CN110054795A - Thermoset macromolecule material processing, healing and welding method - Google Patents

Thermoset macromolecule material processing, healing and welding method Download PDF

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Publication number
CN110054795A
CN110054795A CN201810054186.7A CN201810054186A CN110054795A CN 110054795 A CN110054795 A CN 110054795A CN 201810054186 A CN201810054186 A CN 201810054186A CN 110054795 A CN110054795 A CN 110054795A
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macromolecule material
thermoset macromolecule
dynamic
processed
covalent bond
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CN110054795B (en
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吉岩
杨洋
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Tsinghua University
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Tsinghua University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G59/4207—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G59/686—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 containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Abstract

The invention discloses a kind of thermoset macromolecule material processing methods, the following steps are included: providing thermoset macromolecule material, the thermoset macromolecule material has position to be processed, and the position to be processed has cross-linked network, and the cross-linked network contains dynamic covalent bond；Solvent is provided, for being swollen the position to be processed；The position to be processed is handled using the solvent, is swollen the position to be processed, makes the position to be processed that dynamic covalent bond exchange reaction occur, forms new cross-linked network；And the dry thermoset macromolecule material, fix the shape of the new cross-linked network at the position to be processed.The invention also discloses a kind of thermoset macromolecule material healing process and a kind of thermoset macromolecule material welding method.

Description

Thermoset macromolecule material processing, healing and welding method
Technical field
The present invention relates to polymeric material fields, more particularly to a kind of processing of thermoset macromolecule material, healing and weldering Connect method.
Background technique
High molecular material can simply be divided into thermosetting property and two kinds of thermoplasticity.Thermal plastic high polymer is linear polymer, can It is reprocessed by way of heating melting or solvent dissolution.Thermosetting polymer is three-dimensional crosslinked network, have it is insoluble not Molten property cannot process again after machine-shaping.Thermoset macromolecule material after molding is if there is damage or needs It is utilized after splicing, just faces and need the problem of processing again.
Currently, although the method for the environmental stimulis such as existing light, heat, electricity induction adds after being able to achieve the molding of high molecular material Work, but it is complicated using these method building process, and preparation process, stimulus modality and operating condition still need to improve.Heating is common Stimulus, but it is only applicable to laboratory research.In actual application, if material is used for electronic device, high temperature adds Heat not only will affect the performance of electronic device, it is also possible to bring security risk.If material only needs partial operation, directly heat It can not achieve the effect that local heating.When material volume is larger or in irregular shape, the heating ability that takes a long time Entirety is set to reach uniform temperature, quickly cooling is then a bigger problem.Though and light source have can locally, remotely, it is former The advantage of position control, it also requires special MOLECULE DESIGN or introducing light absorption substance, there are difficulties in dispersion and polymer body for this It is incompatible problem, part photoresponsive polymer material also needs special light source, this not only higher cost, also upper in application It is very limited.Therefore, be badly in need of developing a kind of easy, efficient method can be realized high molecular material partial operation and it is whole plus Work.
Summary of the invention
Based on this, it is necessary to provide a kind of easy, efficient method, realize processing, the healing of thermoset macromolecule material And welding.
A kind of thermoset macromolecule material processing method, comprising the following steps:
Thermoset macromolecule material is provided, the thermoset macromolecule material has position to be processed, the Ministry of worker to be added Position has cross-linked network, and the cross-linked network contains dynamic covalent bond；
Solvent is provided, for being swollen the position to be processed；
The position to be processed is handled using the solvent, is swollen the position to be processed, makes the position hair to be processed Lively state covalent bond exchange reaction, forms new cross-linked network；And
The dry thermoset macromolecule material keeps the shape of the new cross-linked network at the position to be processed solid It is fixed.
The position load to be processed has dynamic covalent bond exchange reaction catalyst in one of the embodiments,.
The step of offer thermoset macromolecule material in one of the embodiments, comprising the following steps:
Thermosetting polymer precursor, curing agent and the dynamic covalent bond exchange reaction catalyst are provided；
The thermosetting polymer precursor, the curing agent and the dynamic covalent bond exchange reaction catalyst are mixed, Obtain mixture；And
The solidification temperature for heating the mixture to the thermosetting polymer precursor, obtains thermoset macromolecule material.
The dynamic covalent bond is dynamic ester bond in one of the embodiments, and the thermoset macromolecule material is ring Oxygen resin, the thermosetting polymer precursor are glycidol ether, and the curing agent is aliphatic anhydride, the dynamic covalent bond Exchange reaction catalyst is 1,5,7- tri- azabicyclic [4.4.0] decyl- 5- alkene, and the solvent is tetrahydrofuran.
Thermoset macromolecule material includes having heat cured rubber, polymer fiber, tree in one of the embodiments, One of rouge, macromolecule adhesive, high-molecular coating and polymer-based composite are a variety of.
The thermoset macromolecule material is thermosetting resin, the thermosetting resin packet in one of the embodiments, Include one of polyurethane, epoxy resin, unsaturated polyester resin, phenolic resin and bimaleimide resin or a variety of.
In one of the embodiments, the dynamic covalent bond include dynamic ester bond, dynamic disulfide bond, dynamic imine linkage and One of dynamic acylhydrazone key is a variety of.
The dynamic covalent bond is dynamic ester bond in one of the embodiments, and the solvent is the organic of not hydroxyl Solvent.
The organic solvent of the not hydroxyl includes methylene chloride, chloroform, tetrahydro furan in one of the embodiments, It mutters and one of trichloro-benzenes or a variety of.
Described the step of handling the position to be processed using the solvent, includes: in one of the embodiments,
The solvent is coated in the surface at the position to be processed, or the position to be processed is made to be locally bathed in institute It states in solvent.
It is described in one of the embodiments, to handle the position to be processed using the solvent, it is swollen described to be processed The step of position, carries out at 15 DEG C to 30 DEG C；
The drying temperature of the thermoset macromolecule material is 15 DEG C to 30 DEG C.
A kind of thermoset macromolecule material healing process, comprising the following steps:
Thermoset macromolecule material is provided, the thermoset macromolecule material has damage location, the damage location tool Crosslinking network, the cross-linked network contain dynamic covalent bond；
Solvent is provided, for being swollen the damage location；
The damage location is handled using the solvent, is swollen the damage location, makes the damage location that dynamic occur Covalent bond exchange reaction forms new cross-linked network；And
The dry thermoset macromolecule material, fixes the shape of the new cross-linked network of the damage location.
A kind of thermoset macromolecule material welding method, comprising the following steps:
First thermoset macromolecule material and the second thermoset macromolecule material, the first thermosetting polymer material are provided Material has the first welding position, and first welding position has the first cross-linked network, and first cross-linked network contains first Dynamic covalent bond, second thermoset macromolecule material have the second welding position, and second welding position has second Cross-linked network, second cross-linked network contain the second dynamic covalent bond, the first dynamic covalent bond and second dynamic Covalent bond is dynamic covalent bond of the same race；
Solvent is provided, for being swollen first welding position and the second welding position；
Contact first welding position and the second welding position；
The position that the contact is handled using the solvent is swollen the position of the contact, sends out the position of the contact Lively state covalent bond exchange reaction, forms new cross-linked network；And
The dry thermoset macromolecule material, connect first welding position with second welding position.
It is described in one of the embodiments, to contact first welding position and the second welding position including applied force Effect, so that first welding position and the second welding position is contacted and is mutually compressed.
By handling the position to be processed of the thermoset macromolecule material containing dynamic covalent bond with solvent, make the Ministry of worker to be added Position is swollen, and dynamic covalent bond exchange reaction occurs in the dynamic covalent bond for being supported on the position to be changed, to be formed New cross-linked network.This method is simple, efficient, in the case where not influencing the performance of thermoset macromolecule material, makes existing deposit Thermoset macromolecule material realize reprocessing.Handling position to be processed with solvent can be realized fixed point deformation, make to be processed Position forms partial operation or overall processing, wound healing and welding applied to thermoset macromolecule material.
Detailed description of the invention
Fig. 1 is the thermoset macromolecule material processing method flow chart of one embodiment of the invention；
Fig. 2 is the thermoset macromolecule material healing schematic diagram of one embodiment of the invention；
Fig. 3 is that the thermoset macromolecule material shape of another embodiment of the present invention welds schematic diagram.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, by the following examples, it and combines attached Thermoset macromolecule material processing, healing and welding method of the invention is further elaborated in figure.It should be appreciated that Described herein specific examples are only used to explain the present invention, is not intended to limit the present invention.
Referring to Fig. 1, one embodiment of the invention provides a kind of thermoset macromolecule material processing method, including following step It is rapid:
S100 provides thermoset macromolecule material, and the thermoset macromolecule material has position to be processed, described to be added Ministry of worker position has cross-linked network, and the cross-linked network contains dynamic covalent bond；
S200 provides solvent, for being swollen the position to be processed；
S300 handles the position to be processed using the solvent, is swollen the position to be processed, makes the Ministry of worker to be added Dynamic covalent bond exchange reaction occurs for position, forms new cross-linked network；And
S400, the dry thermoset macromolecule material, makes the shape of the new cross-linked network at the position to be processed Shape is fixed.
By handling the position to be processed of thermoset macromolecule material with solvent, it is swollen position to be processed, negative Dynamic covalent bond exchange reaction occurs for the dynamic covalent bond for being loaded in the position to be changed, to form new cross-linked network.It should Method is simple, efficient, in the case where not influencing the performance of thermoset macromolecule material, makes existing thermosetting polymer Material realizes reprocessing.Handling position to be processed with solvent can be realized fixed point deformation, and position to be processed is made to form partial operation Or overall processing, wound healing and welding applied to thermoset macromolecule material.
Dynamic covalent bond is a kind of reversible covalent bond, they can be in certain environmental condition (such as temperature, pH value, light) Lower fracture and recombination, and reach thermodynamical equilibrium, this balanced reaction is also known as the exchange reaction of dynamic covalent bond.The dynamic is total Valence link includes the dynamics covalent bonds such as dynamic ester bond, dynamic disulfide bond, dynamic imine linkage and dynamic acylhydrazone key.It is pierced by solvent Swash, fracture-regrouping process of the dynamic covalent bond can be activated, to form new cross-linked network, realizes thermosetting property high score The processing of sub- material.
The thermoset macromolecule material of offer includes having heat cured rubber, polymer fiber, resin macromolecule gluing The thermosetting materials such as agent, high-molecular coating and polymer-based composite.Thermosetting resin is a kind of thermoset plastic material, heat Thermosetting resin may include polyurethane, epoxy resin, epoxy rubber unsaturated polyester resin, phenolic resin and bismaleimide One of resin is a variety of.Position to be changed is the part of the thermosetting resin provided.
The thermoset macromolecule material provided in one of the embodiments, contains dynamic ester bond, and load has transesterification Catalyst, addition can activate ester exchange reaction not the organic solvent of hydroxyl, hand over the topology of thermoset macromolecule material The change for joining network structure, can simply and efficiently realize the processing of thermosetting resin.
The thermosetting polymer provided in one of the embodiments, is epoxy resin, there are two epoxy resin refers to and contains Or the resin of multiple epoxy groups.Epoxy resin is by Direct Bonding, epoxy group between epoxy group with aromatic hydroxyl or rouge The bonding of fat race hydroxyl or the resin with network structure synthesized in such a way that various groups are with curing agent crosslinking.In this implementation In example, synthesized by thermosetting polymer precursor with the crosslinking method of curing agent, thermosetting polymer precursor and curing agent are in ester Ester exchange reaction occurs under the catalytic action of exchange catalysts, the thermosetting polymer precursor and curing agent are in 180 DEG C of temperature Ester exchange reaction occurs for lower heating, solidifies 4h, obtains epoxy resin.Epoxy inner forms more stable ester bond, and Specific cross-linked network is formed in epoxy inner, having resin, hardness is high, the strong advantage of flexibility.
In the present embodiment, thermosetting polymer precursor is glycidol ether, and curing agent is aliphatic anhydride.Glycidol ether With aliphatic anhydride under the catalytic action of ester exchange catalyst, the epoxy resin containing dynamic ester bond is formed.Transesterification catalysis Agent is preferably tri- azabicyclic of 1,5,7- [4.4.0] decyl- 5- alkene (TBD), zinc acetate, acetoacetate zinc.
In step s 200, the solvent provided can be swollen thermoset macromolecule material, preferably low boiling point, high volatile Solvent.The molecular weight of solvent is smaller.Thermoset macromolecule material material internal has dynamic covalent bond, and the solvent activation of addition is dynamic State covalent bond exchange reaction makes the dynamic covalent bond of material internal start fracture-regrouping process under the catalytic action of catalyst, The domain topology of material is set to change.
In one of the embodiments, in the thermosetting epoxy resin material containing dynamic ester bond, preferred solvent is The not organic solvent of hydroxyl.Preferably, solvent is specifically as follows methylene chloride, chloroform, tetrahydrofuran (THF) and trichlorine One of benzene is a variety of.Can according to actual needs, such as type of the ester exchange catalyst of addition, thermosetting property to be treated The type etc. of high molecular material selects different solvents or is used in mixed way to different solvents.
In another embodiment, the thermoset macromolecule material provided is the thermosetting polymer with dynamic imine linkage Material, such as polyimides.The polyimides synthesize when with terephthalaldehyde, diethylenetriamine and three (2- amino-ethyl) amine be original Material forms the cross-linked network containing dynamic imine linkage under conditions of being not necessarily to catalyst.With the heat containing dynamic imine linkage Solidity high molecular material is raw material, coats aqueous solvent, makes the position swelling to be changed, activates imine linkage exchange reaction, make The topological cross-linked network structure of thermoset macromolecule material changes, and can simply and efficiently realize thermoset macromolecule material Processing.
In step S300, small solvent molecule infiltration is diffused into the cross-linked network of thermoset macromolecule material, is weakened Interaction force between thermoset macromolecule material polymer molecule stretches polymer molecule grid, volume expansion, solvent Addition, can reduce the activation energy of dynamic covalent bond exchange reaction, activate dynamic covalent bond exchange reaction, make position to be changed Dynamic covalent bond occur fracture-regrouping process, form new topological cross-linked network structure, thermoset macromolecule material is by again Processing sizing.Step S300 can be carried out at normal temperature, and temperature range can be 15 DEG C to 30 DEG C.
When being swollen to thermoset macromolecule material, the solvent can be coated in the table at the position to be processed Face, or it is locally bathed in the position to be processed in the solvent.Preferably drop coating or spin coating, in thermosetting polymer The position that material needs to process structure targetedly carries out the addition of solvent, it is possible to reduce unnecessary reagent waste, simultaneously It can be realized Point architecture processing, avoid extra structure change.
After S300, including step S400, the dry thermoset macromolecule material make the solvent volatilize, and make new The shape of cross-linked network fix.The presence of solvent can make position to be changed continue occur dynamic covalent bond exchange reaction, make to Network structure in transformation position is not capable of fixing, and influences the progress of subsequent reactions.Solvent can be made to volatilize by dry mode, To remove the solvent for being attached to position to be processed, drying process can be dried slowly at room temperature；Vacuum drying can also be used, Accelerate dry speed.
Preferably, the drying temperature of the drying thermoset macromolecule material is 15 DEG C to 30 DEG C.The present embodiment is real The method that existing thermoset macromolecule material shape changes does not need to heat, and can be achieved at normal temperature, can overcome heating cannot The shortcomings that fixed point is processed.Method by coating the solvent at position to be processed, making position to be processed, deformation occurs, The shape invariance at his position, deformation method are more flexible.
The embodiment of the present invention also provides a kind of thermoset macromolecule material healing process, comprising the following steps:
S110, provides thermoset macromolecule material, and the thermoset macromolecule material has damage location, the pars affecta Position has cross-linked network, and the cross-linked network contains dynamic covalent bond；
S210 provides solvent, for being swollen the damage location；
S310 handles the damage location using the solvent, is swollen the damage location, the damage location occurs Dynamic covalent bond exchange reaction, forms new cross-linked network；And
S410, the dry thermoset macromolecule material, makes the shape of the new cross-linked network of the damage location It is fixed.
The present embodiment is the expansion application of the thermoset macromolecule material processing method, described in the processing method Position to be processed is the damage location in the present embodiment.The damage is the thermosetting property high score of the generations such as pin hole or stroke Sub- material damage.By handling the damage location of thermoset macromolecule material with solvent, it is swollen damage location, is being loaded Dynamic covalent bond exchange reaction occurs in the dynamic covalent bond of the damage location, to form new cross-linked network.This method Simply, efficiently, in the case where not influencing the performance of thermoset macromolecule material, make the existing thermosetting polymer that there is damage Material realizes healing.The healing that can be realized fixed point damage location with solvent processing damage location, makes damage location form part Healing or whole healing.
The thermoset macromolecule material provided in one of the embodiments, is that the thermosetting property containing dynamic ester bond is high Molecular material, the thermoset macromolecule material containing dynamic ester bond have damage location, and the damage location has crosslinking Network, the cross-linked network, which contains dynamic ester bond and loads, catalyst for ester exchange reaction.It provides and holds agent, be swollen the pars affecta The cross-linked network of position.Make the damage location that ester exchange reaction occur, new cross-linked network is formed, to realize the pars affecta The healing of position.
The embodiment of the present invention also provides a kind of thermoset macromolecule material welding method, comprising the following steps:
S120, provides the first thermoset macromolecule material and the second thermoset macromolecule material, and first thermosetting property is high Molecular material has the first welding position, and first welding position has the first cross-linked network, and first cross-linked network contains There is the first dynamic covalent bond, second thermoset macromolecule material has the second welding position, the second welding position tool There is the second cross-linked network, second cross-linked network contains the second dynamic covalent bond, the first dynamic covalent bond and described Two dynamic covalent bonds are dynamic covalent bond of the same race；
S220 provides solvent, for being swollen first welding position and the second welding position；
S321 contacts first welding position and the second welding position；
S322 handles the position of the contact using the solvent, is swollen the position of the contact, makes the portion of the contact Dynamic covalent bond exchange reaction occurs for position, forms new cross-linked network；And
S420, the dry thermoset macromolecule material, connects first welding position and second welding position It connects.
It is described in one of the embodiments, to contact first welding position and the second welding position including applied force Effect, so that first welding position and the second welding position is contacted and is mutually compressed.
The present embodiment is that another expansion of the thermoset macromolecule material processing method is applied, in the processing method The position to be processed be the welding position in the present embodiment.It is high by handling the first, second thermosetting property with solvent The contact site of molecular material, is swollen contact site, covalent in the dynamic for being supported on first, second welding position Dynamic covalent bond exchange reaction occurs for key, so that new cross-linked network is formed, by first, second thermoset macromolecule material It is connected by the first welding position with second welding position.This method is simple, efficient, is not influencing thermosetting polymer material In the case where the performance of material, existing thermoset macromolecule material is made to realize welding.It can with solvent processing welding position Realize fixed point welding.
First thermoset macromolecule material and the second thermosetting polymer material provided in one of the embodiments, Material is the thermoset macromolecule material containing dynamic ester bond, the cross-linked network of first welding position and second weld part The cross-linked network of position, which contains dynamic ester bond and loads, catalyst for ester exchange reaction.It provides and holds agent, be swollen first, second heat The contact site of solidity high molecular material.Make first, second welding position that ester exchange reaction occur, forms new cross-linked network Network, to realize the welding of first, second thermoset macromolecule material.
The preparation of 1 thermosetting epoxy resin of embodiment
Prepare tri- azepine of bisphenol A diglycidyl ether, adipic acid and ester exchange catalyst 1,5,7- of molar ratio 1:1:0.1 The mixture of two rings [4.4.0] decyl- 5- alkene (TBD)；
Mixture is melted and is uniformly mixed under the conditions of 180 DEG C；
Mixture after melting is placed in mold, keep it is temperature-resistant start gel to system after system is placed in Hot pressing under the conditions of 5MPa continues to solidify 4h, reacts bisphenol A diglycidyl ether completely with adipic acid, obtain containing ester bond Thermosetting epoxy resin.Wherein, mold is from molding jig, and centre has square hole, is used for thermosetting epoxy resin system It is prepared as rectangular film.Mold can be the aluminium flake with a thickness of 0.2mm.The rectangular membrane structure of preparation is as initial thermosetting Property epoxy rouge material 10.
The healing of 2 thermosetting epoxy resin of embodiment
Referring to Fig. 2, pricking pin hole 21 in initial thermosetting epoxy resin material surface prepared by embodiment 1 with sharp equipment Or stroke generates scratch 22；
THF solvent is smeared at dog-ear, is swollen pin hole 21 and scratch 22；
Volatilize the THF solvent, and after the THF solvent gives full play to, pin hole 21 and scratch 22 heal, after obtaining healing Thermosetting epoxy resin material 31.
The vitrifying that thermosetting epoxy resin material 31 after above-mentioned healing is warming up to epoxy resin glass polymer is turned Temperature (Tg), when such as 80 DEG C or more, the form of healing is still remained unchanged.
The welding of 3 thermosetting epoxy resin of embodiment
Referring to Fig. 3, the initial thermosetting epoxy resin material of two panels prepared by embodiment 1 is provided, i.e., the first initial thermosetting Property epoxide resin material 11 and the second initial thermosetting epoxy resin material 12；
Make 24 overlying contact of the first welding position 23 and the second welding position, applies pressure and mutually compress；
THF solvent is smeared in contact site, is swollen contact site；
Volatilize the THF solvent, after the THF solvent gives full play to, the first initial thermosetting epoxy resin material 11 Weld together with the second initial thermosetting epoxy resin material 12, forms thermosetting epoxy resin material after integrated welding 42。
The vitrifying that thermosetting epoxy resin material 42 after above-mentioned welding is warming up to epoxy resin glass polymer is turned Temperature (Tg), when such as 80 DEG C or more, welding position will not loosen.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (14)

1. a kind of thermoset macromolecule material processing method, comprising the following steps:
Thermoset macromolecule material is provided, the thermoset macromolecule material has position to be processed, the position tool to be processed Crosslinking network, the cross-linked network contain dynamic covalent bond；
Solvent is provided, for being swollen the position to be processed；
The position to be processed is handled using the solvent, is swollen the position to be processed, the position to be processed occurs dynamic State covalent bond exchange reaction, forms new cross-linked network；And
The dry thermoset macromolecule material, fixes the shape of the new cross-linked network at the position to be processed.
2. thermoset macromolecule material processing method according to claim 1, which is characterized in that the position to be processed is negative It is loaded with dynamic covalent bond exchange reaction catalyst.
3. thermoset macromolecule material processing method according to claim 2, which is characterized in that the offer thermosetting property is high The step of molecular material, comprising the following steps:
Thermosetting polymer precursor, curing agent and the dynamic covalent bond exchange reaction catalyst are provided；
The thermosetting polymer precursor, the curing agent and the dynamic covalent bond exchange reaction catalyst are mixed, obtained Mixture；And
The solidification temperature for heating the mixture to the thermosetting polymer precursor, obtains thermoset macromolecule material.
4. thermoset macromolecule material processing method according to claim 3, which is characterized in that the dynamic covalent bond is Dynamic ester bond, the thermoset macromolecule material are epoxy resin, and the thermosetting polymer precursor is glycidol ether, described Curing agent is aliphatic anhydride, and the dynamic covalent bond exchange reaction catalyst is 1,5,7- tri- azabicyclic [4.4.0] decyl- 5- Alkene, the solvent are tetrahydrofuran.
5. thermoset macromolecule material processing method according to claim 1, which is characterized in that thermoset macromolecule material Including with heat cured rubber, polymer fiber, resin, macromolecule adhesive, high-molecular coating and polymer-based composite wood One of material is a variety of.
6. thermoset macromolecule material processing method according to claim 1, which is characterized in that the thermosetting polymer Material is thermosetting resin, the thermosetting resin include polyurethane, epoxy resin, unsaturated polyester resin, phenolic resin and One of bimaleimide resin is a variety of.
7. thermoset macromolecule material processing method according to claim 1, which is characterized in that the dynamic covalent bond packet Include one of dynamic ester bond, dynamic disulfide bond, dynamic imine linkage and dynamic acylhydrazone key or a variety of.
8. thermoset macromolecule material processing method according to claim 1, which is characterized in that the dynamic covalent bond is Dynamic ester bond, the solvent are the organic solvent of not hydroxyl.
9. thermoset macromolecule material processing method according to claim 8, which is characterized in that the not hydroxyl has Solvent includes one of methylene chloride, chloroform, tetrahydrofuran and trichloro-benzenes or a variety of.
10. thermoset macromolecule material processing method according to claim 1, which is characterized in that described using described molten Agent handle the position to be processed the step of include:
The solvent is coated in the surface at the position to be processed, or to be locally bathed in the position to be processed described molten In agent.
11. thermoset macromolecule material processing method according to claim 1, which is characterized in that described using described molten The step of agent handles the position to be processed, is swollen the position to be processed carries out at 15 DEG C to 30 DEG C；
The drying temperature of the thermoset macromolecule material is 15 DEG C to 30 DEG C.
12. a kind of thermoset macromolecule material healing process, which comprises the following steps:
Thermoset macromolecule material is provided, the thermoset macromolecule material has damage location, and the damage location, which has, to be handed over Networking network, the cross-linked network contain dynamic covalent bond；
Solvent is provided, for being swollen the damage location；
The damage location is handled using the solvent, is swollen the damage location, makes the damage location that dynamic occur covalent Key exchange reaction forms new cross-linked network；And
The dry thermoset macromolecule material, fixes the shape of the new cross-linked network of the damage location.
13. a kind of thermoset macromolecule material welding method, which comprises the following steps:
First thermoset macromolecule material and the second thermoset macromolecule material, the first thermoset macromolecule material tool are provided There is the first welding position, first welding position has the first cross-linked network, and first cross-linked network contains the first dynamic Covalent bond, second thermoset macromolecule material have the second welding position, and second welding position has the second crosslinking Network, second cross-linked network contain the second dynamic covalent bond, and the first dynamic covalent bond and second dynamic are covalently Key is dynamic covalent bond of the same race；
Solvent is provided, for being swollen first welding position and the second welding position；
Contact first welding position and the second welding position；
The position that the contact is handled using the solvent is swollen the position of the contact, the position of the contact occurs dynamic State covalent bond exchange reaction, forms new cross-linked network；And
The dry thermoset macromolecule material, connect first welding position with second welding position.
14. thermoset macromolecule material welding method according to claim 13, which is characterized in that described to make described first Welding position and the contact of the second welding position include the effect of applied force, connect first welding position and the second welding position It touches and mutually compresses.
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