CN106832220A - A kind of preparation of epoxy acrylate of Graphene graft modification and its application in photocureable coating - Google Patents
A kind of preparation of epoxy acrylate of Graphene graft modification and its application in photocureable coating Download PDFInfo
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- CN106832220A CN106832220A CN201611259655.6A CN201611259655A CN106832220A CN 106832220 A CN106832220 A CN 106832220A CN 201611259655 A CN201611259655 A CN 201611259655A CN 106832220 A CN106832220 A CN 106832220A
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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
- C08G59/14—Polycondensates modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Abstract
The invention discloses a kind of preparation method of the epoxy acrylate of Graphene graft modification; reacted with the acrylate containing active group, acid binding agent again after graphene oxide and acylation reaction; it is last again with epoxy resin copolymerization, the epoxy acrylate of Graphene graft modification is obtained.Additionally, the application of the epoxy acrylate the invention also discloses Graphene graft modification, and it is added with the polymer-modified photocureable coating.The present invention is by acylating agent by graphene oxide and acrylate in situ bonding; then again with epoxy resin copolymerization; in making graphene oxide in situ bonding to polymer; both there is good dispersion to help emulsification effect; there is the incomparable dispersion stabilization of physical blending again, the properties for being added with the polymer-modified coating of the Graphene can be obviously improved.
Description
Technical field
The invention belongs to epoxy acrylate coating technical field, and in particular to a kind of epoxy third of Graphene graft modification
The preparation method of olefin(e) acid ester, and it is added with the photocureable coating of described modified epoxy acrylate.
Background technology
Used as a kind of maximum UV photocuring corrosion resistant coating matrix resins of consumption, it has bisphenol A epoxy acrylate
Corrosion Protection is excellent and quick-setting advantage, and its mechanical property preferably, thus is widely used in many industrial circles in addition.
But bisphenol A epoxy acrylate coating products viscosity is very high, light aging resisting and yellowing resistance are poor, and the crosslinking of its solidfied material is close
Degree is big, as a result causes toughness poor, is susceptible to the disengaging of coating and substrate, largely reduces the comprehensive of it
Energy[1,2]。
Graphene with two-dimensional structure, can be in corrosive gas, liquid or high because of the heterocycle structure of its stabilization
Stabilization is kept under warm environment.Although the excellent performance of Graphene, because the graphene oxide of oxidation-reduction method preparation is molten
There are π-π to stack tendency in agent and be agglomerated into the phenomenon of bulky grain graphite oxide, so that it cannot enough long-time stables be dispersed in water with
And in polar organic solvent.This agglomeration seriously hinders Graphene in electronic device, coating system and composite
In application.
At present, the research for improving bisphenol A epoxy acrylate coating property using inorganic material has been developed rapidly, but
Using Graphene, this star's material modification bisphenol A epoxy acrylate is still less.Among these, on Graphene modified bisphenol
The report of A epoxy acrylates is mostly using blending or the method for solution intercalation method.Blending modification method can actually be by graphite
The mechanical performance of alkene material and the corrosion resistance of bisphenol A epoxy acrylate coating, rapidly-curable are combined well, play association
With the effect of effect, but blending modification method dispersiveness is poor, and Graphene can not be uniformly dispersed in bisphenol-A epoxy acrylic acid
In ester.Dispersiveness of the Graphene in epoxy acrylate be not good, easily reunites, and the graphene-based epoxy acrylate for obtaining is applied
The overall performance of material is unsatisfactory.Wei and partner prepare by graphene oxide and epoxy acrylic ester prepolymer are compound
GO/EA, prepared product tensile strength improves 8.39%, and bending modulus have dropped 46.79%[3].In this work
In, graphene oxide is mixed with Epoxy Acrylates in the way of being blended, and causes last composite homogeneity still
Cannot ensure.
[1] Zhang j y, Windall g, Boyd i w.UV curing of optical fiber coatings
Using excimer lamps [J] .Applied Surface Science, 2002,186 (1-4)：568-572.
[2] Sun Xingping, Wang De sea epoxy acrylics Lipase absobed and progress [J] coatings industries of application, 2007,37
(11)：53-57.
[3] the modified UV of Wei Yanyan, Wang Hu Graphenes solidifies research [J] coating of bisphenol-A epoxy acrylic resin performance
Industry, 2016,46 (6)：12-27.
The content of the invention：
Material after easily reuniting, adulterate for the method generally existing for solving existing Graphene doping vario-property epoxy acrylate
The material technical problem such as performance is undesirable, the invention provides a kind of preparation side of the epoxy acrylate of Graphene graft modification
Method, it is intended to avoid Graphene from reuniting, the performance of the material after lifting doping.
Present invention also offers the application of the epoxy acrylate of described Graphene graft modification.
Additionally, present invention additionally comprises the painting of the epoxy acrylate for being added with Graphene graft modification of the present invention
Material, it is intended to lift the performances such as impact resistance, adhesive force, the abrasion resisting of coating.
A kind of preparation method of the epoxy acrylate of Graphene graft modification, comprises the following steps：
Step (1)：Graphene oxide and acylation reaction, are obtained acylated graphene oxide；
Step (2)：Acylated graphene oxide, the acrylate containing active group, acid binding agent reaction, prepared Graphene are changed
Property acrylate；
Step (3)：Again by Graphene modification acrylate, epoxy resin copolymerization, the epoxy of Graphene graft modification is obtained
Acrylate.
In the present invention, it is esterified by the hydroxyl of acylating agent and graphene oxide, carboxyl isoreactivity group, so as in oxidation stone
Black alkene surface bond is modified with acylated active group (acylated graphene oxide)；Then again under the catalysis of acid binding agent, Graphene
The acylated active group of surface modification and the acrylate reactions containing active group, so that graphene oxide is answered with acrylate
Close, prepared in situ bonding has the double bond compound (Graphene modification acrylate) of graphene oxide；Oxidation stone will be bonded with again
The acrylate of black alkene and epoxy resin copolymerization, make graphene oxide original position, main polymer chain are uniformly bonded to, so that can be effective
Avoid the reunion of graphene oxide；Effectively lifting is added with the performance of the modified epoxy acrylic ester coating.In the present invention, make
With polymerizable Graphene (Graphene modification acrylate), emulsification effect both was helped with good dispersion, but it is common with physics
Mixed incomparable dispersion stabilization so that especially adhesive force obtains very big to epoxy acrylate photocureable coating mechanical performance
Raising.
In the present invention, described acylating agent can be with the active group of surface of graphene oxide such as hydroxyl, carboxyl isoreactivity
Radical reaction, so that surface of graphene oxide modifies active acylate group, described acylate group is, for example, acid halide group
Group, sulfonyl halide groups, sulfenyl halogen group, phosphoryl halogen group etc.；More preferably acid chloride groups, sulfonic acid chloride group, sub- sulphur
Acid chloride groups, phosphinylidyne cl radical etc..
Preferably, described acylating agent is at least one in thionyl chloride, phosphorus trichloride, phosphorus pentachloride.
Further preferably, described acylating agent is thionyl chloride.
In the present invention, described graphene oxide can be obtained by improved Hummers methods.
In the present invention, with Hummers methods prepare graphene oxide be divided into three steps, i.e. low-temp reaction stage (0-5 DEG C), in
The warm stage of reaction (35-40 DEG C) and pyroreaction stage (90-95 DEG C).Also to be washed and be post-processed after having reacted and just be obtained
Desired product.
In the present invention, the preparation process of graphene oxide is preferably：
Step (a)：The low-temp reaction stage：2.0-2.5 weight portions natural flake graphite (particle diameter 0.1um) and 1-1.25 weight
Part sodium nitrate NaNO3The 500ml there-necked flasks being placed in ice bath environment are added to, 55.2-110.4 is added during being slowly stirred
The weight portion concentrated sulfuric acid (95%-98%), 6-7.5 weight portion potassium permanganate KMnO is dividedly in some parts after insulation 30-40min4, about very
Clock continues ice bath insulation 1-2h after adding；
Step (b)：The middle temperature stage of reaction：System is transferred in 30-35 DEG C of constant temperature water bath apparatus, 3-6h is incubated；Use constant pressure
Funnel is slowly added dropwise deionized water to reaction system；
Step (c)：The pyroreaction stage：It is rapid that bath temperature is increased to 80-95 DEG C, it is incubated one hour；Afterwards with perseverance
Pressure funnel is added dropwise deionized water and continues to accelerate mixing speed, continues that deionized water is added dropwise again after stirring 5-10min；Completion of dropping
Then it is slowly added into hydrogen peroxide (>=30%) afterwards；
Step (d)：Washing and post processing：Rear direct filter paper suction filtration while hot is reacted, suction filtration filters brown color after finishing
Cake is transferred in beaker；The hydrochloric acid that concentrated hydrochloric acid is diluted is added in beaker, continues to take out after 80-95 DEG C of stir about half an hour of insulation
Filter, continues the suction filtration that adds water, untill suction filtration does not get off after draining；Product on filter cake is transferred in 500ml beakers；By beaker
Middle product low speed centrifuge is in 3500-5000r/min, 10-15min/ centrifuge washing, until test centrifuge tube upper liquid pH
Value is no longer reduced；Centrifuge tube lower floor thing is transferred in surface plate, is placed in 50-60 DEG C of vacuum drying chamber and is dried until completely dry
It is dry；By dried graphite oxide grind into powder.
In step (1), acylating agent is with respect to graphene oxide excess, preferably, acylating agent adds volume with oxidation stone
Black alkene weight ratio is 0.07~0.15mL/g.
Preferably, in step (1), thionyl chloride add volume and graphene oxide weight ratio be 0.07~
0.15mL/g。
Preferably, in step (1), reaction temperature is 60-70 DEG C, and the reaction time is 19-24h.
After the acylation reaction of step (1) terminates, remaining thionyl chloride is removed under reduced pressure；Product through chloroform wash after again
It is dispersed in standby in chloroform soln.
By obtained acylated graphene oxide ultrasonic disperse in chloroform, it is 0.5-1mg/ml's that preparation obtains concentration
Dispersion liquid.
Preferably, ultrasonic time is 1~3h.
In the present invention, described acid binding agent is well known to those skilled in the art can for example may be used with the compound of acid reaction
It is the compound with tertiary ammonia, inorganic base etc..
Preferably, described acid binding agent is pyridine and/or triethylamine.
Further preferably, described acid binding agent is pyridine.
In the present invention, the described acrylate containing active group be containing can with acylate group react with active hydrogen
Acrylate；Preferably, the described acrylate containing active group is the acrylic acid containing hydroxyl and/or primary amino radical
Ester.
In step (2), will acylated graphene oxide obtained in step (1) under the catalysis of acid binding agent, and containing active group
Acrylate be esterified or amidation process, Graphene modification acrylate is obtained.
For example, the active group that the described acrylate containing active group is included is OH, by OH and acylate group
Esterification is carried out, by the form of ester bond by graphene oxide and acrylate compound；For another example, it is described containing active group
The active group that acrylate is included is NH2, and amidation process is carried out by NH2 and acylate group, by amido link by oxygen
Graphite alkene and acrylate compound.
Further preferably, in step (2), by acylated graphene oxide obtained in step (1) under the catalysis of acid binding agent, with
Acrylate containing active group carries out alcoholic extract hydroxyl group and is reacted with acid chloride groups, and Graphene modification acrylate is obtained.
Further preferably, the described acrylate containing active group is the compound with the structure of formula 1：
In formula 1, Y is the alkyl of C1~5；R is H or methyl.
Described Y is the side chain or straight-chain alkyl of C1~5.
Still more preferably, the described acrylate containing active group is (methyl) hydroxy-ethyl acrylate, (methyl) third
At least one in olefin(e) acid hydroxypropyl acrylate, (methyl) acrylic acid hydroxyl N-butyl.
Most preferably, the described acrylate containing active group is hydroxyethyl methacrylate.
Preferably, in step (2), acylated graphene oxide and the acrylate containing active group are in the temperature less than 2 DEG C
Degree is lower to be added dropwise excessive acid binding agent；Room temperature is warming up to after being added dropwise to complete, continues to react 1~3h.After reaction terminates, washed with distillation
Wash, dry prepared Graphene modification acrylate.
In step (3), epoxy resin is dissolved in reactive diluent, then add step (2) obtained in Graphene change
Property acrylate, catalyst and polymerization inhibitor and at 115 DEG C -135 DEG C copolymerization the epoxy third of the Graphene graft modification is obtained
Olefin(e) acid ester.
Preferably, in step (3), the acid number of polymerization process control system is less than 4.5-5mg KOH/g.
Preferably, in step (3), described catalyst is N, N- dimethyl benzylamines, triphenylphosphine, tetraethylammonium bromide
In at least one.
Preferably, in step (3), described polymerization inhibitor is hydroquinones, 2,5- di-tert-butyl hydroquinones, to hydroxyl
At least one in methyl phenyl ethers anisole.
Preferably, in step (3), described reactive diluent is epoxy propane butyl ether, expoxy propane phenyl ether, second
At least one in Hexanediol diglycidyl ether.
Preferably, Graphene modification acrylate is 0.25-0.35: 1, reactive diluent with the mass ratio of epoxy resin
Be 0.8-1.0 with the mass ratio of epoxy resin, catalyst is 0.005-0.015: 1 with the mass ratio of epoxy resin, polymerization inhibitor with
The mass ratio of epoxy resin is 0.001-0.002: 1.
Described epoxy resin is preferably epoxy resin E-44.
Present invention additionally comprises a kind of application of the epoxy acrylate of described Graphene graft modification, consolidate for preparing light
Change coating.
It is also solid including a kind of light of the described epoxy acrylate for being added with the Graphene graft modification in the present invention
Change coating, including following weight portion component：
In the present invention, in described photocureable coating (also referred to as UV light-cured epoxies acrylate paint), preferably,
Described light trigger is isopropyl thioxanthone anthraquinone, diphenyl phosphine oxide, hydroxycyclohexyl phenyl ketone, 1- hydroxycyclohexylphenylketones
In at least one.
Preferably, described levelling agent is organic silicon polyether copolymer and/or dimethyl silicone polymer.
Preferably, described defoamer is GPE types and/or higher alcohols.
The preparation method of photocureable coating of the present invention, described each component is uniformly mixed and is obtained final product.
In the present invention, a kind of preparation method of preferred UV light-cured epoxies acrylate paint is comprised the following steps：
Step (A)：By powdered graphite oxide and thionyl chloride (SOCl2) there-necked flask is added to, system is placed in 60-70
Condensing reflux reacts 19-24 hours in DEG C oil bath pan；It is then that remaining thionyl chloride in system is straight in 40-50 DEG C of vacuum distillation
Remaining (can not be evaporated, prevent the product of chloride from assembling, influence dispersion) to only minimal amount, product vavuum pump suction filtration is washed
Wash；The product of chloride is washed with chloroform, and uses chloroform dispersion product, the Graphene concentration for adjusting chloride is
0.5-1mg/ml, by product ultrasonic disperse 1-3h after acyl chloride reaction；
Step (B)：Chloride graphene oxide：
Chloride Graphene graft polymerization preformer hydroxyethyl methacrylate：
The chloroform soln that 80-100ml is contained into chloride Graphene is added drop-wise under low temperature (0-2 DEG C) stirring condition
10-20ml pyridines, in 30-40ml hydroxyethyl methacrylate mixed solutions, are then raised to room temperature, continue to stir 1-3h.Use
Distilled water washed product, last freeze-drying obtains chloride Graphene grafted methacrylic acid hydroxyl ethyl ester sample；
Step (C)：It is prepared by modified epoxy acrylic ester
Epoxy resin is added in reactive diluent, stirring reaction 40-50min, in stating reactive diluent then up
The modified hydroxyethyl methacrylate of Graphene, catalyst and polymerization inhibitor are slowly added to, intensification is reacted, and keeps reaction temperature
115 DEG C -135 DEG C, keep system acid number to be less than 4.5-5mg KOH/g, be finally cooled to room temperature, the modified epoxy of Graphene is obtained
Acrylate.
Wherein, modified graphene grafted methacrylic acid hydroxyl ethyl ester and the mass ratio of epoxy resin are 0.25-0.35: 1, living
Property diluent and epoxy resin mass ratio be 0.8-1.0, catalyst and the mass ratio of epoxy resin are 0.005-0.015: 1,
Polymerization inhibitor is 0.001-0.002: 1 with the mass ratio of epoxy resin；
Step (D)：It is prepared by UV light-cured epoxies acrylate paint
By modified epoxy acrylic ester 70-90 weight portions, light trigger 1-7 weight portions, levelling agent 0.04-0.4 weight portions,
Defoamer 0.02-0.12 weight portions, dispersed with stirring 3-6h is obtained UV light-cured epoxy acrylate paints under agitator.
The preparation method of UV light-cured epoxy acrylate paints preferred for this invention, first by thionyl chloride
(SOCl2) chloride graphene oxide, and then reacted with hydroxyethyl methacrylate using base catalysis chloride Graphene, obtain
To the Graphene (the modified hydroxyethyl methacrylate of Graphene) for introducing polymerizable double bond.Then Graphene is modified again
Hydroxyethyl methacrylate obtains being grafted with the epoxy acrylate of Graphene with epoxy resin copolymerization in reactive diluent.
Beneficial effect
The present invention by acylating agent (such as thionyl chloride) by graphene oxide and acrylate in situ bonding, then again with
Epoxy resin copolymerization, makes in graphene oxide in situ bonding to polymer, both helps emulsification effect with good dispersion, has again
The incomparable dispersion stabilization of physical blending, can be obviously improved the items for being added with the polymer-modified coating of the Graphene
Performance, is obtained the epoxy acrylate photocureable coating with high adhesion force, adhesive force and anti-in the mechanical property of the coating
Abrasion ability is greatly enhanced, and impact resistance is that toughness is significantly improved.
Specific embodiment：
Embodiment 1：
Step (1)：Synthesize graphite oxide with improved Hummers methods：
Graphene oxide is prepared with Hummers methods be divided into three steps, i.e. low-temp reaction stage (0-5 DEG C), middle temperature reaction rank
Section (35-40 DEG C) and pyroreaction stage (90-95 DEG C).Also to be washed and be post-processed after having reacted and just obtain desired product
Thing.
The low-temp reaction stage：10g natural flake graphites (particle diameter 0.1um) and 5g sodium nitrate NaNO3It is added to and is placed in ice bath
500ml there-necked flasks in environment, add the 404.8g concentrated sulfuric acids (95%-98%) during being slowly stirred, be incubated 30-40min
After be dividedly in some parts 30g potassium permanganate KMnO4, ice bath insulation 2h is continued after adding within about ten minutes；
The middle temperature stage of reaction：System is transferred in 30-35 DEG C of constant temperature water bath apparatus, 3-6h is incubated.With constant pressure funnel to anti-
Answer system that 460g deionized waters are slowly added dropwise.
The pyroreaction stage：It is rapid that bath temperature is increased to 95 DEG C, it is incubated 1h.480g is added dropwise with constant pressure funnel afterwards to go
Ionized water and continuation quickening mixing speed, continue that 240g deionized waters are added dropwise again after stirring 10min.After completion of dropping and then slowly
Add 88.8g hydrogen peroxide (30%).
Washing and post processing：Rear direct filter paper suction filtration while hot is reacted, be transferred to for brown color filter cake after finishing by suction filtration
In beaker.Subsequent 235.8g concentrated hydrochloric acids and 800g deionized waters mixed liquor are added in beaker, continue suction filtration, continue to add water after draining
Suction filtration, untill suction filtration does not get off.Product on filter cake is transferred in 500ml beakers.By product low-speed centrifugal in beaker
Machine is in 5000r/min, 15min/ centrifuge washing, until test centrifuge tube upper liquid pH value is no longer reduced.By centrifuge tube lower floor
Thing is transferred in surface plate, is placed in 50-60 DEG C of vacuum drying chamber and is dried until being completely dried.By dried graphene oxide
Grind into powder.
Step (2)：Chloride graphene oxide：
The powdered graphene oxides of 350g and 65.5g thionyl chlorides (SOCl2) there-necked flask is added to, system is placed in 60-
Condensing reflux reacts 19-24 hours in 70 DEG C of oil bath pans.Afterwards by remaining thionyl chloride in system in 50 DEG C of vacuum distillations until
Only minimal amount is remaining (can not be evaporated, prevent the product of chloride from assembling, influence dispersion), product vavuum pump filtering and washing.
The product of chloride is washed with chloroform, and uses chloroform dispersion product, the Graphene concentration for adjusting chloride is
0.5mg/ml, by product ultrasonic disperse 1-3h after acyl chloride reaction.
Step (3)：Chloride Graphene graft polymerization preformer hydroxyethyl methacrylate：
The chloroform soln that 85ml is contained into chloride Graphene is added drop-wise under low temperature (0-2 DEG C) stirring condition
19.6g pyridines, in 37.5g hydroxyethyl methacrylate mixed solutions, are then raised to room temperature, continue to stir 3h.Use distilled water
Washed product, last freeze-drying obtains chloride Graphene grafted methacrylic acid hydroxyl ethyl ester sample.
Step (4)：It is prepared by modified epoxy acrylic ester
30g epoxy resin (E-44) (mean molecule quantity is 454.5) is added into 27g reactive diluents, and (ethylene glycol two contracts
Water glycerin ether) in, stirring reaction 40-50min to be stated be slowly added to graphite obtained in step (3) in reactive diluent then up
Alkene modified hydroxyethyl methacrylate 8.6g, catalyst 0.15g (tetraethylammonium bromide) and polymerization inhibitor 0.03g (para hydroxybenzenes
Methyl ether), intensification is reacted, and keeps 115 DEG C -135 DEG C of reaction temperature, keeps system acid number to be less than 4.5-5mg KOH/g, finally
Room temperature is cooled to, the modified epoxy acrylate of Graphene is obtained.
Step (5)：It is prepared by UV light-cured epoxies acrylate paint
By modified epoxy acrylic ester 35g, light trigger 2g (hydroxycyclohexyl phenyl ketone), levelling agent 0.1g (poly dimethyls
Siloxanes), defoamer 0.02g (Defoamer CN-117), dispersed with stirring 3-6h is obtained UV light-cured epoxies third under agitator
Olefin(e) acid ester paint.
Embodiment 2：
Step (1)：Synthesize graphite oxide with improved Hummers methods：Referring to the step of embodiment 1 (1)；
Step (2)：Chloride graphene oxide：
The powdered graphene oxides of 350g and 65.5g thionyl chlorides (SOCl2) are added to there-necked flask, and system is placed in 60-
Condensing reflux reacts 19-24 hours in 70 DEG C of oil bath pans.Afterwards by remaining thionyl chloride in system in 50 DEG C of vacuum distillations until
Only minimal amount is remaining (can not be evaporated, prevent the product of chloride from assembling, influence dispersion), product vavuum pump filtering and washing.
The product of chloride is washed with chloroform, and uses chloroform dispersion product, the Graphene concentration for adjusting chloride is
0.5mg/ml, by product ultrasonic disperse 1-3h after acyl chloride reaction.
Step (3)：Chloride Graphene graft polymerization preformer hydroxyethyl methacrylate：
The chloroform soln that 90ml is contained into chloride Graphene is added drop-wise under low temperature (0-2 DEG C) stirring condition
19.6g pyridines, in 37.5g hydroxyethyl methacrylate mixed solutions, are then raised to room temperature, continue to stir 3h.Use distilled water
Washed product, last freeze-drying obtains chloride Graphene grafted methacrylic acid hydroxyl ethyl ester sample.
Step (4)：It is prepared by modified epoxy acrylic ester
30g epoxy resin (E-44) (mean molecule quantity is 454.5) is added into 27g reactive diluents, and (ethylene glycol two contracts
Water glycerin ether) in, stirring reaction 40-50min to be stated be slowly added to graphite obtained in step (3) in reactive diluent then up
Alkene modified hydroxyethyl methacrylate 8.6g, catalyst 0.15g (tetraethylammonium bromide) and polymerization inhibitor 0.03g (para hydroxybenzenes
Methyl ether), intensification is reacted, and keeps 115 DEG C -135 DEG C of reaction temperature, keeps system acid number to be less than 4.5-5mg KOH/g, finally
Room temperature is cooled to, the modified epoxy acrylate of Graphene is obtained.
Step (5)：It is prepared by UV light-cured epoxies acrylate paint
By modified epoxy acrylic ester 35g, light trigger 2g (hydroxycyclohexyl phenyl ketone), levelling agent 0.1g (poly dimethyls
Siloxanes), defoamer 0.02g (Defoamer CN-117), dispersed with stirring 3-6h is obtained UV light-cured epoxies third under agitator
Olefin(e) acid ester paint.
Embodiment 3：
Step (1)：Synthesize graphite oxide with improved Hummers methods：Referring to the step of embodiment 1 (1)；
Step (2)：Chloride graphene oxide：
The powdered graphene oxides of 350g and 65.5g thionyl chlorides (SOCl2) are added to there-necked flask, and system is placed in 60-
Condensing reflux reacts 19-24 hours in 70 DEG C of oil bath pans.Afterwards by remaining thionyl chloride in system in 50 DEG C of vacuum distillations until
Only minimal amount is remaining (can not be evaporated, prevent the product of chloride from assembling, influence dispersion), product vavuum pump filtering and washing.
The product of chloride is washed with chloroform, and uses chloroform dispersion product, the Graphene concentration for adjusting chloride is
0.5mg/ml, by product ultrasonic disperse 1-3h after acyl chloride reaction.
Step (3)：Chloride Graphene graft polymerization preformer hydroxyethyl methacrylate：
The chloroform soln that 90ml is contained into chloride Graphene is added drop-wise under low temperature (0-2 DEG C) stirring condition
19.6g pyridines, in 37.5g hydroxyethyl methacrylate mixed solutions, are then raised to room temperature, continue to stir 3h.Use distilled water
Washed product, last freeze-drying obtains chloride Graphene grafted methacrylic acid hydroxyl ethyl ester sample.
Step (4)：It is prepared by modified epoxy acrylic ester
30g epoxy resin (E-44) (mean molecule quantity is 454.5) is added into 27g reactive diluents, and (ethylene glycol two contracts
Water glycerin ether) in, stirring reaction 40-50min to be stated be slowly added to graphite obtained in step (3) in reactive diluent then up
Alkene modified hydroxyethyl methacrylate 9g, catalyst 0.15g (tetraethylammonium bromide) and polymerization inhibitor 0.03g (para hydroxybenzene first
Ether), intensification is reacted, and keeps 115 DEG C -135 DEG C of reaction temperature, keeps system acid number to be less than 4.5-5mg KOH/g, last cold
But room temperature is arrived, the modified epoxy acrylate of Graphene is obtained.
Step (5)：It is prepared by UV light-cured epoxies acrylate paint
By modified epoxy acrylic ester 35g, light trigger 2g (hydroxycyclohexyl phenyl ketone), levelling agent 0.1g (poly dimethyls
Siloxanes), defoamer 0.02g (Defoamer CN-117), dispersed with stirring 3-6h is obtained UV light-cured epoxies third under agitator
Olefin(e) acid ester paint.
Embodiment 4：
Step (1)：Synthesize graphite oxide with improved Hummers methods：Referring to the step of embodiment 1 (1)；
Step (2)：Chloride graphene oxide：
The powdered graphene oxides of 350g and 65.5g thionyl chlorides (SOCl2) are added to there-necked flask, and system is placed in 60-
Condensing reflux reacts 19-24 hours in 70 DEG C of oil bath pans.Afterwards by remaining thionyl chloride in system in 50 DEG C of vacuum distillations until
Only minimal amount is remaining (can not be evaporated, prevent the product of chloride from assembling, influence dispersion), product vavuum pump filtering and washing.
The product of chloride is washed with chloroform, and uses chloroform dispersion product, the Graphene concentration for adjusting chloride is
0.5mg/ml, by product ultrasonic disperse 1-3h after acyl chloride reaction.
Step (3)：Chloride Graphene graft polymerization preformer hydroxyethyl methacrylate：
The chloroform soln that 90ml is contained into chloride Graphene is added drop-wise under low temperature (0-2 DEG C) stirring condition
19.6g pyridines, in 37.5g hydroxyethyl methacrylate mixed solutions, are then raised to room temperature, continue to stir 3h.Use distilled water
Washed product, last freeze-drying obtains chloride Graphene grafted methacrylic acid hydroxyl ethyl ester sample.
Step (4)：It is prepared by modified epoxy acrylic ester
30g epoxy resin (E-44) (mean molecule quantity is 454.5) is added into 27g reactive diluents, and (ethylene glycol two contracts
Water glycerin ether) in, stirring reaction 40-50min to be stated be slowly added to graphite obtained in step (3) in reactive diluent then up
Alkene modified hydroxyethyl methacrylate 9.3g, catalyst 0.15g (tetraethylammonium bromide) and polymerization inhibitor 0.03g (para hydroxybenzenes
Methyl ether), intensification is reacted, and keeps 115 DEG C -135 DEG C of reaction temperature, keeps system acid number to be less than 4.5-5mg KOH/g, finally
Room temperature is cooled to, the modified epoxy acrylate of Graphene is obtained.
Step (5)：It is prepared by UV light-cured epoxies acrylate paint
By modified epoxy acrylic ester 35g, light trigger 2g (hydroxycyclohexyl phenyl ketone), levelling agent 0.1g (poly dimethyls
Siloxanes), defoamer 0.02g (Defoamer CN-117), dispersed with stirring 3-6h is obtained UV light-cured epoxies third under agitator
Olefin(e) acid ester paint.
Comparative example 1：
Compared with embodiment 1, difference is to substitute described modified epoxy acrylic ester using ordinary epoxy resin.
Step (1)：It is prepared by epoxy acrylate
30g epoxy resin (E-44) (mean molecule quantity is 454.5) is added into 27g reactive diluents, and (ethylene glycol two contracts
Water glycerin ether) in, stirring reaction 40-50min to be stated be slowly added to hydroxyethyl methacrylate in reactive diluent then up
9.3g, catalyst 0.15g (tetraethylammonium bromide) and polymerization inhibitor 0.03g (MEHQ), intensification are reacted, and keep anti-
115 DEG C -135 DEG C of temperature is answered, keeps system acid number to be less than 4.5-5mgKOH/g, be finally cooled to room temperature, epoxy acrylic is obtained
Ester.
Step (2)：It is prepared by UV light-cured epoxies acrylate paint
By epoxy acrylate 35g, light trigger 2g (hydroxycyclohexyl phenyl ketone), levelling agent 0.1g (polydimethylsiloxanes
Alkane), defoamer 0.02g (Defoamer CN-117), dispersed with stirring 3-6h is obtained UV light-cured epoxy acrylic acid under agitator
Ester paint.
Beneficial effects of the present invention are further illustrated below by experimental data：
With GB/T1732-1993《Paint film impact resistance assay method》It is standard, weight quality is 1Kg, not cause paint film
The maximum height of destruction represents, unit is Kgcm determines the pliability of paint film
Abrasion performance presses GB/T1768-79 (89) execution
Adhesive force is performed by GB/T9286-88, with one-level as qualified
The detection data of each embodiment and comparative example is shown in Table 1：
Table 1
As it can be seen from table 1 after addition graft polymerization preformer Graphene, adhesive force and abrasion resisting ability are obtained greatly in mechanical property
Ground lifting, and above all its impact resistance is that toughness is significantly improved.
Claims (10)
1. a kind of preparation method of the epoxy acrylate of Graphene graft modification, it is characterised in that comprise the following steps：
Step (1)：Graphene oxide and acylation reaction, are obtained acylated graphene oxide；
Step (2)：By acylated graphene oxide, the acrylate containing active group, acid binding agent reaction, Graphene modified third is obtained
Olefin(e) acid ester；
Step (3)：Again by Graphene modification acrylate, epoxy resin copolymerization, the propylene oxide of Graphene graft modification is obtained
Acid esters.
2. the preparation method of the epoxy acrylate of Graphene graft modification as claimed in claim 1, it is characterised in that described
Acylating agent be at least one in thionyl chloride, phosphorus trichloride, phosphorus pentachloride.
3. the preparation method of the epoxy acrylate of Graphene graft modification as claimed in claim 2, it is characterised in that step
(1) in, reaction temperature is 60-70 DEG C, and the reaction time is 19-24h.
4. the preparation method of the epoxy acrylate of Graphene graft modification as claimed in claim 1, it is characterised in that step
(2) in, described acid binding agent is pyridine and/or triethylamine.
5. the preparation method of the epoxy acrylate of the Graphene graft modification as described in any one of Claims 1 to 4, its feature
It is that the described acrylate containing active group is the compound with the structure of formula 1：
In formula 1, Y is the alkyl of C1~5；R is H or methyl.
6. the preparation method of the epoxy acrylate of Graphene graft modification as claimed in claim 5, it is characterised in that described
The acrylate containing active group be (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxyl
At least one in N-butyl.
7. the preparation method of the epoxy acrylate of Graphene graft modification as claimed in claim 1, it is characterised in that step
(3) in, epoxy resin is dissolved in reactive diluent, then adds Graphene modification acrylate obtained in step (2), urges
Agent and polymerization inhibitor and at 115 DEG C -135 DEG C copolymerization the epoxy acrylate of the Graphene graft modification is obtained；It was polymerized
The acid number of process control system is less than 4.5-5mg KOH/g；
The mass ratio of Graphene modification acrylate and epoxy resin is 0.25-0.35: 1, reactive diluent and epoxy resin
Mass ratio is 0.8-1.0, and catalyst is 0.005-0.015: 1 with the mass ratio of epoxy resin, the matter of polymerization inhibitor and epoxy resin
Amount is than being 0.001-0.002: 1.
8. the preparation method of the epoxy acrylate of Graphene graft modification as claimed in claim 7, it is characterised in that described
Catalyst be N, at least one in N- dimethyl benzylamines, triphenylphosphine, tetraethylammonium bromide；
Described polymerization inhibitor is at least one in hydroquinones, 2,5- di-tert-butyl hydroquinones, MEHQ；
Described reactive diluent be epoxy propane butyl ether, expoxy propane phenyl ether, ethylene glycol diglycidylether in extremely
Few one kind.
9. the application of the epoxy acrylate of Graphene graft modification obtained in a kind of method of any one of claim 1~8, its
It is characterised by, for preparing photocureable coating.
10. a kind of photocureable coating, it is characterised in that the component including following weight portion：
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