CN108059798A - A kind of graphene light curable conductive resin and preparation method thereof - Google Patents
A kind of graphene light curable conductive resin and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of graphene light curable conductive resin and preparation method thereof, and wherein graphene light-cured resin includes the ingredient of following weight proportion：50~80 parts of epoxy resin, 50~60 parts of methacrylic acid, 2~6 parts of amino-polyethyleneglycols, 4~6 parts of graphene, 10~15 parts of doped polyaniline, 2~4 parts of isocyanates, 3~6 parts of tarine sodium, 1~4 part of adipic acid, 3~8 parts of reactive diluent, 0.5~1 part of catalyst, 0.5~0.8 part of polymerization inhibitor, 0.8~1.4 part of antioxidant, 40~60 parts of solvent.The present invention also provides the preparation methods of graphene light curable conductive resin, the graphene light curable conductive resin prepared by above-mentioned formula and preparation method, solve the problems, such as that graphene and doped polyaniline are easily reunited, conductive energy is outstanding, the advantages of electric conductivity is evenly distributed, suitable for technical fields such as coating, bonding agents, have wide range of applications.
Description
Technical field
The present invention relates to light curable conductive resin technology field, more particularly to a kind of graphene light curable conductive resin and its
Preparation method.
Background technology
Electroconductive resin is the macromolecule resin polymer with certain electric conductivity, is mainly used in conductive adhesive
In conductive coating paint.Wherein bonding agent is widely used in conducting wire bonding with electrode, bonding of semiconductor element, electromagnetism wave screen
Cover bonding of functional component etc..Electroconductive resin is used in coating generally require the solvent of addition low viscosity, has transmission electric current
Effect with accumulation electrostatic charge is excluded, is widely used in the functions such as anticorrosion, radiation protection, antistatic, invisible coating, conductive film
Field.
Light-cured resin can occur rapidly physics and chemistry becomes in the short period of time after ultraviolet light is subject to
Change, and then crosslinking curing, it is a kind of relatively low photoresist of relative molecular mass, has the reactivity that can carry out photocuring
Group, such as unsaturated both shoulders or epoxy group.Light-cured resin is primarily applicable for photocureable coating, as photocureable coating
It may make up photocureable coating, photocureable coating tool after matrix resin, with photoinitiator, reactive diluent and various additive compounds
There is the advantages of curing rate is fast, organic volatile matter is few, has wide range of applications.
Graphene is the tightly packed single layer of carbon atom into two-dimentional six side's honeycomb crystal lattice structures, between each carbon atom with
sp2Hybrid form is connected.On microcosmic, single-layer graphene film is not the flat structure of two dimension, but with " on nanoscale "
The single layer structure of stable wavy is presently found unique existing Two Dimensional Free state atomic crystal；Macroscopically, graphene
The fullerene of zero dimension can be warped into, be rolled into one-dimensional carbon nanotubes or is stacked to three-dimensional graphite.The two of graphene uniqueness
The presence for the carbon hexatomic ring stablized in cycle honeycomb lattice structure is tieed up, imparts its excellent performance：The thickness of single-layer graphene
Degree is only 0.35nm, is to be currently known most light most thin material；Its electron mobility at room temperature is 2 × 105cm2·V-1·
s-1, it is the 1/300 of the light velocity, theoretical specific surface area can reach 2630m2·g-1, all band light absorption only has 2.3%, thermal conductivity
Up to 5000Wm-1·K-1, Young's modulus is more than 1100GPa, and tensile strength is more than 130GPa, and toughness is very good, works as application
During external mechanical force, carbon atom can be bent and deformed to adapt to external force, without rearranging carbon atom, so be maintained for
The stabilization of structure.Therefore, graphene is a kind of very extensive carbon material of application potential, novel reaction separation, new material,
There is huge application prospect in numerous industries such as energy conservation and environmental protection.
Wherein, electroconductive resin is usually that conducting particles is distributed to height by the even action of covalent bond or non-covalent bond
In polymeric systems, make between conducting particles that mutually touching forms conductive network after high polymer curing, therefore, conducting particles is mixed
It is miscellaneous into light-cured resin, corresponding electric conductivity light-cured resin can be obtained.
Polyaniline is a kind of typical high molecular material, has special electricity, optical property after doped, has excellent
Electric conductivity.Existing electrically conductive polyaniline is generally the polyaniline using protonic acid doping, but its dissolution rate in a solvent
It is extremely low, and be oxidized easily, dedoping occurs, surface resistivity is made gradually to increase in the solidification process of coating, and it is doped poly-
Aniline is easily reunited in resin matrix, is made resin that can not form uniform conductive network after hardening, is reduced resin
The binding ability of electric conductivity and resin and matrix.Meanwhile graphene is being set as the nano-particle with superior electrical conductivity energy
Equally easily reunite in aliphatic radical body, when graphene and doped polyaniline are added in into resin matrix together, itself
Physical property can form it into more serious agglomeration, greatly influence the electric conductivity of resin.
The content of the invention
It is added in solve graphene in the prior art mentioned above with doped polyaniline to light-cured resin
The problem of more serious agglomeration occurred in matrix, the present invention provides a kind of graphene light curable conductive resin and its
Preparation method, graphene light curable conductive resin provided by the invention add graphene and doping in photocuring matrix resin
State polyaniline solves the problems, such as that graphene and doped polyaniline are easily reunited in resin, has outstanding electric conductivity, can
Suitable for multiple fields such as coating, bonding agents.
The present invention adopts the following technical scheme that：
A kind of graphene light curable conductive resin includes the ingredient of following weight proportion：
Further, the graphene light curable conductive resin includes the ingredient of following weight proportion：
Further, the epoxy resin for bisphenol A type epoxy resin, novolac epoxy resin, aliphatic epoxy resin or
One or more mixing in cycloaliphatic epoxy resin.
Further, the isocyanates is hexamethylene diisocyanate, isophorone diisocyanate and two hexamethylenes
One kind in dicyclohexylmethane diisocyanate.
Further, the catalyst is N, in N- dimethyl benzylamines, tetraethylammonium bromide and trimethyl benzyl ammonia chloride
One kind.
Further, the polymerization inhibitor is in p-hydroxyanisole, hydroquinone and 2,6- toluene di-tert-butyl phenol
It is a kind of.
Further, the antioxidant is in two different certain herbaceous plants with big flowers ester of Wytox 312 and diphosphites pentaerythrite
One kind.
Further, the solvent is n,N-Dimethylformamide, the one or more in ethyl acetate, butyl acetate are mixed
It closes.
Further, the reactive diluent be polyfunctional acrylic ester, selected from tri (propylene glycol) diacrylate,
One or more in trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, pentaerythritol triacrylate
Mixing.
The present invention also provides a kind of preparation methods of graphene light curable conductive resin, comprise the following steps：
Step 1：Epoxy resin is placed in reaction vessel, controlled at 90 DEG C~100 DEG C, using 500 turns of rotating speed/
The speed of min~600 turn/min is stirred, and methacrylic acid and the poly- second of part amino are added dropwise in 40min~50min
The mixture of glycol；
Step 2：On the basis of step 1, adipic acid, catalyst, polymerization inhibitor are added dropwise in 20min~25min
With the mixture of antioxidant, after being stirred to react 80min~90min, 110 DEG C~120 DEG C are warming up to, adds in reactive diluent, after
It is continuous to be stirred to react 25min~35min, stop stirring, be cooled to 75 DEG C~80 DEG C；
Step 3: by graphene dispersion in partial solvent, stirred with the speed of 1000 turns/min~1500 turn/min
After 30min~35min, ultrasonic vibration 20min~25min；
Step 4：On the basis of step 3, the solution for being dispersed with graphene is transferred in stirring container, 500 turns/
Under the stirring condition of min~800 turn/min, part amino-polyethyleneglycols are added in, after being warming up to 70 DEG C~80 DEG C, add in amino second
Sodium sulfonate and doped polyaniline continue after stirring 20min~25min, be warming up to 130 DEG C~160 DEG C constant temperature reflux 90min~
120min, cold filtration wash drying；
Step 5: the product that step 2 and step 4 are obtained is blended in partial solvent, isocyanates is added in, is warming up to
80 DEG C~90 DEG C, after speed stirring 80min~100min of 600 turns/min~700 turn/min, you can obtain the graphene
Light curable conductive resin.
Graphene light curable conductive resin provided by the invention carries out the preparation of epoxy acrylate in preparation process
It improves, reduces the viscosity of epoxy acrylate, improve toughness and intensity after curing, while make epoxy acrylate
Segment spacing increases, convenient for inserting for follow-up graphene and doped polyaniline.The doped polyaniline that the present invention uses is matter
The polyaniline of sub- acid doping, when Bronsted acid polyaniline is used to be doped, Hydrogen Proton is transferred on strand, generates charged member
Excitation state polaron, the quinone ring of intramolecular disappear, electronics member redistribution, the positive charge delocalization on N atoms to big conjugatedπbond
In, make high conductivity at polyaniline presentation.
When handling graphene and doped polyaniline, appropriate amino-polyethyleneglycols are first added in graphene dispersing solution,
In a heated condition amino-polyethyleneglycols is made to uniformly disperse into graphene dispersing solution, iris action is played to graphene, at this time
Graphene agglomeration unobvious after sonic oscillation, add tarine sodium and doped polyaniline, improve temperature into
Row reaction, makes doped polyaniline be covered on graphene particle, forms the interlayer structure of polyaniline-graphite alkene-polyaniline, simultaneously
Amino-polyethyleneglycols generate conjugation with the benzene ring units on polyaniline chain segments, and amino-polyethyleneglycols is made to become barrier material, solve
The problem of doped polyaniline is easy to reunite.Wherein, the preferred N of tarine sodium, N- bis- (2- ethoxys) -2- amino second sulphurs
Sour sodium.
In addition, graphene and doped polyaniline mixture after treatment is being inserted to epoxy acrylate
In after, since the electron cloud on amino-polyethyleneglycols is pullled by the benzene ring units on polyaniline chain segments, polarity increase, with epoxy third
The binding ability of olefin(e) acid ester gets a promotion, and further avoids agglomeration traits.The combination of graphene and doped polyaniline makes tree
Fat possesses outstanding electric conductivity, while is dispersed in the densely covered conductive network formed in resin, also ensures resin
Electric conductivity stability.
A kind of graphene light curable conductive resin provided by the invention and preparation method thereof, by treated graphene and
Doped polyaniline is added in into epoxy acrylate, forms uniformly densely covered conductive network, and resin is made to have excellent conduction
Performance, is applicable to the technical fields such as coating, bonding agent, and application range is very extensive.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme is clearly and completely described, it is clear that described embodiment is that a part of the invention is implemented
Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creativeness
All other embodiments obtained under the premise of work, belong to the scope of protection of the invention.
Embodiment provided by the invention is shown in Table 1：
Table 1
Specific preparation method is as follows：
Embodiment 1：
Step 1：62 parts of epoxy resin are placed in reaction vessel, controlled at 90 DEG C, use 550 turns/min of rotating speed
Speed be stirred, the mixture of 53 parts of methacrylic acids and 1.8 parts of amino-polyethyleneglycols is added dropwise in 45min；
Step 2：On the basis of step 1,1 part of adipic acid, 0.53 part of catalyst, 0.55 are added dropwise in 25min
The mixture of part polymerization inhibitor and 0.87 part of antioxidant after being stirred to react 90min, is warming up to 120 DEG C, adds in 5.6 parts of activity dilutions
Agent continues to be stirred to react 30min, stops stirring, be cooled to 75 DEG C；
Step 3: by 4.5 parts of graphene dispersions in 20 parts of solvents, after the speed stirring 35min of 1200 turns/min, surpass
25min is swung in acoustic shock；
Step 4：On the basis of step 3, the solution for being dispersed with graphene is transferred in stirring container, 700 turns/
Under the stirring condition of min, 1.2 parts of amino-polyethyleneglycols are added in, after being warming up to 70 DEG C, add in 4.5 parts of tarine sodium and 12
Part protonic acid doping state polyaniline continues after stirring 25min, is warming up to 150 DEG C of constant temperature reflux 100min, cold filtration, washing
It is dry；
Step 5: the product that step 2 and step 4 are obtained is blended in 23 parts of solvents, 2.8 parts of isocyanates are added in,
90 DEG C are warming up to, after the speed stirring 100min of 650 turns/min, you can obtain the graphene light curable conductive resin.
Embodiment 2：
Step 1：65 parts of epoxy resin are placed in reaction vessel, controlled at 90 DEG C, use 550 turns/min of rotating speed
Speed be stirred, the mixture of 55 parts of methacrylic acids and 1.8 parts of amino-polyethyleneglycols is added dropwise in 45min；
Step 2：On the basis of step 1,1 part of adipic acid, 0.55 part of catalyst, 0.58 are added dropwise in 25min
The mixture of part polymerization inhibitor and 0.91 part of antioxidant after being stirred to react 90min, is warming up to 120 DEG C, adds in 6.8 parts of activity dilutions
Agent continues to be stirred to react 30min, stops stirring, be cooled to 75 DEG C；
Step 3: by 5 parts of graphene dispersions in 20 parts of solvents, after the speed stirring 35min of 1200 turns/min, ultrasound
Shake 25min；
Step 4：On the basis of step 3, the solution for being dispersed with graphene is transferred in stirring container, 700 turns/
Under the stirring condition of min, 2.2 parts of amino-polyethyleneglycols are added in, after being warming up to 70 DEG C, add in 5.1 parts of tarine sodium and 13
Part protonic acid doping state polyaniline continues after stirring 25min, is warming up to 150 DEG C of constant temperature reflux 100min, cold filtration, washing
It is dry；
Step 5: the product that step 2 and step 4 are obtained is blended in 24 parts of solvents, 3.3 parts of isocyanates are added in,
90 DEG C are warming up to, after the speed stirring 100min of 650 turns/min, you can obtain the graphene light curable conductive resin.
Embodiment 3：
Step 1：68 parts of epoxy resin are placed in reaction vessel, controlled at 90 DEG C, use 550 turns/min of rotating speed
Speed be stirred, the mixture of 58 parts of methacrylic acids and 1.6 parts of amino-polyethyleneglycols is added dropwise in 45min；
Step 2：On the basis of step 1, be added dropwise in 25min 1.5 parts of adipic acids, 0.58 part of catalyst,
The mixture of 0.59 part of polymerization inhibitor and 0.96 part of antioxidant after being stirred to react 90min, is warming up to 120 DEG C, adds in 7.3 parts of activity
Diluent continues to be stirred to react 30min, stops stirring, be cooled to 75 DEG C；
Step 3: by 5.5 parts of graphene dispersions in 20 parts of solvents, after the speed stirring 35min of 1200 turns/min, surpass
25min is swung in acoustic shock；
Step 4：On the basis of step 3, the solution for being dispersed with graphene is transferred in stirring container, 700 turns/
Under the stirring condition of min, 3.4 parts of amino-polyethyleneglycols are added in, after being warming up to 70 DEG C, add in 5.7 parts of tarine sodium and 14
Part protonic acid doping state polyaniline continues after stirring 25min, is warming up to 150 DEG C of constant temperature reflux 100min, cold filtration, washing
It is dry；
Step 5: the product that step 2 and step 4 are obtained is blended in 25 parts of solvents, 3.8 parts of isocyanates are added in,
90 DEG C are warming up to, after the speed stirring 100min of 650 turns/min, you can obtain the graphene light curable conductive resin.
To detect a kind of performance of the practical application of graphene light curable conductive resin provided by the invention, inventor devises
Multigroup check experiment, specific testing program are as follows：
Comparative example 1：Common commercially available light curable conductive resin；
Comparative example 2：It is added in common commercially available light curable conductive resin identical with 1 model of embodiment, dosage doped
Polyaniline and graphene, specific preparation method are：Graphene and doped polyaniline are dispersed in solvent N, N- dimethyl formyl
In amine, mixing is stirred using the rate of 800 turns/min, the product of comparative example 2 is obtained by filtration；
Test procedure：
1. the light curable conductive resin of embodiment 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2 is coated in substrate
On, cured using ultraviolet light, produce the tabular sample of 10cmx10cmx2cm；
2. tabular sample is cut into the rod-like samples of 2cmx10cmx2cm；
3. the volume resistance of rod-like samples is measured.
Result of the test is as shown in table 2：
Table 2
By the comparison of the volumetric resistivity value to embodiment 1, embodiment 2, embodiment 3 and comparative example 1, it can be found that this hair
The electric conductivity of the graphene light curable conductive resin of bright offer is more outstanding.While from
Embodiment 1, embodiment 2, the test result of more than 3 a sample of embodiment, which compare, to be understood, graphene provided by the invention
The volume resistance numeric distribution of light curable conductive resin is uniform, illustrates that graphene is being set with doped polyaniline as conductive filler
It is uniformly distributed in fat, agglomeration does not occur, and in comparative example 2, there is the situation that volume resistance is unevenly distributed, in sample
4 and sample 5 in there is more outstanding electric conductivity, and the electric conductivity of sample 1, sample 2 and sample 3 is poor, this be by
Although in being with the addition of graphene and doped polyaniline in comparative example 2, due to not according to method provided by the invention into
Row processing, causes graphene and doped polyaniline that agglomeration has occurred in the resin matrix of comparative example 2, is used in enhancing
The graphene and doped polyaniline of electric conductivity are gathered in some positions, so as to the situation that electric conductivity is unevenly distributed occur.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe is described in detail the present invention with reference to foregoing embodiments, it will be understood by those of ordinary skill in the art that：Its according to
Can so modify to the technical solution recorded in foregoing embodiments either to which part or all technical characteristic into
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is not made to depart from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
1. a kind of graphene light curable conductive resin, it is characterised in that：The graphene light curable conductive resin includes following heavy
Measure the ingredient of proportioning：
2. a kind of graphene light curable conductive resin according to claim 1, it is characterised in that：The graphene photocuring
Electroconductive resin includes the ingredient of following weight proportion：
3. a kind of graphene light curable conductive resin according to claim 1 or 2, it is characterised in that：The epoxy resin
It is mixed for the one or more in bisphenol A type epoxy resin, novolac epoxy resin, aliphatic epoxy resin or cycloaliphatic epoxy resin
It closes.
4. a kind of graphene light curable conductive resin according to claim 1 or 2, it is characterised in that：The isocyanates
For one kind in hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexyl methyl hydride diisocyanate.
5. a kind of graphene light curable conductive resin according to claim 1 or 2, it is characterised in that：The catalyst is
One kind in N, N- dimethyl benzylamine, tetraethylammonium bromide and trimethyl benzyl ammonia chloride.
6. a kind of graphene light curable conductive resin according to claim 1 or 2, it is characterised in that：The polymerization inhibitor is
One kind in p-hydroxyanisole, hydroquinone and 2,6- toluene di-tert-butyl phenols.
7. a kind of graphene light curable conductive resin according to claim 1 or 2, it is characterised in that：The antioxidant is
One kind in two different certain herbaceous plants with big flowers ester of Wytox 312 and diphosphites pentaerythrite.
8. a kind of graphene light curable conductive resin according to claim 1 or 2, it is characterised in that：The solvent is N,
One or more mixing in dinethylformamide, ethyl acetate, butyl acetate.
9. a kind of graphene light curable conductive resin according to claim 1 or 2, it is characterised in that：The activity dilution
Agent is polyfunctional acrylic ester, selected from tri (propylene glycol) diacrylate, trimethylolpropane trimethacrylate, three contractings third
One or more mixing in omega-diol diacrylate, pentaerythritol triacrylate.
10. a kind of preparation method of graphene light curable conductive resin as claimed in claim 1 or 2, which is characterized in that including
Following steps：
Step 1：Epoxy resin is placed in reaction vessel, controlled at 90 DEG C~100 DEG C, uses 500 turns/mi of rotating speed n
The speed of~600 turns/mi n is stirred, and methacrylic acid and the poly- second of part amino are added dropwise in 40mi n~50mi n
The mixture of glycol；
Step 2：On the basis of step 1, be added dropwise in 20mi n~25mi n adipic acid, catalyst, polymerization inhibitor and
The mixture of antioxidant after being stirred to react 80mi n~90mi n, is warming up to 110 DEG C~120 DEG C, adds in reactive diluent, after
It is continuous to be stirred to react 25mi n~35mi n, stop stirring, be cooled to 75 DEG C~80 DEG C；
Step 3: by graphene dispersion in partial solvent, 30mi is stirred with the speed of 1000 turns/mi n~1500 turn/mi n
After n~35mi n, ultrasonic vibration 20mi n~25mi n；
Step 4：On the basis of step 3, the solution for being dispersed with graphene is transferred in stirring container, 500 turns/mi n~
Under the stirring condition of 800 turns/mi n, part amino-polyethyleneglycols are added in, after being warming up to 70 DEG C~80 DEG C, add in tarine
Sodium and doped polyaniline continue after stirring 20mi n~25mi n, be warming up to 130 DEG C~160 DEG C constant temperature reflux 90mi n~
120mi n, cold filtration wash drying；
Step 5: the product that step 2 and step 4 are obtained is blended in partial solvent, isocyanates is added in, is warming up to 80 DEG C
~90 DEG C, after speed stirring 80mi n~100mi n of 600 turns/mi n~700 turn/mi n, you can obtain the graphene
Light curable conductive resin.
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| CN201810766203.XA CN108912972B (en) | 2018-01-11 | 2018-07-12 | Graphene photocuring conductive resin and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004812A (en) * | 2021-03-30 | 2021-06-22 | 刘新宽 | Graphene modified resin packaging material and preparation method thereof |
| CN113845754A (en) * | 2021-09-30 | 2021-12-28 | 广东博汇新材料科技股份有限公司 | Preparation method of epoxy resin electronic and electric insulating material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101397256B1 (en) * | 2013-02-28 | 2014-05-20 | 포항공과대학교 산학협력단 | Conductive thin films and electronic devices comprising the same |
| CN104592857A (en) * | 2014-12-30 | 2015-05-06 | 安科智慧城市技术（中国）有限公司 | Graphene modified polyaniline conductive coating and preparation method thereof |
| CN104910752B (en) * | 2015-06-10 | 2017-08-25 | 华南理工大学 | A kind of polyaniline graphene nano composite anticorrosion coating and preparation method thereof |
| CN105176310B (en) * | 2015-10-14 | 2017-06-27 | 南昌航空大学 | A kind of preparation method of the conductive anti-corrosion coating of modified graphene |
| CN106832921A (en) * | 2017-03-25 | 2017-06-13 | 山东本源晶体科技有限公司 | A kind of preparation method of ionic liquid doped polymer conductive graphene material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004812A (en) * | 2021-03-30 | 2021-06-22 | 刘新宽 | Graphene modified resin packaging material and preparation method thereof |
| CN113845754A (en) * | 2021-09-30 | 2021-12-28 | 广东博汇新材料科技股份有限公司 | Preparation method of epoxy resin electronic and electric insulating material |
| CN113845754B (en) * | 2021-09-30 | 2022-07-08 | 广东博汇新材料科技有限公司 | Preparation method of epoxy resin electronic and electric insulating material |
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| CN108912972B (en) | 2020-05-22 |
| CN108912972A (en) | 2018-11-30 |
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