CN108659462A - A kind of self-repair type can remold the multiple deformation thermoset shape memory resin material of shape - Google Patents
A kind of self-repair type can remold the multiple deformation thermoset shape memory resin material of shape Download PDFInfo
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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Abstract
The invention discloses a kind of self-repair types can remold the multiple deformation thermoset shape memory resin material of shape, mainly using bismaleimide, aromatic diamine, epoxy resin, dibasic acid anhydride and transesterification accelerating agent as raw material, bimaleimide resin progress chain elongation is reacted by aromatic diamine after forming linear oligomer, epoxy resin, accelerating agent and dibasic acid anhydride are added, a kind of the multiple deformation thermoset shape memory material of shape is remolded with self-repair function through what certain heat curing process was handled.Material prepared by the present invention can not only be remolded as new shape, and deformation recovery, which recycles, still good shape memory effect for 5 times or more, and prepared material, with good self-reparing capability, fracture toughness remediation efficiency reaches 62% or more.Therefore, prepared material has a wide range of applications potentiality in high performance structures function integration material.
Description
The present invention, which is a kind of entitled self-repair type, can remold the multiple deformation thermoset shape memory resin material of shape
And preparation method thereof, the applying date be on December 12nd, 2016, application No. is the divisional application of 201611141129X patents of invention,
Belong to product section.
Technical field
The invention belongs to the technical field of shape memory function high-performance resin matrix, be related to it is a kind of have review one's lessons by oneself reactivation
Power can remodelled shape multiple deformation thermoset shape memory resin system.
Background technology
Shape-memory polymer（SMPs）It is a kind of unique stimulation-responsive polymer, shape can be with sequencing formula
Temporary shapes are fixed into, and under specific environmental stimuli, are returned to original original shape.SMPs can be autonomous as one kind
The intellectual material of deformation has the advantages such as lightweight, at low cost, easy processing, change in shape are easy to control, transition temperature is easily adjusted.Make
For thermosetting property SMPs, there is superior mechanical property, higher thermal transition temperature and preferably resistance to than thermoplasticity SMPs
Hot property and thermal stability, being played in space self-deploys the aerospace fields such as structural member, variable geometry aircraft can not
The effect of replacement.Therefore, the high-performance thermosetting SMPs of novel structure-function integration is developed to widening SMPs potential applications
With great research significance.
But common thermosetting property SMPs can only remember a temporary shapes at present, then be returned to permanent shape, i.e., dual shape
Shape memory effect（It is included in original-shape）.This dual-shaped memory variation is using network cross-linked point as stationary phase, between crosslinking points
For strand as reversible deformation phase, deformation is the change of the chain conformation based on reversible deformation phase.Thermosetting property SMPs change in shape letters
The deficiencies of list, non-programmable deformation, significantly limits its application in emerging technology areas, and the thermosetting of thermal response deformation
Property SMPs in repeating heat treatment process, memory cycle bad stability, deformation cycle-index is limited.And contain multiple temperature
Although degree transformation or the SMPs of wide scope temperature transition can remember various shapes, only dual-shaped memory effect
Superposition, can not realize the reconstruct or remodeling of material shape, cannot be satisfied the reply deformation of two dimension or three dimensions complicated shape.
Moreover when being on active service in complex environment, SMPs materials inevitably result from micro-crack equivalent damage, lead to the mechanical property of material
It can considerable decrease and shortening materials'use service life and safety.Therefore, prepare have service life can grow and it is safe can
The multiple deformation thermoset shape memory resin system of remodelled shape has positive effect.
Invention content
The purpose of the present invention is be directed to current thermoset shape memory resin cannot again it is moulding, cannot effectively realize it is multiple
It miscellaneous shape distortion and and the problems such as will appear micro-cracks damage in use, proposes a kind of with Crack Self function
Can remodelled shape multiple deformation thermoset shape memory resin system and preparation method thereof.
In order to achieve the above objectives, the technical solution adopted by the present invention is, a kind of self-repair type can remold the multiple deformation heat of shape
The preparation method of solidity shape memory resin material, includes the following steps：Bismaleimide and amine compounds are reacted, obtained
Oligomer；Then oligomer is added in epoxy resin, adds accelerating agent；Then acid anhydrides is added, obtains prepolymerization system；Pre-polymerization
System obtains self-repair type by heat cure can remold the multiple deformation thermoset shape memory resin material of shape.
In above-mentioned technical proposal, the bismaleimide, amine compounds, epoxy resin, accelerating agent, acid anhydrides mass ratio
For（5~25）∶（4~18）∶（75~120）∶（12~18）∶（4~8）.
In above-mentioned technical proposal, the bismaleimide includes dimaleoyl imino diphenyl-methane, bismaleimide
Two methyl phenyl ethers anisole of amido；The amine compounds are diamine compound；The epoxy resin includes bisphenol A type epoxy resin, Bisphenol F
Type epoxy resin, hydrogenated epoxy resin, novolac epoxy resin, organosilicon epoxy resin, fire retarding epoxide resin；The accelerating agent is
Metal salt；The acid anhydrides is dibasic acid anhydride.
Preferably, the diamine is aromatic diamine or aliphatic diamine, such as diaminodiphenylmethane, two
It is aminodiphenyl sulfone, diaminodiphenyl ether, double（4- amino -3- methylcyclohexyls）Methane, benzidine；The dibasic acid anhydride is
Aromatic dicarboxylic anhydride or binary aliphatic acid anhydrides, such as dibasic acid anhydride include phthalic anhydride, hexahydrophthalic acid
Acid anhydride, glutaric anhydride, adipic anhydride, dodecenylsuccinic acid acid anhydride, methylcyclohexene tetracid dianhydride, methylnadic anhydride；It is described
Metal salt includes the metal salt of zinc, tin, magnesium, calcium, such as zinc acetylacetonate, zinc acetate, calcium acetate, magnesium acetate, tin dilaurate two
Butyl tin.
In above-mentioned technical proposal, the preferably described bismaleimide and amine compounds react in a solvent；The span comes
The condition that acid imide and amine compounds react in a solvent is 55~110 DEG C and reacts 8~15 hours；After removing solvent, obtain low
Polymers.Solvent is specially that can disperse solvent, such as ketones solvent of bismaleimide and amine compounds etc., after reaction, is done
It is oligomer that dry or revolving, which removes solvent and obtains solid,；Solvent, bismaleimide and amine compounds can not also be used
Frit reaction, reaction controllability is poor under the conditions of this, is unfavorable for industrialized production, the preferred bismaleimide of the present invention and amination
Object is closed to react in the presence of a solvent.
In above-mentioned technical proposal, oligomer is added in epoxy resin, accelerating agent is added after 90~110 DEG C of mixing；Institute
The temperature for stating heat cure is 100~180 DEG C, and the time is 8~15 hours, it is preferred to use staged curing technique.
Preferably, after acid anhydrides being added, prepolymerization system is obtained, addO-on therapy is added, then carries out heat cure；The addition
Component includes cyanate ester resin, phenolic resin, organic siliconresin, furane resins；The additive amount of the addO-on therapy is performed polymer
It is the 5~10% of quality；By the addition of addO-on therapy, the comprehensive performance of material can be improved.
The present invention further discloses can remold the multiple deformation thermoset shape memory resin of shape according to above-mentioned self-repair type
Self-repair type prepared by the preparation method of material can remold the multiple deformation thermoset shape memory resin material of shape.With following skill
Art effect：
（1）Material shape can be remolded automatically as new shape, for example plane vertical bar pattern product after molding are at high temperature（180~200
℃）It is fixed-type inverted U-shaped to stand, in control temperature（20 DEG C about more than glass transition temperature）Under, it is inverted U-shaped to revert to straight
After can be bent upwards automatically as stand it is just U-shaped.
（2）Material deformation recovery cycles, can show very stable shape
Memory performance, deformation fixed rate is close to 100%.
（3）Material has the function of the micro-crack that heals automatically, and Crack healing efficiency is up to 62% or more.
（4）Material has excellent heat resistance, glass transition temperature（DMA methods）At 110 DEG C~140 DEG C.
The invention also discloses the systems that a kind of self-repair type can remold the multiple deformation thermoset shape memory resin system of shape
Preparation Method includes the following steps：Bismaleimide and amine compounds are reacted, oligomer is obtained；Then oligomer is added
In epoxy resin, accelerating agent is added；Then acid anhydrides is added, the multiple deformation thermosetting property shape note of shape can be remolded by obtaining self-repair type
Recall resin system；The bismaleimide, amine compounds, epoxy resin, accelerating agent, acid anhydrides mass ratio be（5~25）∶（4
~18）∶（75~120）∶（12~18）∶（4~8）.
Preferably, after acid anhydrides being added, prepolymerization system is obtained, addO-on therapy is added, then carries out heat cure；The addition
Component includes cyanate ester resin, phenolic resin, organic siliconresin, furane resins；The additive amount of the addO-on therapy is performed polymer
It is the 5~10% of quality；By the addition of addO-on therapy, the comprehensive performance of material can be improved.
It is that epoxy-functional is generated with acid anhydrides respectively there are two kinds of crosslinking points stationary phases in Inventive polymers cross-linked network
Transesterification key and epoxy-functional and amine curing after crosslinking points.In the present invention, when reaching material glass transition temperature
On when, the motility enhancing of chain, the reversible deformation between crosslinking points is mutually the basis of shape memory.When temperature is increased to ester bond
Exchange reaction temperature（180~200 DEG C）, dynamic ester bond fast exchange reaches balance, and the topological structure of cross-linked network changes,
Internal stress relaxes, and temporary shapes for good and all can be fixed up, realize that the reconstruct or remodeling of material shape equally work as material
When micro-crack occurs in inside, the fast exchange based on the strand containing ester bond can repair fine fisssure, bond crack surface.
Compared with prior art, the invention has the advantages that：
1. self-repair type disclosed by the invention can remold the multiple deformation thermoset shape memory resin material use dynamic ester of shape and hand over
The characteristic for changing key, may be implemented the reconstruct etc. to cross-linked network molecular structure, and strand is under catalyst existence condition and appropriate
Under temperature control, exchange reaction can occur and reach dynamic equilibrium, important technical advantage is：Material shape can be remolded automatically
New shape, according to embodiments of the present invention, plane vertical bar pattern product after molding are fixed-type for the U that stands in transesterification temperature
Shape, in control temperature（It is more than glass transition temperature）Under, then by it is inverted U-shaped be fixed into it is just U-shaped, at this time will be just U-shaped in material glass
When being handled on glass transition temperature, will first revert back to can be bent upwards automatically after straight it is just U-shaped as standing；Material deformation returns
Multiple cycle-index is more, after 5 loop tests, can show very stable shape-memory properties, compared with initial deformation, shape
Become fixed rate and is more than 82% close to 100% and response rate；Material has the function of the micro-crack that heals automatically, and Crack healing efficiency is up to 62%
More than.
2. self-repair type disclosed by the invention can remold the multiple deformation thermoset shape memory resin material of shape compared to biography
The shape memory thermosets of system, not only in a short time（In 20 seconds）Can fast implement three-dimensional structure part it is automatic at
Type, deformation-reply 5 times or more remains to keep good shape-memory properties, and has good crack forming mechanism ability, improves
The stability in use of material, in addition, the excellent heat resistance of the more traditional thermoset shape memory material of material prepared by the present invention,
Glass transition temperature（DMA methods）At 110 DEG C~140 DEG C.
3. self-repair type disclosed by the invention can remold the preparation side of the multiple deformation thermoset shape memory resin material of shape
Method technique is controllable, and raw material composition is reasonable, especially under Additive, can obtain more excellent comprehensive performance；It prepares
Process does not have particular/special requirement, is conducive to industrial applications.
Description of the drawings
Fig. 1 is ester exchange reaction and crack forming mechanism mechanism figure；
Fig. 2 is the memory cycle curve graph of 1 material of embodiment；
Fig. 3 is 1 material of embodiment in 180 DEG C of shape deformation recovery remodeling-time diagrams；
Fig. 4 is the memory cycle curve graph of 2 material of embodiment；
Fig. 5 is 2 material of embodiment in 160 DEG C of shape deformation recovery remodeling-time diagrams；
Fig. 6 is 5 cyclic curve figures of shape memory of 3 material of embodiment；
Fig. 7 is 3 material of embodiment in 180 DEG C of shape deformation recovery remodeling-time diagrams.
Specific implementation mode
Embodiment 1
In equipped with cooling and reflux device, by 5g dimaleoyl iminos diphenyl-methane (BMI) and 4g4,4'- diamino hexichol
After sulfone is dissolved in acetone, under stirring condition, control temperature 60 C reacts 12h, by solution after rotary evaporation removes acetone solvent,
70 DEG C of vacuum drying 12h obtain bismaleimide/aromatic dicarboxylic amine oligomer powder.Oligomer is added to 75g epoxies
Resin（E-54）In, after 100 DEG C are melt into clear solution, 4g accelerating agent zinc acetylacetonates, stir about 3 minutes is added, then add
Enter 12g glutaric anhydrides, after being quickly uniformly mixed, be poured into flat plate mold, curing process is pressed after 110 DEG C of vacuum defoamations
110 DEG C/1h+140 DEG C/8h+160 DEG C/2h processing takes out curing materials after natural cooling.
Fig. 1 is ester exchange reaction and crack forming mechanism mechanism figure, and in material of the invention, strand is in catalyst existence condition
Under the control of lower and proper temperature, exchange reaction, which can occur, reaches dynamic equilibrium, when micro-crack occurs in material internal, based on ester-containing
The fast exchange of key strand can repair fine fisssure, bond crack surface.
Fig. 2 is the memory cycle curve of above-mentioned material（Dynamic thermomechanical is analyzed（DMA）Test）.The material of preparation
Glass transition temperature is 110 DEG C, and sample is first heated on 130 DEG C；Then sample stretches under external force, continues
2min, then rate be cooled to room temperature, the length of sample is denoted as at this timeε load；External force then is removed, at this time the length note of sample
Forε unload ；Then sample is reheated to 130 DEG C or more and triggers recovery of shape, and the length reduction of sample at this time is denoted asε rec .Shape
Shape fixed rate（R f ）And shape recovery rate（R r ）It is calculated using following formula：
In the present embodiment, first deformation fixed rate be 95%, first deformation-recovery rate 76%, undergo 5 times cycle, maximum deformation quantity from
10.48% changes to 10.36%, and largest deformation is maintain initial deformation 98.8%；5 cycles of experience, the deformation quantity of recovery of shape
2.82% is changed to from 2.42%, deformation quantity maintains 83.5%, embodies good shape deformation and recovery cycles stability.Material
The heat decomposition temperature of 5wt% weightlessness（Thermal weight loss（TGA）Method）It is 386 DEG C, initial collapse toughness（K ICorginal ）For：1.45MPa.m1 /2, fracture specimens are through 200 DEG C of processing 1h, fracture toughness after crack surface healing（K IChealed ）For：1.1MPa.m1/2, crack healing effect
Rate（K IChealed / K ICorginal ）It is 76%.
Fig. 3 is material plane vertical bar pattern product after molding in transesterification temperature（180℃）Fixed-type is the U that stands
Shape, 150 DEG C again by it is inverted U-shaped be fixed into it is just U-shaped, in 180 DEG C of shape deformation recovery remodeling-time diagrams.It can be seen from the figure that
When the just U-shaped sample that will stand is handled at 180 DEG C, material can be bent downwardly after first reverting back to straight as standing inverted U, material automatically
Material can Quick-return remodelled shape in 13 seconds.
Embodiment 2
In equipped with cooling and reflux device, by 13g dimaleoyl iminos diphenyl-methane (BMI) and 9g4,4'- diamino two
After benzene sulfone is dissolved in acetone, under stirring condition, control temperature 70 C reacts 12h, and solution is removed acetone solvent through rotary evaporation
Afterwards, 70 DEG C of vacuum drying 12h obtain bismaleimide/aromatic dicarboxylic amine oligomer powder.Oligomer is added to 100g
Epoxy resin（E-51）In, after 100 DEG C are melt into clear solution, 6.7g accelerating agent zinc acetylacetonates are added, stir about 3 divides
Clock adds 15g glutaric anhydrides, after being quickly uniformly mixed, is poured into flat plate mold, is pressed after 110 DEG C of vacuum defoamations
Curing process 110 DEG C/1h+140 DEG C/8h+160 DEG C/2h processing takes out curing materials after natural cooling.
Fig. 4 is the memory cycle curve of 2 material of embodiment（DMA is tested）.The glass transition temperature of the material of preparation
Degree is 128 DEG C, and sample is first heated on 150 DEG C；Then sample stretches under external force, continues 2min, then rate
It is cooled to room temperature, the length of sample is denoted as at this timeε load；External force then is removed, the length of sample is at this timeε unload ；Then sample
It is reheated to 150 DEG C or more and triggers recovery of shape, the length of sample is reduced at this timeε rec .In the present embodiment, first shape is fixed
Rate is 96%, shape recovery rate 79%, undergoes 5 cycles, and maximum deformation quantity changes to 10.67% from 10.84%, and largest deformation is dimension
It holds the 98.4% of initial deformation；5 cycles of experience, the deformation quantity of recovery of shape change to 2.75% from 2.36%, and deformation quantity maintains
83.5%, embody good shape deformation and recovery cycles stability.The heat decomposition temperature of material 5wt% weightlessness（TGA methods）For
371 DEG C, initial collapse toughness（K ICorginal ）For：1.59MPa.m1/2, fracture specimens are through 200 DEG C of processing 1h, after crack surface healing
Fracture toughness（K IChealed ）For：1.1MPa.m1/2Crack healing efficiency（K IChealed / K ICorginal ）It is 69%.
Fig. 5 is above-mentioned material plane vertical bar pattern product after molding in transesterification temperature（180℃）Fixed-type is to stand
It is inverted U-shaped, at 150 DEG C, then by it is inverted U-shaped be fixed into it is just U-shaped after in 160 DEG C of shape deformation recovery remodeling-time diagrams.It can from figure
To find out, when just U-shaped sample is handled at 160 DEG C, can be bent upwards automatically as just U-shaped, material of standing after first reverting back to straight
In 19 seconds can Quick-return it is again moulding.
Embodiment 3
In equipped with cooling and reflux device, by two methyl phenyl ethers anisole of 25g dimaleoyl iminos and 18g4,4'- diaminodiphenyl ether
After being dissolved in acetone, under stirring condition, control temperature 70 C reacts 12h, by solution after rotary evaporation removes acetone solvent, 70
DEG C vacuum drying 12h obtain bismaleimide/aromatic dicarboxylic amine oligomer powder.Oligomer is added to 120g phenol aldehyde types
Epoxy resin（F-51）In, after 100 DEG C are melt into clear solution, addition 8g accelerating agent zinc acetylacetonates, stir about 5 minutes,
18g hexahydrophthalic anhydrides are added, after being quickly uniformly mixed, are poured into flat plate mold, in 110 DEG C of vacuum defoamations
Afterwards by curing process 110 DEG C/1h+140 DEG C/8h+160 DEG C/2h processing, curing materials are taken out after natural cooling.
Fig. 6 is the memory cycle curve of above-mentioned material（DMA is tested）.The glass transition temperature of the material of preparation is
130 DEG C, sample is first heated on 150 DEG C；Then sample stretches under external force, continues 2min, and then rate cools down
To room temperature, the length of sample is denoted as at this timeε load；External force then is removed, the length of sample is at this timeε unload ；Then sample is again
It is heated to 150 DEG C or more and triggers recovery of shape, the length of sample is reduced at this timeε rec .In the present embodiment, first shape fixed rate is
92%, shape recovery rate 76% undergoes 5 cycles, and largest deformation is maintain initial deformation 98.3%；5 cycles of experience,
Maximum deformation quantity changes to 7.53% from 7.66%, and the deformation quantity of recovery of shape changes to 2.03% from 1.72%, and deformation quantity maintains 82%,
Embody good shape deformation and recovery cycles stability.The heat decomposition temperature of material 5wt% weightlessness（TGA methods）It is 283 DEG C,
Initial collapse toughness（K ICorginal ）For：1.76MPa.m1/2, through 200 DEG C of processing 1h, crack surface is broken tough fracture specimens after healing
Property（K IChealed ）For：1.35MPa.m1/2Crack healing efficiency（K IChealed / K ICorginal ）It is 77%.
Fig. 7 is 3 material of embodiment plane vertical bar pattern product after molding in transesterification temperature（180℃）Fixed-type is station
It is vertical inverted U-shaped, 150 DEG C again by it is inverted U-shaped be fixed into it is just U-shaped, can be with from figure in 180 DEG C of shape deformation recovery remodeling-time diagrams
Find out, when the just U-shaped sample that will stand is handled at 180 DEG C, material can be bent downwardly after first reverting back to straight as the U that stands automatically
Type, material in 21 seconds can Quick-return it is again moulding.
Embodiment 4
Two methyl phenyl ethers anisole of 20g dimaleoyl iminos and 15g is bis-（4- amino -3- methylcyclohexyls）Methane under agitation,
Frit reaction 4h obtains bismaleimide/binary amine oligomer powder.Oligomer is added to 100g hydrogenated bisphenol A epoxies
In resin, after 110 DEG C are melt into clear solution, 7g accelerating agent zinc acetylacetonates are added, stir about 10 minutes adds 13g
Hexahydrophthalic anhydride after being quickly uniformly mixed, is poured into flat plate mold, by solidification work after 90 DEG C of vacuum defoamations
Skill 100 DEG C/1h+130 DEG C/10h+150 DEG C/4h processing, takes out curing materials after natural cooling, Crack healing efficiency 62%,
Glass transition temperature is 116 DEG C, and after five cycles (DMA methods, test method is with embodiment 1), largest deformation is to maintain just
The 98.9% of beginning deformation；5 cycles of experience, deformation quantity maintain 85%.
Embodiment 5
In equipped with cooling and reflux device, by two methyl phenyl ethers anisole of 25g dimaleoyl iminos and 14g4,4'- diaminodiphenyl ether
After being dissolved in acetone, under stirring condition, solution is obtained bismaleimide/virtue by back flow reaction 8h after drying and removing solvent
Fragrant race's binary amine oligomer powder.Oligomer is added in 90g phosphorous epoxy resins, after 90 DEG C are melt into clear solution,
5g accelerating agent zinc acetylacetonates are added, 12g methylcyclohexene tetracid dianhydrides are added under stirring, after being quickly uniformly mixed,
Be poured into flat plate mold, after 90 DEG C of vacuum defoamations by 110 DEG C/2h+140 DEG C/5h+160 DEG C/3h of curing process at
It manages, curing materials, Crack healing efficiency 69% is taken out after natural cooling, glass transition temperature is 135 DEG C, after five cycles
(DMA methods, test method is with embodiment 1), largest deformation are maintain initial deformation 98.5%；5 cycles of experience, deformation quantity
Maintain 84%.
Embodiment 6
In equipped with cooling and reflux device, two methyl phenyl ethers anisole of 20g dimaleoyl iminos and 6g benzidines are dissolved in acetone
In after, under stirring condition, it is oligomeric to be obtained after drying and removing solvent bismaleimide/diamine by 55 DEG C of reaction 15h for solution
Object powder.Oligomer is added in 110g organosilicon epoxy resins, after 90 DEG C are melt into clear solution, 6g accelerating agents are added
Zinc acetylacetonate, stir about 20 minutes, adds 17g methylnadic anhydrides, after being quickly uniformly mixed, is poured into tablet
In mold, by curing process 110 DEG C/2h+150 DEG C/6h+180 DEG C/1h processing, natural cooling after 90 DEG C of vacuum defoamations
After take out curing materials, Crack healing efficiency 64%, glass transition temperature is 129 DEG C, (DMA methods, test side after five cycles
Method is with embodiment 1), largest deformation is maintain initial deformation 99%；5 cycles of experience, deformation quantity maintain 85%.
Embodiment 7
In equipped with cooling and reflux device, by two methyl phenyl ethers anisole of 25g dimaleoyl iminos and 18g4,4'- diaminodiphenyl ether
After being dissolved in cyclohexanone, under stirring condition, 110 DEG C of reaction 10h of control temperature, by solution after rotary evaporation removes solvent, 70
DEG C vacuum drying 12h obtain bismaleimide/aromatic dicarboxylic amine oligomer powder.Oligomer is added to 120g phenol aldehyde types
Epoxy resin（F-51）In, after 100 DEG C are melt into clear solution, addition 8g accelerating agent zinc acetylacetonates, stir about 5 minutes,
18g hexahydrophthalic anhydrides are added, after being quickly uniformly mixed, add 18.9g cyanate ester resins（Bisphenol-A type cyanogen
Acid ester resin）, stirring is poured into after cyanate dissolving in flat plate mold, by curing process 110 after 110 DEG C of vacuum defoamations
DEG C/1h+140 DEG C/8h+160 DEG C/2h processing, curing materials are taken out after natural cooling.Measure Crack healing efficiency 81%, glass
Glass transition temperature is 139 DEG C, the heat decomposition temperature of material 5wt% weightlessness（TGA methods）It is 298 DEG C, after five cycles (DMA methods,
Test method is with embodiment 3), largest deformation is maintain initial deformation 98%；5 cycles of experience, deformation quantity maintain
82.4%, embody good shape deformation and recovery cycles stability.
Embodiment 8
In equipped with cooling and reflux device, by 5g dimaleoyl iminos diphenyl-methane (BMI) and 4g4,4'- diamino hexichol
After sulfone is dissolved in acetone, under stirring condition, control temperature 60 C reacts 12h, by solution after rotary evaporation removes acetone solvent,
70 DEG C of vacuum drying 12h obtain bismaleimide/aromatic dicarboxylic amine oligomer powder.Oligomer is added to 75g epoxies
Resin（E-54）In, after 100 DEG C are melt into clear solution, 4g accelerating agent zinc acetylacetonates, stir about 3 minutes is added, then add
Enter 12g glutaric anhydrides, after being quickly uniformly mixed, then adds 5g organic siliconresins（Model 9502）, quickly it is poured into after stirring
It is natural by curing process 110 DEG C/1h+140 DEG C/8h+160 DEG C/2h processing after 110 DEG C of vacuum defoamations in flat plate mold
Curing materials are taken out after cooling.Crack healing efficiency 71% is measured, glass transition temperature is 126 DEG C, the heat of material 5wt% weightlessness
Decomposition temperature（TGA methods）It it is 393 DEG C, five times cycle can restore original-shape 98%.(DMA methods, test method are same after five cycles
Embodiment 1), largest deformation is maintain initial deformation 98.1%；5 cycles of experience, deformation quantity maintain 82%, embody good
Good shape deformation and recovery cycles stability.
Claims (8)
1. a kind of self-repair type can remold the multiple deformation thermoset shape memory resin material of shape, which is characterized in that described to review one's lessons by oneself
The preparation method that replica can remold the multiple deformation thermoset shape memory resin material of shape includes the following steps：By bismaleimide
Amine and amine compounds reaction, obtain oligomer；Then oligomer is added in epoxy resin, adds accelerating agent；Then it is added
Acid anhydrides obtains prepolymerization system；Prepolymerization system obtains self-repair type by heat cure can remold the multiple deformation thermosetting property shape note of shape
Recall resin material.
2. self-repair type can remold the multiple deformation thermoset shape memory resin material of shape, feature according to claim 1
Be, the bismaleimide, amine compounds, epoxy resin, accelerating agent, acid anhydrides mass ratio be（5~25）∶（4~18）∶
（75~120）∶（12~18）∶（4~8）.
3. self-repair type can remold the multiple deformation thermoset shape memory resin material of shape, feature according to claim 1
It is, the bismaleimide includes dimaleoyl imino diphenyl-methane, two methyl phenyl ethers anisole of dimaleoyl imino；The amine
Compound is diamine compound；The epoxy resin includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, hydrogenated epoxy
Resin, novolac epoxy resin, organosilicon epoxy resin, fire retarding epoxide resin；The accelerating agent is metal salt；The acid anhydrides is two
First acid anhydrides.
4. self-repair type can remold the multiple deformation thermoset shape memory resin material of shape, feature according to claim 3
It is, the diamine is aromatic diamine or aliphatic diamine；The dibasic acid anhydride be aromatic dicarboxylic anhydride or
Person's binary aliphatic acid anhydrides；The metal salt includes the metal salt of zinc, tin, magnesium, calcium.
5. self-repair type can remold the multiple deformation thermoset shape memory resin material of shape, feature according to claim 4
It is, the diamine includes diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, double（4- amino -3- methyl
Cyclohexyl）Methane, benzidine；The dibasic acid anhydride includes phthalic anhydride, hexahydrophthalic anhydride, glutaric acid
Acid anhydride, adipic anhydride, dodecenylsuccinic acid acid anhydride, methylcyclohexene tetracid dianhydride, methylnadic anhydride；The metal salt includes
Zinc acetylacetonate, zinc acetate, calcium acetate, magnesium acetate, dibutyl tin laurate.
6. self-repair type can remold the multiple deformation thermoset shape memory resin material of shape, feature according to claim 1
It is, the bismaleimide and amine compounds react in a solvent；The bismaleimide and amine compounds are in solvent
The condition of middle reaction is 55~110 DEG C and reacts 8~15 hours；After removing solvent, oligomer is obtained.
7. self-repair type can remold the multiple deformation thermoset shape memory resin material of shape, feature according to claim 1
It is, oligomer is added in epoxy resin, accelerating agent is added after 90~110 DEG C of mixing；The temperature of the heat cure is 100
~180 DEG C, the time is 8~15 hours.
8. self-repair type can remold the multiple deformation thermoset shape memory resin material of shape, feature according to claim 1
It is, after acid anhydrides is added, obtains prepolymerization system, add addO-on therapy, then carry out heat cure；The addO-on therapy includes cyanogen
Acid ester resin, phenolic resin, organic siliconresin, furane resins；The additive amount of the addO-on therapy be prepolymerization system quality 5~
10%。
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| CN110054863B (en) * | 2018-01-19 | 2020-07-03 | 清华大学 | Method for changing shape of thermosetting polymer material |
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| CN108559224A (en) | 2018-09-21 |
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| CN108559224B (en) | 2020-05-08 |
| CN106589819A (en) | 2017-04-26 |
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