CN106832783A - A kind of method of the toughening modifying of epoxy resin - Google Patents
A kind of method of the toughening modifying of epoxy resin Download PDFInfo
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- CN106832783A CN106832783A CN201710095628.8A CN201710095628A CN106832783A CN 106832783 A CN106832783 A CN 106832783A CN 201710095628 A CN201710095628 A CN 201710095628A CN 106832783 A CN106832783 A CN 106832783A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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Abstract
The invention provides a kind of method of the toughening modifying of epoxy resin, including：Using atom transition free radical polymerization reaction ATRP in the hydroxy position of Graphene graft polymers long-chain, prepare functionalization graphene；Functionalization graphene is well mixed with epoxy resin, modified epoxy resin is obtained.The toughness of epoxy resin can be effectively improved using the present invention, while being also not in two phase structure, disperseing the problem of the inherent characteristic of the influence epoxy resin such as uneven.
Description
Technical field
The application is related to organic high molecular compound preparing technical field, more particularly to a kind of toughening modifying of epoxy resin
Method.
Background technology
Epoxy resin is because of the chemically-resistant of its excellent physical and mechanical properties, heat endurance, superior electrical property and protrusion
Corrosivity, has been widely used in the neck such as coating, composite, high-performance adhesive, electrically insulating material and Aeronautics and Astronautics
Domain.But, substantial amounts of epoxide group is contained in epoxy resin, product crosslink density after solidification is big, therefore existence is crisp, anti-impact
The problems such as hitting property difference.In recent years, the toughening modifying to epoxy resin is always the domestic and international heat subject studied.
The modified predominantly physical modification of traditional epoxy resin, its main thought is that modifying agent is total to epoxy resin
It is mixed, two phase structure is presented after blending.The approach of traditional modified epoxy mainly has：Caoutchouc elasticity is modifies, thermoplastic resin
Fat is modified, rigid particles are modified etc..Modifying agent typically has preferable toughness, modulus higher.Modified epoxy resin exists
Toughness aspect is improved really, but it is also apparent from the drawbacks of bring with problem：Modified epoxy resin
Glass transition temperature elastic modelling quantity and viscosity etc. receive a certain degree of influence, limit epoxy resin application and
Field operation.
The content of the invention
In view of this, the invention provides a kind of method of the toughening modifying of epoxy resin, such that it is able to be effectively improved ring
The toughness of oxygen tree fat, while being also not in two phase structure, disperseing the inherent characteristic of the influence epoxy resin such as uneven
Problem.
What technical scheme was specifically realized in：
A kind of method of the toughening modifying of epoxy resin, the method includes：
Using atom transition free radical polymerization reaction ATRP in the hydroxy position of Graphene graft polymers long-chain, prepare
Functionalization graphene；
Functionalization graphene is well mixed with epoxy resin, modified epoxy resin is obtained.
Preferably, utilization ATRP graft polymers long-chains in the hydroxy position of Graphene, prepare function graphite
Alkene includes：
The side base with ATRP active halogen atoms is introduced in the hydroxy position of graphene oxide, synthesis graphene oxide is big
Initiator molecule；
Trigger monomer that polymerisation occurs using ATRP, polymeric long chain is grafted on graphene oxide, prepare
Functionalization graphene.
Preferably, described introduce the side base with ATRP active halogen atoms, synthesis in the hydroxy position of graphene oxide
Graphene oxide macromole evocating agent includes：
It is 0.6~2.1 according to the hydroxy functional group of graphene oxide and the mol ratio of halo nucleopilic reagent:1 or 0.5~
2.0:1, the hydroxy functional group of graphene oxide is 5.0~20.0 with the weight ratio of catalyst:1, by graphene oxide, halo parent
Core reagent and catalyst are added in a flask equipped with stirring, under inert gas shielding, are placed in oil bath and are reacted, and obtain oxygen
Graphite alkene macromole evocating agent.
Preferably, the halo nucleopilic reagent be on α-carbon it is active substitution base halogenated carboxylic acid class nucleopilic reagent or
The halogenated carboxylic acid class nucleopilic reagent containing weak R-X keys on α-carbon；
Wherein, R is N, S or O, and X is Cl or Br.
Preferably, the active substituent is aryl, carbonyl or pi-allyl.
Preferably, the catalyst is reaction between hydroxy groups and carboxylic acids nucleopilic reagent to graphene oxide having
The alkali compounds of catalytic action.
Preferably, the catalyst is NaOH, KOH or tetramethyl ammonium.
Preferably, the state of the graphene oxide is solution state.
Preferably, the graphene oxide is graphene oxide that degree of oxidation is 1%~60%.
Preferably, the graphene oxide solution is by graphene oxide powder and the tetrahydrofuran or first as the first solvent
Benzene is obtained after fully dissolving.
Preferably, the method is still further comprised：
Before halo nucleopilic reagent and catalyst is added, Na is used2CO3The pH value of the graphene oxide solution is adjusted
Save to 7~10.
Preferably, the halo nucleopilic reagent be 2- bromo acids, 2 bromopropionic acid, to bromo methyl acid and to carboxyl
At least one in benzene sulfonyl chloride.
Preferably, the method is still further comprised：
The functionalization graphene that will be prepared is cleaned with one or several of absolute ethyl alcohol, acetone or water, repeats 4~8
It is secondary；And be vacuum dried at 40~80 DEG C.
Preferably, the use ATRP triggers monomer that polymerisation occurs, polymeric long chain is grafted to graphene oxide
On, preparing functionalization graphene includes：
According to the halogen atom in graphene oxide macromole evocating agent and ATRP catalyst, ligand mol ratio for 1~
1.5:1~1.5:1~3, graphene oxide macromole evocating agent, ATRP catalyst and ligand are added to one together and are furnished with
In the flask of stirring, reaction flask is tightly sealed, vacuumize and be filled with inert gas, repeated 2~4 times；Then, with syringe plus
Enter the second solvent and monomer, be placed in oil bath and react, system occurs ATRP reactions under solution state；After reaction terminates, polymerization
Product obtains functionalization graphene through precipitation, washing and vacuum drying.
Preferably, the ATRP catalyst is CuX, FeX2、CuX2Or FeX3；
Wherein, X is Cl or the type of Br, X is consistent with the type of halogen atom in halo nucleopilic reagent.
Preferably, the ligand is one or more ligand containing N- or P-, it was coordinated to σ-key or π-key
Cross on metal.
Preferably, the ligand is 2,2 ＇-bipyridine (bpy), 4,4 ＇-two (five-nonyl) -2,2 ＇-bipyridine
(dNbpy), 4,4 ＇-＇ of di-n-butyl-2,2-bipyridine (dTbpy), N, N, N ＇, N ＇ ＇, N ＇ ＇-five methyl diethylentriamine
(PMDETA), the mixture of one or more in triphenylphosphine (TPP) or tributylphosphine (TBUP).
Preferably, the monomer is methyl methacrylate, methacrylic acid or GMA.
Preferably, second solvent is the organic solvent that can dissolve graphene oxide macromole evocating agent.
Preferably, second solvent is toluene, tetrahydrofuran or acetone.
Preferably, described be well mixed functionalization graphene with epoxy resin, obtaining modified epoxy resin includes：
By functionalization graphene be dissolved in tetrahydrofuran, acetone or toluene one or several in, be configured to solution；In ice
Under the conditions of bath, it is allowed to be completely dispersed by ultrasound in ultrasonic wave；Epoxy resin is added in the solution, by mechanical agitation so that work(
Energy graphite alkene is completely dispersed in the epoxy；It is placed in again in vacuum drying chamber and is vacuum dried, obtains modified epoxy resin.
Preferably, the state of the functionalization graphene is solution state.
Preferably, the functionalization graphene is in surface of graphene oxide grafted methacrylic acid methyl esters, metering system
Acid or GMA.
As seen from the above technical solution, in the inventive solutions, due to make use of hydroxy groups and nucleopilic reagent
Between reactivity, in the hydroxy position of graphene oxide introduce side base with ATRP active halogen atoms, synthesis aoxidize stone
Black alkene macromole evocating agent；Then trigger monomer that polymerisation occurs using ATRP, polymeric long chain is successfully grafted to oxygen
On graphite alkene, functionalization graphene is prepared；Finally epoxy resin is spiked into functionalization graphene solution, is well mixed,
Prepare modified epoxy resin.Therefore, Graphene provided by the present invention is epoxy resin toughened can be effectively improved epoxy
The toughness of resin, simultaneously because the polymer long-chain of graphene oxide grafting can produce chemical bonding with epoxide group again
Effect, is not in two phase structure, disperses uneven problem, influence the inherent characteristic of epoxy resin, it is to avoid physical modification
The drawbacks of being brought Deng traditional method of modifying.The present invention changes the rigid chain segment of epoxy resin into flexible chain by MOLECULE DESIGN means
Section, such that it is able to fundamentally improve the toughness of epoxy resin.For example, by using the modified asphalt mixtures modified by epoxy resin of the method for the present invention
Fat toughness improves 42%-86%.
Brief description of the drawings
Fig. 1 is the flow chart of the method for the toughening modifying of the epoxy resin in the embodiment of the present invention.
Fig. 2 be the graphene oxide macromolecular in the embodiment of the present invention synthesis and ATRP method in graphene oxide hydroxyl
The synthetic route chart of graft polymers long-chain on position.
Specific embodiment
To make technical scheme and advantage become more apparent, below in conjunction with drawings and the specific embodiments, to this
Invention is described in further detail.
In an embodiment of the present invention, there is provided a kind of method of the toughening modifying of epoxy resin.
Fig. 1 is the flow chart of the method for the toughening modifying of the epoxy resin in the embodiment of the present invention, and Fig. 2 is implementation of the present invention
Synthesis and ATRP method the graft polymers long-chain in graphene oxide hydroxy position of the big institute's molecule of graphene oxide in example
Synthetic route chart.Such as Fig. 1 is simultaneously combined shown in Fig. 2, and the method for the toughening modifying of the epoxy resin in the embodiment of the present invention includes
Step as described below：
Step 11, using atom transition free radical polymerization reaction (ATRP) in the hydroxy position of Graphene graft polymers
Long-chain, prepares functionalization graphene；
In the inventive solutions, it is possible to use various ways realize above-mentioned step 11.
For example, preferably, in a particular embodiment of the present invention, the step 11 is specifically as follows：
Step 111, introduces the side base with ATRP active halogen atoms, synthesis oxidation in the hydroxy position of graphene oxide
Graphene macromole evocating agent；
In this step, it is possible to use the reactivity between hydroxy groups and nucleopilic reagent, in the hydroxyl of graphene oxide
The side base with ATRP active halogen atoms is introduced on position, synthesizes graphene oxide macromole evocating agent.
Step 112, triggers monomer that polymerisation occurs using ATRP, and polymeric long chain is grafted on graphene oxide,
Prepare functionalization graphene.
By above-mentioned step 111 and 112, functionalization graphene can be prepared.
Step 12, functionalization graphene is well mixed with epoxy resin, obtains modified epoxy resin.
Two-dimensional nanostructure Graphene is due to excellent mechanical property, heat endurance, superior electrical property and protrusion
Magnetic property, therefore can be used for strengthen macromolecular material.
In order to improve the performance of graphene/polymer composite material to greatest extent, it is necessary to meet two big key factors：1)
Graphene being uniformly distributed in macromolecule matrix；2) effective transfer of the external load between Graphene-polymer-based body interface.
To solve these problems, functional modification can be carried out to Graphene and its derivative.Wherein, it is most effective, most normal
What is seen is covalent modification Graphene.The graphene oxide as obtained in oxidation-reduction method, its sheet surfaces contain hydroxyl, carboxyl,
Epoxide group isoreactivity functional group, these functional groups exist for by covalent modified that to realize that graphene functionalized is provided good
Condition.
Inventor after research by having found, it is possible to use surface of graphene oxide contains the officials such as carboxyl, hydroxyl, epoxide group
Can roll into a ball, initiator is reacted to organohalogen compounds.It is then possible to using transient metal complex as halogen atom carrier, with
Initiator is with the use of initiation monomer reaction so that surface of graphene oxide success graft polymers long-chain.After grafting
Graphene oxide shows good dispersiveness, therefore functionalization graphene can be uniformly dispersed in a solvent, adds epoxy
Mixed with resin is uniform, so as to realize being modified epoxy resin.
In the inventive solutions, it is possible to use various ways realize above-mentioned step 111.
For example, preferably, in a particular embodiment of the present invention, the step 111 can be implemented by following
Mode is realized：
It is 0.6~2.1 according to the hydroxy functional group of graphene oxide and the mol ratio of halo nucleopilic reagent:1 (can also be
0.5~2.0:1), the hydroxy functional group of graphene oxide and the weight ratio of catalyst are 5.0~20.0:1, by graphene oxide,
Halo nucleopilic reagent and catalyst are added in a flask equipped with stirring, under inert gas shielding, are placed in oil bath and are reacted
(for example, 0.25~2.5h is reacted in 25~90 DEG C of oil bath), obtains graphene oxide macromole evocating agent (for example, surface band
Active halogen atom, the graphene oxide macromole evocating agent that halogen atom loading is 1%~60%).
In addition, preferably, in a particular embodiment of the present invention, the halo nucleopilic reagent is active on α-carbon
Replace the halogenated carboxylic acid class nucleopilic reagent or the halogenated carboxylic acid class nucleopilic reagent containing weak R-X keys on α-carbon of base；Wherein, R
Can be N, S or O, X can be Cl or Br.
Preferably, in a particular embodiment of the present invention, the active substituent can be aryl, carbonyl or pi-allyl.
Preferably, in a particular embodiment of the present invention, the catalyst is the hydroxy groups and carboxylic to graphene oxide
Alkali compounds of the reaction with catalytic action between acids nucleopilic reagent.
For example, in the preferred embodiment, the catalyst can be NaOH, KOH or tetramethyl ammonium.
Preferably, in a particular embodiment of the present invention, the state of the graphene oxide is solution state.
Preferably, in a particular embodiment of the present invention, the graphene oxide can be that degree of oxidation is 1%~60%
Graphene oxide.
Preferably, in a particular embodiment of the present invention, add other reaction reagents (for example, halo nucleopilic reagent and
Catalyst) before, use Na2CO3The pH value of the graphene oxide solution is adjusted to 7~10.
Preferably, in a particular embodiment of the present invention, the graphene oxide solution can be by graphene oxide powder
With fully dissolved as the tetrahydrofuran or toluene of the first solvent after be obtained.
Preferably, in a particular embodiment of the present invention, the halo nucleopilic reagent is 2- bromo acids, 2- bromines third
Acid, to bromo methyl acid and at least one in carboxylphenylsulphonyl chloride.
Preferably, in a particular embodiment of the present invention, the method is still further comprised：
The functionalization graphene that will be prepared is cleaned with one or several of absolute ethyl alcohol, acetone or water, repeats 4~8
It is secondary；And be vacuum dried at 40~80 DEG C.
In the inventive solutions, it is also possible to realize above-mentioned step 112 using various ways.
For example, preferably, in a particular embodiment of the present invention, the step 112 can be implemented by following
Mode is realized：
According to the halogen atom in graphene oxide macromole evocating agent and ATRP catalyst, ligand mol ratio for 1~
1.5:1~1.5:1~3, graphene oxide macromole evocating agent, ATRP catalyst and ligand are added to one together and are furnished with
In the flask of stirring, reaction flask is tightly sealed, vacuumize and be filled with inert gas, repeated 2~4 times；Then, with syringe plus
Enter the second solvent and monomer, be placed in oil bath (for example, in 25~110 DEG C oil bath) reaction, system occurs under solution state
ATRP reacts；After reaction terminates, polymerizate obtains functionalization graphene through precipitation, washing and vacuum drying.
In addition, preferably, in a particular embodiment of the present invention, the ATRP catalyst can be CuX, FeX2、CuX2Or
FeX3；Wherein, X can be Cl or Br, X type it is consistent with the type of halogen atom in halo nucleopilic reagent.
Preferably, in a particular embodiment of the present invention, the ligand can contain N- or P- one or more
Ligand, is coordinated on transition metal (for example, Fe or Cu) with σ-key or π-key.
For example, in the preferred embodiment, the ligand can be 2,2 ＇-bipyridine (bpy), 4,4 ＇-
Two (five-nonyl)-2,2 ＇-bipyridines (dNbpy), 4,4 ＇-＇ of di-n-butyl-2,2-bipyridine (dTbpy), N, N, N ＇,
One kind or many in N ＇ ＇, N ＇ ＇-five methyl diethylentriamine (PMDETA), triphenylphosphine (TPP) or tributylphosphine (TBUP)
The mixture planted.
Preferably, in a particular embodiment of the present invention, the monomer can be methyl methacrylate (MMA), methyl
Acrylic acid (MA) or GMA (GMA).
Preferably, in a particular embodiment of the present invention, second solvent is that can dissolve graphene oxide macromolecular
The organic solvent of initiator.
For example, in the preferred embodiment, second solvent can be toluene, tetrahydrofuran or acetone.
In the inventive solutions, it is also possible to realize above-mentioned step 12 using various ways.
For example, preferably, in a particular embodiment of the present invention, the step 12 can be by the following side of implementing
Formula is realized：
By functionalization graphene be dissolved in tetrahydrofuran, acetone or toluene one or several in, be configured to solution (example
Such as, concentration is the solution of 0.025~0.25mg/mL)；Under condition of ice bath, by ultrasound in ultrasonic wave (for example, 20~
2~5h of ultrasound in 65kHZ ultrasonic waves) it is allowed to be completely dispersed；Epoxy resin is added in the solution, by mechanical agitation (for example, machine
Tool stirs 1~5h) such that functionalization graphene is completely dispersed in the epoxy；It is placed in again in vacuum drying chamber and is vacuum dried
(for example, 2~6h is vacuum dried at 45~75 DEG C), obtains modified epoxy resin.
Preferably, in a particular embodiment of the present invention, the state of the functionalization graphene is solution state.
Preferably, in a particular embodiment of the present invention, the functionalization graphene can be in surface of graphene oxide
Grafted methacrylic acid methyl esters (MMA), methacrylic acid (MA) or GMA (GMA).
Below by the way of three are embodied, Jie further, detailed is carried out to technical scheme
Continue.
Embodiment one,
In the present embodiment one, it is possible to use the following step that implements obtains modified epoxy resin：
(1) graphene oxide macromole evocating agent is prepared；
Specifically, can first take 25g graphene oxides fully to be dissolved in 150mL dichloromethane, with 1.734g 2- bromines
The tetramethyl ammonium of propionic acid and 0.0835g 2 bromopropionic acids is added in a flask equipped with stirring together, in nitrogen protection
Under, 28 hours (h) of reaction in 56 DEG C of oil bath is placed in, after reaction terminates, organic phase is separated through hydrochloric acid/water, steam solvent；Then
Precipitate in acetone, filter, be dried under vacuum to constant weight, obtain graphene oxide macromolecular of the surface with active halogen atom and draw
Hair agent.
(2) functionalization graphene is prepared：
Specifically, can first by 1g graphene oxides initiator and 0.341g CuBr, 0.325g N, N, N ＇, N ＇ ＇,
N ＇ ＇-five methyl diethylentriamine (PMDETA) is added in a flask equipped with stirring together, seals reaction flask, takes out true
Sky is simultaneously filled with nitrogen, is repeated 4 times；Then, 25mL toluene and 10g GMAs are introduced by syringe
(GMA), it is placed in 24 hours (h) of reaction in 85 DEG C of oil bath；Reaction terminate after, polymerizate through acetone precipitation, distillation water washing,
60 DEG C of vacuum dryings, obtain functionalization graphene.
(3) modified epoxy resin is prepared：
Specifically, first 0.3g functionalization graphenes can be dissolved in 240mL toluene, be configured to concentration for 0.125mg/
The solution of mL；Under condition of ice bath, ultrasound 3h in 40kHz ultrasonic waves, functionalization graphene is completely dispersed in the solution；Pour into ring
Oxygen tree fat 300g, in mechanical agitation 2h so that functionalization graphene is completely dispersed in the epoxy；It is placed on 60 DEG C of vacuum
Solvent is removed in drying box, room temperature is cooled to；Add curing agent to pour into mould to solidify, test the power of modified epoxy resin
Learn performance.When functionalization graphene content is 0.1wt.%, tensile toughness amplification is up to 253.4%, toughness amplification
Up to 120.5%；When functionalization graphene content is 0.2wt.%, tensile toughness amplification is up to 168.3%, toughness
Amplification is up to 97.5%.
Embodiment two,
In the present embodiment two, it is possible to use the following step that implements obtains modified epoxy resin：
(1) graphene oxide macromole evocating agent is prepared；
Specifically, in graphene oxide powder first being dissolved in into acetone, tetrahydrofuran mixed liquor.5g graphite oxides
Alkene solution and 0.683g to being added in a flask equipped with stirring together with bromo methyl acid and 0.0183g NaOH, in argon
Under gas shielded, it is placed in and 24h is reacted in 55 DEG C of oil bath, after reaction terminates, through distilled water and methyl alcohol cyclic washing, filtering, 45 DEG C
Under be dried under vacuum to constant weight, obtain graphene oxide macromole evocating agent.
(2) functionalization graphene is prepared：
Specifically, can first by 1g graphene oxides and 0.343g CuCl, 0.404g N, N, N ＇, N ＇ ＇, N ＇ ＇-five first
Base diethylenetriamines (PMDETA) is added in a flask equipped with stirring together, tightly seals reaction flask；Vacuumize simultaneously
Argon gas is filled with, is repeated 4 times；Then, 35mL tetrahydrofurans and 10g methyl methacrylates (MMA) are introduced by syringe, is placed in
24h is reacted in 90 DEG C of oil bath；Reaction terminate after, polymerizate through methanol extraction, distillation water washing and 50 DEG C of vacuum dryings extremely
Constant weight, obtains functionalization graphene.
(3) modified epoxy resin is prepared：
Specifically, first 0.3g functionalization graphenes can be dissolved in 500mL toluene, be configured to concentration for 0.6mg/mL
Solution.Under condition of ice bath, ultrasound 4h in 40kHz ultrasonic waves, functionalization graphene is completely dispersed in the solution；Pour into epoxy
Resin 150g, then mechanical agitation 3h so that functionalization graphene is completely dispersed in the epoxy；45 DEG C of vacuum are placed on to do
Solvent is removed in dry case, room temperature is cooled to.Add curing agent to pour into mould to solidify, test the mechanics of modified epoxy resin
Performance.When functionalization graphene content is 0.1wt.%, tensile toughness amplification is up to 267.5%, and toughness amplification is high
Up to 102.7%；When functionalization graphene content is 0.2wt.%, tensile toughness amplification is up to 173.9%, and toughness increases
Panel height is up to 81.9%.
Embodiment three,
In the present embodiment three, it is possible to use the following step that implements obtains modified epoxy resin：
(1) graphene oxide macromole evocating agent is prepared；
Specifically, can first take 5g graphene oxides fully to be dissolved in 35mL dichloromethane, with 0.609g 2- bromos
The tetramethyl ammonium of isobutyric acid and 0.0232g 2- bromo acids is added in a flask equipped with stirring together, in nitrogen
Under protection, it is placed in 75 DEG C of oil bath and reacts 24h；After reaction terminates, through distilled water and methyl alcohol cyclic washing, filtering, at 65 DEG C
Constant weight is dried under vacuum to, graphene oxide macromole evocating agent is obtained.
(2) functionalization graphene is prepared：
Specifically, can first by 0.5g graphene oxides initiator and 0.176g CuBr, 0.124g 2,2 ＇-di- pyrrole
Pyridine (bpy) is added in a flask equipped with stirring together, seals reaction flask, vacuumizes and be filled with nitrogen, is repeated 4 times；So
Afterwards, 35mL toluene and 12g methyl methacrylates (MMA) are introduced by syringe, is placed in 50 DEG C of oil bath and reacts 24h；Instead
After should terminating, polymerizate obtains functionalization graphene through acetone precipitation, distillation water washing, 60 DEG C of vacuum dryings.
(3) modified epoxy resin is prepared：
Specifically, first 0.4g functionalization graphenes can be dissolved in 600mL toluene, be configured to concentration for 0.667mg/
The solution of mL.Under condition of ice bath, ultrasound 4h in 40kHz ultrasonic waves, functionalization graphene is completely dispersed in the solution；Pour into epoxy
Resin 445g, in mechanical agitation 3.5h so that functionalization graphene is completely dispersed in the epoxy；It is placed on 55 DEG C of vacuum
Solvent is removed in drying box, room temperature is cooled to；Add curing agent to pour into mould to solidify, test the power of modified epoxy resin
Learn performance.When functionalization graphene content is 0.1wt.%, tensile toughness amplification is up to 189.2%, toughness amplification
Up to 73.8%；When functionalization graphene content is 0.2wt.%, tensile toughness amplification is up to 158.7%, toughness
Amplification is up to 72.1%.
In sum, in the inventive solutions, due to make use of the reaction between hydroxy groups and nucleopilic reagent to live
Property, the side base with ATRP active halogen atoms is introduced in the hydroxy position of graphene oxide, synthesize graphene oxide macromolecular
Initiator；Then trigger monomer that polymerisation occurs using ATRP, successfully polymeric long chain be grafted on graphene oxide,
Prepare functionalization graphene；Finally epoxy resin is spiked into functionalization graphene solution, is well mixed, prepared modified
Epoxy resin.Therefore, the epoxy resin toughened shock resistance that can be effectively improved epoxy resin of Graphene provided by the present invention
Toughness, simultaneously because the polymer long-chain of graphene oxide grafting can produce chemical bonding effect with epoxide group again, will not go out
Existing two phase structure, disperse uneven problem, influence the inherent characteristic of epoxy resin, it is to avoid the modified side of tradition such as physical modification
The drawbacks of method is brought.The present invention changes the rigid chain segment of epoxy resin into soft segment by MOLECULE DESIGN means, such that it is able to
Fundamentally improving the toughness of epoxy resin.For example, tough by using the modified epoxy resin shock resistance of the method for the present invention
Property improve 42%-86%.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Within god and principle, any modification, equivalent substitution and improvements done etc. should be included within the scope of protection of the invention.
Claims (23)
1. a kind of method of the toughening modifying of epoxy resin, it is characterised in that the method includes：
Using atom transition free radical polymerization reaction ATRP in the hydroxy position of Graphene graft polymers long-chain, prepare function
Graphite alkene；
Functionalization graphene is well mixed with epoxy resin, modified epoxy resin is obtained.
2. method according to claim 1, it is characterised in that the utilization ATRP is grafted in the hydroxy position of Graphene
Polymer long-chain, preparing functionalization graphene includes：
The side base with ATRP active halogen atoms is introduced in the hydroxy position of graphene oxide, synthesizes graphene oxide macromolecular
Initiator；
Trigger monomer that polymerisation occurs using ATRP, polymeric long chain is grafted on graphene oxide, prepare function
Graphite alkene.
3. method according to claim 2, it is characterised in that described to introduce band in the hydroxy position of graphene oxide
The side base of ATRP active halogen atoms, synthesis graphene oxide macromole evocating agent includes：
It is 0.6~2.1 according to the hydroxy functional group of graphene oxide and the mol ratio of halo nucleopilic reagent:1 or 0.5~2.0:1,
The hydroxy functional group of graphene oxide is 5.0~20.0 with the weight ratio of catalyst:1, by graphene oxide, halo nucleopilic reagent
In adding one equipped with the flask for stirring with catalyst, under inert gas shielding, it is placed in oil bath and reacts, obtains graphite oxide
Alkene macromole evocating agent.
4. method according to claim 3, it is characterised in that：
The halo nucleopilic reagent be on α-carbon it is active substitution base halogenated carboxylic acid class nucleopilic reagent or contain on α-carbon
There is the halogenated carboxylic acid class nucleopilic reagent of weak R-X keys；
Wherein, R is N, S or O, and X is Cl or Br.
5. method according to claim 4, it is characterised in that：
The active substituent is aryl, carbonyl or pi-allyl.
6. method according to claim 3, it is characterised in that：
The catalyst is that the reaction between hydroxy groups and carboxylic acids nucleopilic reagent to graphene oxide has catalytic action
Alkali compounds.
7. method according to claim 6, it is characterised in that：
The catalyst is NaOH, KOH or tetramethyl ammonium.
8. method according to claim 2, it is characterised in that：
The state of the graphene oxide is solution state.
9. method according to claim 2, it is characterised in that：
The graphene oxide is graphene oxide that degree of oxidation is 1%~60%.
10. the method according to claim 2,8 or 9, it is characterised in that：
The graphene oxide solution is fully dissolved by graphene oxide powder with the tetrahydrofuran or toluene as the first solvent
After be obtained.
11. methods according to claim 3, it is characterised in that the method is still further comprised：
Before halo nucleopilic reagent and catalyst is added, Na is used2CO3The pH value of the graphene oxide solution is adjusted to 7
~10.
12. methods according to claim 3, it is characterised in that：
The halo nucleopilic reagent is 2- bromo acids, 2 bromopropionic acid, to bromo methyl acid and in carboxylphenylsulphonyl chloride
At least one.
13. methods according to claim 2, it is characterised in that the method is still further comprised：
The functionalization graphene that will be prepared is cleaned with one or several of absolute ethyl alcohol, acetone or water, is repeated 4~8 times；And
It is vacuum dried at 40~80 DEG C.
14. methods according to claim 3, it is characterised in that the use ATRP triggers monomer that polymerisation occurs, will
Polymeric long chain is grafted on graphene oxide, and preparing functionalization graphene includes：
It is 1~1.5 according to the halogen atom in graphene oxide macromole evocating agent and ATRP catalyst, the mol ratio of ligand:1
~1.5:1~3, graphene oxide macromole evocating agent, ATRP catalyst and ligand are added to one equipped with stirring together
Flask in, tightly seal reaction flask, vacuumize and be filled with inert gas, repeat 2~4 times；Then, the is added with syringe
Two solvents and monomer, are placed in oil bath and react, and system occurs ATRP reactions under solution state；After reaction terminates, polymerizate
Through precipitation, washing and vacuum drying, functionalization graphene is obtained.
15. methods according to claim 14, it is characterised in that：
The ATRP catalyst is CuX, FeX2、CuX2Or FeX3；
Wherein, X is Cl or the type of Br, X is consistent with the type of halogen atom in halo nucleopilic reagent.
16. methods according to claim 15, it is characterised in that：
The ligand is one or more ligand containing N- or P-, is coordinated on transition metal with σ-key or π-key.
17. methods according to claim 15, it is characterised in that：
The ligand be 2,2 ＇-bipyridine (bpy), 4,4 ＇-two (five-nonyl) -2,2 ＇-bipyridine (dNbpy), 4,
4 ＇-the ＇ of di-n-butyl-2,2-bipyridine (dTbpy), N, N, N ＇, N ＇ ＇, N ＇ ＇-five methyl diethylentriamine (PMDETA), three
One or more in Phenylphosphine (TPP) or tributylphosphine (TBUP) of mixture.
18. methods according to claim 14, it is characterised in that：
The monomer is methyl methacrylate, methacrylic acid or GMA.
19. methods according to claim 14, it is characterised in that：
Second solvent is the organic solvent that can dissolve graphene oxide macromole evocating agent.
20. methods according to claim 14, it is characterised in that：
Second solvent is toluene, tetrahydrofuran or acetone.
21. methods according to claim 1, it is characterised in that described to mix functionalization graphene with epoxy resin
Even, obtaining modified epoxy resin includes：
By functionalization graphene be dissolved in tetrahydrofuran, acetone or toluene one or several in, be configured to solution；In ice bath bar
Under part, it is allowed to be completely dispersed by ultrasound in ultrasonic wave；Epoxy resin is added in the solution, by mechanical agitation so that functionalization
Graphene is completely dispersed in the epoxy；It is placed in again in vacuum drying chamber and is vacuum dried, obtains modified epoxy resin.
22. methods according to claim 21, it is characterised in that：
The state of the functionalization graphene is solution state.
23. methods according to claim 1, it is characterised in that：
The functionalization graphene is in surface of graphene oxide grafted methacrylic acid methyl esters, methacrylic acid or metering system
Acid glycidyl ester.
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