minutes, adding 17g of methyl nadic anhydride, quickly stirring and uniformly mixing, pouring the mixture into a flat plate mold, performing vacuum defoaming at 90 ℃, treating according to a curing process of 110 ℃/2h +150 ℃/6h +180 ℃/1h, naturally cooling, taking out the cured material, wherein the crack healing efficiency is 64%, the glass transition temperature is 129 ℃, and after five cycles (DMA method, the testing method is the same as that of example 1), the maximum deformation is 99% of the initial deformation; after 5 cycles, the amount of deformation was maintained at 85%.
Example 7
Dissolving 25g of bismaleimide diphenyl methyl ether and 18g of 4,4' -diaminodiphenyl ether in cyclohexanone in a cooling reflux device, reacting for 10 hours at the temperature of 110 ℃ under the stirring condition, removing the solvent by rotary evaporation of the solution, and drying for 12 hours in vacuum at the temperature of 70 ℃ to obtain bismaleimide/aromatic diamine oligomer powder. Adding the oligomer into 120g of phenolic epoxy resin (F-51), melting the oligomer into a transparent solution at 100 ℃, adding 8g of accelerator zinc acetylacetonate, stirring for about 5 minutes, adding 18g of hexahydrophthalic anhydride, quickly stirring and uniformly mixing, adding 18.9g of cyanate resin (bisphenol A cyanate resin), stirring until cyanate is dissolved, pouring the dissolved cyanate into a flat plate mold, carrying out vacuum defoaming at 110 ℃, treating according to the curing process of 110 ℃/1h +140 ℃/8h +160 ℃/2h, and naturally cooling and taking out the cured material. The crack healing efficiency was determined to be 81%, the glass transition temperature was 139 ℃, the thermal decomposition temperature for 5wt% weight loss of the material (TGA method) was 298 ℃, and after five cycles (DMA method, test method same as example 3), the maximum deformation was 98% of the initial deformation; after 5 cycles, the deformation amount is maintained at 82.4 percent, and good shape deformation and recovery cycle stability are reflected.
Example 8
Dissolving 5g of bismaleimide diphenylmethane (BMI) and 4g of 4,4' -diaminodiphenyl sulfone in acetone in a cooling reflux device, reacting for 12 hours at the controlled temperature of 60 ℃ under stirring, removing the acetone solvent by rotary evaporation of the solution, and drying for 12 hours at 70 ℃ in vacuum to obtain bismaleimide/aromatic diamine oligomer powder. Adding the oligomer into 75g of epoxy resin (E-54), melting the oligomer into a transparent solution at 100 ℃, adding 4g of promoter zinc acetylacetonate, stirring for about 3 minutes, adding 12g of glutaric anhydride, quickly stirring and uniformly mixing, then adding 5g of organic silicon resin (model 9502), quickly stirring and pouring into a flat plate mold, carrying out vacuum defoaming at 110 ℃, treating according to a curing process of 110 ℃/1h +140 ℃/8h +160 ℃/2h, naturally cooling and then taking out the cured material. The crack healing efficiency was measured to be 71%, the glass transition temperature was 126 ℃, the thermal decomposition temperature for 5wt% weight loss of the material (TGA method) was 393 ℃, and the original shape was recovered for five cycles to 98%. After five cycles (DMA method, test method same as example 1), the maximum deformation is maintained at 98.1% of the initial deformation; after 5 cycles, the deformation amount is maintained at 82 percent, and good shape deformation and recovery cycle stability are reflected.
Claims (3)
1. A self-repairing type remoldable multiple deformation thermosetting shape memory resin material is characterized in that the preparation method of the self-repairing type remoldable multiple deformation thermosetting shape memory resin material comprises the following steps: reacting bismaleimide with an amine compound to obtain an oligomer; then adding the oligomer into epoxy resin, and then adding an accelerator; then adding acid anhydride to obtain a prepolymerization system; the prepolymerization system is subjected to thermosetting to obtain a self-repairing type remolding multi-deformation thermosetting shape memory resin material; the mass ratio of the bismaleimide to the amine compound to the epoxy resin to the acid anhydride to the accelerator is (5-25) to (4-18) to (75-120) to (12-18) to (4-8); the bismaleimide comprises bismaleimide diphenylmethane and bismaleimide diphenyl methyl ether; the amine compound is a diamine compound; the epoxy resin comprises bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated epoxy resin, novolac epoxy resin, organic silicon epoxy resin and flame-retardant epoxy resin; the promoter is a metal salt; the acid anhydride is binary acid anhydride or methyl cyclohexene tetracid dianhydride; the diamine is aromatic diamine or aliphatic diamine; the binary acid anhydride is aromatic binary acid anhydride or aliphatic binary acid anhydride; the metal salt comprises metal salts of zinc, tin, magnesium and calcium; reacting the bismaleimide and the amine compound in a solvent; the reaction condition of the bismaleimide and the amine compound in the solvent is that the bismaleimide and the amine compound react for 8-15 hours at the temperature of 55-110 ℃; removing the solvent to obtain an oligomer; adding the oligomer into epoxy resin, mixing at 90-110 ℃, and then adding an accelerator; the temperature of the thermocuring is 100-180 ℃, and the time is 8-15 hours.
2. A self-repairing, shape-transformable multi-deforming thermosetting shape-memory resin material according to claim 1, characterized in that said diamines comprise diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, bis (4-amino-3-methylcyclohexyl) methane, diaminobiphenyl; the dibasic acid anhydride comprises phthalic anhydride, hexahydrophthalic anhydride, glutaric anhydride, adipic anhydride, dodecenyl succinic anhydride and methyl nadic anhydride; the metal salt comprises zinc acetylacetonate, zinc acetate, calcium acetate, magnesium acetate and dibutyltin dilaurate.
3. A self-repairing type remoldable multiple deformation thermosetting shape memory resin material according to claim 1, characterized in that after adding acid anhydride, a prepolymerization system is obtained, then adding the additive components, and then performing heat curing; the additive component comprises cyanate ester resin, phenolic resin, organic silicon resin and furan resin; the addition amount of the addition component is 5-10% of the mass of the prepolymerization system.
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| CN110054863B (en) * | 2018-01-19 | 2020-07-03 | 清华大学 | Method for changing shape of thermosetting polymer material |
| CN110054795B (en) * | 2018-01-19 | 2020-07-03 | 清华大学 | Thermosetting polymer material processing, healing and welding method |
| WO2019165583A1 (en) * | 2018-02-27 | 2019-09-06 | 苏州大学张家港工业技术研究院 | Reversible self-repairing epoxy resin and preparation and recovery remoulding method therefor |
| CN108484910B (en) * | 2018-04-13 | 2020-05-22 | 苏州大学 | Bismaleimide-based thermosetting shape memory resin and preparation method thereof |
| CN113004497B (en) * | 2019-01-22 | 2022-06-21 | 苏州大学 | Shape memory recovery method of thermoadaptive shape memory polymer |
| CN110078896B (en) * | 2019-05-14 | 2021-06-04 | 中国科学院大学 | Intrinsic self-repairing epoxy elastomer material and preparation method thereof |
| CN110105544B (en) * | 2019-06-04 | 2021-09-07 | 安徽工业大学 | Preparation method of self-repairing material based on double repairing mechanisms |
| CN110330649B (en) * | 2019-07-30 | 2021-04-27 | 苏州大学 | Remodelable bismaleimide resin and application thereof |
| CN110330650B (en) * | 2019-07-30 | 2021-07-09 | 苏州大学 | Bismaleimide resin prepolymer and application thereof |
| CN110330647B (en) * | 2019-07-30 | 2021-06-18 | 苏州大学 | Remodelable shape memory bismaleimide resin and application thereof |
| CN110330648B (en) * | 2019-07-30 | 2021-06-18 | 苏州大学 | Prepolymer for remoldable bismaleimide resin and application thereof |
| CN111004473B (en) * | 2019-12-15 | 2021-05-25 | 苏州大学 | Epoxy resin system with split-phase structure and preparation method and application thereof |
| WO2021119874A1 (en) * | 2019-12-15 | 2021-06-24 | 苏州大学 | Epoxy resin system having phase separation structure, preparation method therefor and application thereof |
| CN111423580B (en) * | 2020-05-23 | 2021-06-18 | 苏州大学 | Shape memory resin based on biomass benzoxazine and preparation method and application thereof |
| CN112961463B (en) * | 2021-02-07 | 2022-04-08 | 四川大学 | Super-tough self-repairing epoxy resin glass polymer material and preparation method thereof |
| CN113321785B (en) * | 2021-05-27 | 2023-10-17 | 五邑大学 | Shape memory material and preparation method and application thereof |
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