CN106832220B - A kind of preparation of the epoxy acrylate of graphene graft modification and its application in photocureable coating - Google Patents
A kind of preparation of the epoxy acrylate of graphene graft modification and its application in photocureable coating Download PDFInfo
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- CN106832220B CN106832220B CN201611259655.6A CN201611259655A CN106832220B CN 106832220 B CN106832220 B CN 106832220B CN 201611259655 A CN201611259655 A CN 201611259655A CN 106832220 B CN106832220 B CN 106832220B
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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 methods of the epoxy acrylate of graphene graft modification; graphene oxide with reacted again with acrylate, acid binding agent containing active group after acylation reaction; it is finally copolymerized again with epoxy resin, the epoxy acrylate of graphene graft modification is made.In addition, the invention also discloses the applications of the epoxy acrylate of graphene graft modification, and added with the polymer-modified photocureable coating.The present invention is by acylating agent by graphene oxide and acrylate in situ bonding; then it is copolymerized again with epoxy resin; make graphene oxide in situ bonding into polymer; both had effects that good dispersion helped emulsification; the dispersion stabilization incomparable with physical blending again, can be obviously improved the properties added with the polymer-modified coating of the graphene.
Description
Technical field
The invention belongs to epoxy acrylate coating technical fields, and in particular to a kind of epoxy third of graphene graft modification
The preparation method of olefin(e) acid ester, and the photocureable coating of the epoxy acrylate added with the modification.
Background technique
Bisphenol A epoxy acrylate has as a kind of maximum UV photocuring corrosion resistant coating matrix resin of dosage
The advantages of Corrosion Protection is excellent and rapid curing, furthermore its mechanical property is preferable, thus is widely used in many industrial circles.
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 easy to happen 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 its stable heterocycle structure
It keeps stablizing under warm environment.Although graphene is had excellent performance, since the graphene oxide of oxidation-reduction method preparation is molten
There is π-π to stack tendency the phenomenon that being agglomerated into bulky grain graphite oxide in agent, 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 material
In application.
Currently, having rapid development using the research that inorganic material improves bisphenol A epoxy acrylate coating property, still
Using graphene, this star's material modification bisphenol A epoxy acrylate is still less.Among these, about graphene modified bisphenol
The method that the report of A epoxy acrylate mostly uses blending or solution intercalation method greatly.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 combine well, play association
With the effect of effect, but blending modification method dispersibility is poor, and graphene can not be uniformly dispersed in bisphenol-A epoxy acrylic acid
In ester.Dispersibility of the graphene in epoxy acrylate is bad, is easy to reunite, obtained graphene-based epoxy acrylate applies
The overall performance of material is unsatisfactory.Wei and partner are by graphene oxide and the compound preparation of epoxy acrylic ester prepolymer
GO/EA, prepared product tensile strength improve 8.39%, and bending modulus has dropped 46.79%[3].In this work
In, graphene oxide is to be mixed in a manner of blending with Epoxy Acrylates, leads to last composite material homogeneity still
It not can guarantee.
[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 Dehai epoxy acrylic Lipase absobed and progress [J] coatings industry of application, 2007,37
(11): 53-57.
[3] the modified UV of Wei Yanyan, Wang Hu graphene solidifies research [J] coating of bisphenol-A epoxy acrylic resin performance
Industry, 2016,46 (6): 12-27.
Summary of the invention:
The material after the generally existing easy reunion of method, doping to solve existing graphene doping vario-property epoxy acrylate
Expect the technical problems such as performance is undesirable, the present invention provides a kind of preparation sides of the epoxy acrylate of graphene graft modification
Method, it is intended to avoid graphene from reuniting, the performance of the material after promoting doping.
The present invention also provides the applications of the epoxy acrylate of the graphene graft modification.
In addition, the invention also includes the paintings of the epoxy acrylate added with graphene graft modification of the present invention
Material, it is intended to promote the performances such as the impact resistance, adhesive force, abrasion resisting of coating.
A kind of preparation method of the epoxy acrylate of graphene graft modification, comprising the following steps:
Step (1): acylated graphene oxide is made in graphene oxide and acylation reaction；
Step (2): acylated graphene oxide, the acrylate containing active group, acid binding agent are reacted, obtained graphene changes
Property acrylate；
Step (3): graphene modification acrylate, epoxy resin are copolymerized again, the epoxy of graphene graft modification is made
Acrylate.
It in the present invention, is esterified by the hydroxyl of acylating agent and graphene oxide, carboxyl isoreactivity group, thus 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 acylation active group of surface modification and the acrylate reactions containing active group, to keep graphene oxide and acrylate multiple
It closes, obtained in situ bonding has the double bond compound (graphene modification acrylate) of graphene oxide；It will be bonded with oxidation stone again
The acrylate and epoxy resin of black alkene are copolymerized, and are made graphene oxide original position, are uniformly bonded to main polymer chain, so as to effective
Avoid the reunion of graphene oxide；Effectively promote the performance for being added with the modified epoxy acrylic ester coating.In the present invention, make
With polymerizable graphene (graphene modification acrylate), not only had effects that good dispersion helped emulsification, but also total with physics
Incomparable dispersion stabilization is mixed, so that epoxy acrylate photocureable coating mechanical performance especially adhesive force obtains greatly
Raising.
In the present invention, the acylating agent can be with the active group such as hydroxyl, carboxyl isoreactivity of surface of graphene oxide
Group reaction, so that surface of graphene oxide be made to modify active acylate group, the acylate group is, for example, acid halide group
Group, sulfonyl halide groups, sulfenyl halogen group, phosphoryl halogen group etc.；Further preferably acid chloride groups, sulfonic acid chloride group, sub- sulphur
Acid chloride groups, phosphinylidyne cl radical etc..
Preferably, the acylating agent is at least one of thionyl chloride, phosphorus trichloride, phosphorus pentachloride.
Further preferably, the acylating agent is thionyl chloride.
In the present invention, the graphene oxide can be made by improved Hummers method.
In the present invention, prepare graphene oxide with Hummers method and be divided into three steps, i.e., the 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).It also to be washed and be post-processed after having reacted and just be obtained
Desired product.
In the present invention, the preparation step of graphene oxide is preferred are as follows:
Step (a): low-temp reaction stage: 2.0-2.5 parts by weight natural flake graphite (partial size 0.1um) and 1-1.25 weight
Part sodium nitrate NaNO3It is added to the 500ml three-necked flask being placed in ice bath environment, 55.2-110.4 is added during being slowly stirred
6-7.5 parts by weight potassium permanganate KMnO is added portionwise after keeping the temperature 30-40min in the parts by weight concentrated sulfuric acid (95%-98%)4, about very
Clock continues ice bath heat preservation 1-2h after adding；
Step (b): the medium temperature stage of reaction: system is transferred in 30-35 DEG C of constant temperature water bath apparatus, keeps the temperature 3-6h；Use constant pressure
Deionized water is slowly added dropwise to reaction system in funnel；
Step (c): the pyroreaction stage: being increased to 80-95 DEG C for bath temperature rapidly, keeps the temperature one hour；Later 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；It is added dropwise
Then it is slowly added into hydrogen peroxide (>=30%) afterwards；
Step (d): it washing and post-processing: is directly filtered with filter paper after having reacted, filters brown color while hot after suction filtration
Cake is transferred in beaker；The diluted hydrochloric acid of concentrated hydrochloric acid is added in beaker, continues to take out after keeping the temperature 80-95 DEG C of stir about half an hour
Filter, continues after draining plus water filters, until suction filtration does not get off；Product on filter cake is transferred in 500ml beaker；By beaker
Middle product low speed centrifuge is in 3500-5000r/min, 10-15min/ centrifuge washing, until test centrifuge tube upper liquid pH
Value no longer reduces；Centrifuge tube lower layer object is transferred in surface plate, is placed in 50-60 DEG C of vacuum oven and dries until completely dry
It is dry；By the graphite oxide grind into powder after drying.
In step (1), acylating agent is with respect to graphene oxide excess, preferably, acylating agent adds volume and 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, reaction temperature is 60-70 DEG C, reaction time 19-24h in step (1).
After the acylation reaction of step (1), remaining thionyl chloride is removed under reduced pressure；Product after chloroform washs again
It is dispersed in spare in chloroform soln.
By acylated graphene oxide ultrasonic disperse obtained in chloroform, preparing and obtaining concentration is 0.5-1mg/ml's
Dispersion liquid.
Preferably, ultrasonic time is 1~3h.
In the present invention, the acid binding agent is well known to those skilled in the art the compound that can be reacted with acid, such as can
For compound, inorganic base etc. with tertiary ammonia.
Preferably, the acid binding agent is pyridine and/or triethylamine.
Further preferably, the acid binding agent is pyridine.
In the present invention, the acrylate containing active group is to have active hydrogen containing what can be reacted with acylate group
Acrylate；Preferably, the acrylate containing active group is the acrylic acid containing hydroxyl and/or primary amino group
Ester.
In step (2), will acylated graphene oxide made from step (1) under the catalysis of acid binding agent, and contain active group
Acrylate carry out esterification or amidation process, be made graphene modification acrylate.
For example, the active group that the acrylate containing active group is included is OH, pass through OH and acylate group
Esterification is carried out, by graphene oxide and acrylate compound by way of ester bond；For another example, described containing active group
The active group that acrylate is included is NH2, carries out amidation process by NH2 and acylate group, by amido bond by oxygen
Graphite alkene and acrylate compound.
Further preferably, in step (2), by acylated graphene oxide made from step (1) under the catalysis of acid binding agent, with
Acrylate containing active group carries out alcoholic extract hydroxyl group and reacts with acid chloride groups, and graphene modification acrylate is made.
Further preferably, the acrylate containing active group is the compound with 1 structure of formula:
In formula 1, Y is the alkyl of C1~5；R is H or methyl.
The Y is the branch or straight-chain alkyl of C1~5.
Still more preferably, the acrylate containing active group is (methyl) hydroxy-ethyl acrylate, (methyl) third
At least one of olefin(e) acid hydroxypropyl acrylate, (methyl) acrylic acid hydroxyl N-butyl.
Most preferably, the acrylate containing active group is hydroxyethyl methacrylate.
Preferably, acylated graphene oxide and the acrylate containing active group are being lower than 2 DEG C of temperature in step (2)
Degree is lower to be added dropwise excessive acid binding agent；Room temperature is warming up to after being added dropwise to complete, the reaction was continued 1~3h.After reaction, it is washed with distillation
It washs, dry obtained graphene modification acrylate.
In step (3), epoxy resin is dissolved in reactive diluent, graphene made from step (2) is then added and changes
Property acrylate, catalyst and polymerization inhibitor and at 115 DEG C -135 DEG C copolymerization the epoxy third of the graphene graft modification is made
Olefin(e) acid ester.
Preferably, the acid value of polymerization process control system is less than 4.5-5mg KOH/g in step (3).
Preferably, the catalyst is N, N- dimethyl benzylamine, triphenylphosphine, tetraethylammonium bromide in step (3)
At least one of.
Preferably, the polymerization inhibitor is hydroquinone, 2,5- di-tert-butyl hydroquinone, to hydroxyl in step (3)
At least one of methyl phenyl ethers anisole.
Preferably, the reactive diluent is epoxy propane butyl ether, propylene oxide phenyl ether, second in step (3)
At least one of Hexanediol diglycidyl ether.
Preferably, the mass ratio of graphene modification acrylate and epoxy resin is 0.25-0.35: 1, reactive diluent
Be 0.8-1.0 with the mass ratio of epoxy resin, the mass ratio of catalyst and epoxy resin is 0.005-0.015: 1, polymerization inhibitor with
The mass ratio of epoxy resin is 0.001-0.002: 1.
The epoxy resin is preferably epoxy resin E-44.
The invention also includes the applications of the epoxy acrylate of the graphene graft modification described in one kind, and it is solid to be used to prepare light
Change coating.
In the present invention, further include the epoxy acrylate described in one kind added with the graphene graft modification light it is solid
Change coating, comprise the following components in parts by weight:
In the present invention, in the photocureable coating (also referred to as UV light-cured epoxy acrylate paint), preferably,
The photoinitiator is isopropyl thioxanthone anthraquinone, diphenyl phosphine oxide, hydroxycyclohexyl phenyl ketone, 1- hydroxycyclohexylphenylketone
At least one of.
Preferably, the levelling agent is organic silicon polyether copolymer and/or dimethyl silicone polymer.
Preferably, the defoaming agent is GPE type and/or higher alcohols.
The each component is uniformly mixed to obtain the final product by the preparation method of photocureable coating of the present invention.
In the present invention, a kind of preparation method of preferred UV light-cured epoxy acrylate paint, comprising the following steps:
Step (A): by powdered graphite oxide and thionyl chloride (SOCl2) it is added to three-necked flask, system is placed in 60-70
Reaction 19-24 hours is condensed back in DEG C oil bath pan；It is then that thionyl chloride remaining in system is straight in 40-50 DEG C of vacuum distillation
Remaining (cannot be evaporated, prevent the product of chloride from assembling, influence to disperse) to only minimal amount, product vacuum pump suction filtration is washed
It washs；The product of chloride is washed with chloroform, and with 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 contains chloride graphene is added drop-wise under low temperature (0-2 DEG C) stirring condition
10-20ml pyridine in 30-40ml hydroxyethyl methacrylate mixed solution, is then raised to room temperature, continues to stir 1-3h.It uses
Distilled water washed product, finally freeze-drying obtains chloride graphene grafted methacrylic acid hydroxyl ethyl ester sample；
Step (C): modified epoxy acrylic ester preparation
Epoxy resin is added in reactive diluent, 40-50min is stirred to react, states in reactive diluent then up
It is slowly added to graphene modified hydroxyethyl methacrylate, catalyst and polymerization inhibitor, heating is reacted, and reaction temperature is kept
It 115 DEG C -135 DEG C, keeps system acid value to be less than 4.5-5mg KOH/g, is finally cooled to room temperature, the modified epoxy of graphene is made
Acrylate.
Wherein, the mass ratio of modified graphene grafted methacrylic acid hydroxyl ethyl ester and epoxy resin is 0.25-0.35: 1, living
Property diluent and the mass ratio of epoxy resin be 0.8-1.0, the mass ratio of catalyst and epoxy resin is 0.005-0.015: 1,
The mass ratio of polymerization inhibitor and epoxy resin is 0.001-0.002: 1；
Step (D): UV light-cured epoxy acrylate paint preparation
By modified epoxy acrylic ester 70-90 parts by weight, photoinitiator 1-7 parts by weight, levelling agent 0.04-0.4 parts by weight,
Defoaming agent 0.02-0.12 parts by weight are dispersed with stirring 3-6h under blender and UV light-cured epoxy acrylate paint are made.
The preparation method of UV light-cured epoxy acrylate paint preferred for this invention uses thionyl chloride first
(SOCl2) chloride graphene oxide, it is and then reacted, is obtained with hydroxyethyl methacrylate using base catalysis chloride graphene
To the graphene (the modified hydroxyethyl methacrylate of graphene) for introducing polymerizable double bond.Then graphene is modified again
Hydroxyethyl methacrylate and epoxy resin are copolymerized the epoxy acrylate for obtaining being grafted with graphene 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 graphene oxide in situ bonding into polymer, has not only had effects that good dispersion helps emulsification, but also have
The incomparable dispersion stabilization of physical blending, can be obviously improved the items added with the polymer-modified coating of the graphene
The epoxy acrylate photocureable coating with high adhesion force is made in performance, adhesive force and anti-in the mechanical property of the coating
Abrasion ability is greatly enhanced, and impact resistance, that is, toughness is significantly improved.
Specific embodiment:
Embodiment 1:
Step (1): graphite oxide is synthesized with improved Hummers method:
Graphene oxide is prepared with Hummers method and is divided into three steps, i.e. low-temp reaction stage (0-5 DEG C), medium temperature reacts rank
Section (35-40 DEG C) and pyroreaction stage (90-95 DEG C).It also to be washed and be post-processed after having reacted and just obtain desired production
Object.
The low-temp reaction stage: 10g natural flake graphite (partial size 0.1um) and 5g sodium nitrate NaNO3It is added to and is placed in ice bath
500ml three-necked flask in environment is added the 404.8g concentrated sulfuric acid (95%-98%) during being slowly stirred, keeps the temperature 30-40min
After 30g potassium permanganate KMnO is added portionwise4, continue ice bath after adding within about ten minutes and keep the temperature 2h；
The medium temperature stage of reaction: system is transferred in 30-35 DEG C of constant temperature water bath apparatus, keeps the temperature 3-6h.With constant pressure funnel to anti-
Answer system that 460g deionized water is slowly added dropwise.
The pyroreaction stage: being increased to 95 DEG C for bath temperature rapidly, keeps the temperature 1h.480g is added dropwise with constant pressure funnel later to go
Ionized water and continue accelerate mixing speed, continue stir 10min after 240g deionized water is added dropwise again.After being added dropwise then slowly
It is added 88.8g hydrogen peroxide (30%).
Washing and post-processing: it is directly filtered with filter paper after having reacted, is transferred to brown color filter cake while hot after suction filtration
In beaker.Subsequent 235.8g concentrated hydrochloric acid and 800g deionized water mixed liquor are added in beaker, continue to filter, and continue to add water after draining
It filters, until suction filtration does not get off.Product on filter cake is transferred in 500ml beaker.By product low-speed centrifugal in beaker
Machine is in 5000r/min, 15min/ centrifuge washing, until test centrifuge tube upper liquid pH value no longer reduces.By centrifuge tube lower layer
Object is transferred in surface plate, is placed in 50-60 DEG C of vacuum oven and is dried until being completely dried.By the graphene oxide after drying
Grind into powder.
Step (2): chloride graphene oxide:
The powdered graphene oxide of 350g and 65.5g thionyl chloride (SOCl2) it is added to three-necked flask, system is placed in 60-
Reaction 19-24 hours is condensed back in 70 DEG C of oil bath pans.Afterwards by thionyl chloride remaining in system in 50 DEG C vacuum distillation until
Only minimal amount is remaining (cannot be evaporated, prevent the product of chloride from assembling, influence to disperse), product vacuum pump filtering and washing.
The product of chloride is washed with chloroform, and with 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 contains chloride graphene is added drop-wise under low temperature (0-2 DEG C) stirring condition
19.6g pyridine in 37.5g hydroxyethyl methacrylate mixed solution, is then raised to room temperature, continues to stir 3h.Use distilled water
Washed product, finally freeze-drying obtains chloride graphene grafted methacrylic acid hydroxyl ethyl ester sample.
Step (4): modified epoxy acrylic ester preparation
30g epoxy resin (E-44) (average molecular weight 454.5) is added to 27g reactive diluent, and (ethylene glycol two contracts
Water glycerin ether) in, it is stirred to react 40-50min, states be slowly added to graphite made from step (3) in reactive diluent then up
Alkene modified hydroxyethyl methacrylate 8.6g, catalyst 0.15g (tetraethylammonium bromide) and polymerization inhibitor 0.03g (para hydroxybenzene
Methyl ether), heating is reacted, and is kept for 115 DEG C -135 DEG C of reaction temperature, keeps system acid value to be less than 4.5-5mg KOH/g, finally
It is cooled to room temperature, the modified epoxy acrylate of graphene is made.
Step (5): UV light-cured epoxy acrylate paint preparation
By modified epoxy acrylic ester 35g, photoinitiator 2g (hydroxycyclohexyl phenyl ketone), levelling agent 0.1g (poly dimethyl
Siloxanes), defoaming agent 0.02g (Defoamer CN-117), be dispersed with stirring under blender 3-6h be made UV light-cured epoxy third
Olefin(e) acid ester paint.
Embodiment 2:
Step (1): graphite oxide is synthesized with improved Hummers method: referring to 1 step of embodiment (1)；
Step (2): chloride graphene oxide:
The powdered graphene oxide of 350g and 65.5g thionyl chloride (SOCl2) are added to three-necked flask, and system is placed in 60-
Reaction 19-24 hours is condensed back in 70 DEG C of oil bath pans.Afterwards by thionyl chloride remaining in system in 50 DEG C vacuum distillation until
Only minimal amount is remaining (cannot be evaporated, prevent the product of chloride from assembling, influence to disperse), product vacuum pump filtering and washing.
The product of chloride is washed with chloroform, and with 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 contains chloride graphene is added drop-wise under low temperature (0-2 DEG C) stirring condition
19.6g pyridine in 37.5g hydroxyethyl methacrylate mixed solution, is then raised to room temperature, continues to stir 3h.Use distilled water
Washed product, finally freeze-drying obtains chloride graphene grafted methacrylic acid hydroxyl ethyl ester sample.
Step (4): modified epoxy acrylic ester preparation
30g epoxy resin (E-44) (average molecular weight 454.5) is added to 27g reactive diluent, and (ethylene glycol two contracts
Water glycerin ether) in, it is stirred to react 40-50min, states be slowly added to graphite made from step (3) in reactive diluent then up
Alkene modified hydroxyethyl methacrylate 8.6g, catalyst 0.15g (tetraethylammonium bromide) and polymerization inhibitor 0.03g (para hydroxybenzene
Methyl ether), heating is reacted, and is kept for 115 DEG C -135 DEG C of reaction temperature, keeps system acid value to be less than 4.5-5mg KOH/g, finally
It is cooled to room temperature, the modified epoxy acrylate of graphene is made.
Step (5): UV light-cured epoxy acrylate paint preparation
By modified epoxy acrylic ester 35g, photoinitiator 2g (hydroxycyclohexyl phenyl ketone), levelling agent 0.1g (poly dimethyl
Siloxanes), defoaming agent 0.02g (Defoamer CN-117), be dispersed with stirring under blender 3-6h be made UV light-cured epoxy third
Olefin(e) acid ester paint.
Embodiment 3:
Step (1): graphite oxide is synthesized with improved Hummers method: referring to 1 step of embodiment (1)；
Step (2): chloride graphene oxide:
The powdered graphene oxide of 350g and 65.5g thionyl chloride (SOCl2) are added to three-necked flask, and system is placed in 60-
Reaction 19-24 hours is condensed back in 70 DEG C of oil bath pans.Afterwards by thionyl chloride remaining in system in 50 DEG C vacuum distillation until
Only minimal amount is remaining (cannot be evaporated, prevent the product of chloride from assembling, influence to disperse), product vacuum pump filtering and washing.
The product of chloride is washed with chloroform, and with 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 contains chloride graphene is added drop-wise under low temperature (0-2 DEG C) stirring condition
19.6g pyridine in 37.5g hydroxyethyl methacrylate mixed solution, is then raised to room temperature, continues to stir 3h.Use distilled water
Washed product, finally freeze-drying obtains chloride graphene grafted methacrylic acid hydroxyl ethyl ester sample.
Step (4): modified epoxy acrylic ester preparation
30g epoxy resin (E-44) (average molecular weight 454.5) is added to 27g reactive diluent, and (ethylene glycol two contracts
Water glycerin ether) in, it is stirred to react 40-50min, states be slowly added to graphite made from 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), heating is reacted, and is kept for 115 DEG C -135 DEG C of reaction temperature, and system acid value is kept to be less than 4.5-5mg KOH/g, last cold
But room temperature is arrived, the modified epoxy acrylate of graphene is made.
Step (5): UV light-cured epoxy acrylate paint preparation
By modified epoxy acrylic ester 35g, photoinitiator 2g (hydroxycyclohexyl phenyl ketone), levelling agent 0.1g (poly dimethyl
Siloxanes), defoaming agent 0.02g (Defoamer CN-117), be dispersed with stirring under blender 3-6h be made UV light-cured epoxy third
Olefin(e) acid ester paint.
Embodiment 4:
Step (1): graphite oxide is synthesized with improved Hummers method: referring to 1 step of embodiment (1)；
Step (2): chloride graphene oxide:
The powdered graphene oxide of 350g and 65.5g thionyl chloride (SOCl2) are added to three-necked flask, and system is placed in 60-
Reaction 19-24 hours is condensed back in 70 DEG C of oil bath pans.Afterwards by thionyl chloride remaining in system in 50 DEG C vacuum distillation until
Only minimal amount is remaining (cannot be evaporated, prevent the product of chloride from assembling, influence to disperse), product vacuum pump filtering and washing.
The product of chloride is washed with chloroform, and with 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 contains chloride graphene is added drop-wise under low temperature (0-2 DEG C) stirring condition
19.6g pyridine in 37.5g hydroxyethyl methacrylate mixed solution, is then raised to room temperature, continues to stir 3h.Use distilled water
Washed product, finally freeze-drying obtains chloride graphene grafted methacrylic acid hydroxyl ethyl ester sample.
Step (4): modified epoxy acrylic ester preparation
30g epoxy resin (E-44) (average molecular weight 454.5) is added to 27g reactive diluent, and (ethylene glycol two contracts
Water glycerin ether) in, it is stirred to react 40-50min, states be slowly added to graphite made from step (3) in reactive diluent then up
Alkene modified hydroxyethyl methacrylate 9.3g, catalyst 0.15g (tetraethylammonium bromide) and polymerization inhibitor 0.03g (para hydroxybenzene
Methyl ether), heating is reacted, and is kept for 115 DEG C -135 DEG C of reaction temperature, keeps system acid value to be less than 4.5-5mg KOH/g, finally
It is cooled to room temperature, the modified epoxy acrylate of graphene is made.
Step (5): UV light-cured epoxy acrylate paint preparation
By modified epoxy acrylic ester 35g, photoinitiator 2g (hydroxycyclohexyl phenyl ketone), levelling agent 0.1g (poly dimethyl
Siloxanes), defoaming agent 0.02g (Defoamer CN-117), be dispersed with stirring under blender 3-6h be made UV light-cured epoxy third
Olefin(e) acid ester paint.
Comparative example 1:
It is compared with embodiment 1, difference is, using the ordinary epoxy resin substitution modified epoxy acrylic ester.
Step (1): epoxy acrylate preparation
30g epoxy resin (E-44) (average molecular weight 454.5) is added to 27g reactive diluent, and (ethylene glycol two contracts
Water glycerin ether) in, it is stirred to react 40-50min, states be slowly added to hydroxyethyl methacrylate in reactive diluent then up
9.3g, catalyst 0.15g (tetraethylammonium bromide) and polymerization inhibitor 0.03g (p-hydroxyanisole), heating are reacted, and keep anti-
115 DEG C -135 DEG C of temperature are answered, keeps system acid value to be less than 4.5-5mgKOH/g, is finally cooled to room temperature, epoxy acrylic is made
Ester.
Step (2): UV light-cured epoxy acrylate paint preparation
By epoxy acrylate 35g, photoinitiator 2g (hydroxycyclohexyl phenyl ketone), levelling agent 0.1g (polydimethylsiloxanes
Alkane), defoaming agent 0.02g (Defoamer CN-117), be dispersed with stirring under blender 3-6h be made UV light-cured epoxy acrylic acid
Ester paint.
Beneficial effects of the present invention are further illustrated below by experimental data:
With GB/T1732-1993 " paint film impact resistance measuring method " for standard, weight quality 1Kg, not cause paint film
The maximum height expression of destruction, unit Kgcm, to measure the flexibility of paint film
Abrasion performance is executed by GB/T1768-79 (89)
Adhesive force is executed by GB/T9286-88, is qualification with level-one
The detection data of each embodiment and comparative example is shown in Table 1:
Table 1
As it can be seen from table 1 adhesive force and abrasion resisting ability obtain greatly in mechanical property after addition graft polymerization preformer graphene
Ground is promoted, and most importantly its impact resistance, that is, toughness is significantly improved.
Claims (7)
1. a kind of preparation method of the epoxy acrylate of graphene graft modification, which comprises the following steps:
Step (1): acylated graphene oxide is made in graphene oxide and acylation reaction；The acylating agent is thionyl chloride；
Step (2): acylated graphene oxide, the acrylate containing active group, acid binding agent are reacted, and graphene modified third is made
Olefin(e) acid ester；
Step (3): epoxy resin is dissolved in reactive diluent, then adds graphene modified propylene made from step (2)
Acid esters, catalyst and polymerization inhibitor are simultaneously copolymerized the epoxy acrylate that the graphene graft modification is made at 115 DEG C -135 DEG C；
The acid value of polymerization 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 the mass ratio of catalyst and epoxy resin is 0.005-0.015:1, the matter of polymerization inhibitor and epoxy resin
Amount is than being 0.001-0.002:1；
The catalyst is N, at least one of N- dimethyl benzylamine, triphenylphosphine, tetraethylammonium bromide；
The polymerization inhibitor is at least one of hydroquinone, 2,5 di tert butyl hydroquinone, p-hydroxyanisole；
The reactive diluent be epoxy propane butyl ether, propylene oxide phenyl ether, in ethylene glycol diglycidylether extremely
Few one kind；
The epoxy resin is epoxy resin E-44.
2. the preparation method of the epoxy acrylate of graphene graft modification as described in claim 1, which is characterized in that step
(1) in, reaction temperature is 60-70 DEG C, reaction time 19-24h.
3. the preparation method of the epoxy acrylate of graphene graft modification as described in claim 1, which is characterized in that step
(2) in, the acid binding agent is pyridine and/or triethylamine.
4. the preparation method of the epoxy acrylate of graphene graft modification as claimed in any one of claims 1 to 3, feature
It is, the acrylate containing active group is the compound with 1 structure of formula:
In formula 1, Y is the alkyl of C1~5；R is H or methyl.
5. the preparation method of the epoxy acrylate of graphene graft modification as claimed in claim 4, which is characterized in that described
The acrylate containing active group be (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxyl
At least one of N-butyl.
6. the application of the epoxy acrylate of graphene graft modification made from a kind of method of any one of Claims 1 to 5,
It is characterized in that, is used to prepare photocureable coating.
7. a kind of photocureable coating, which is characterized in that comprise the following components in parts by weight:
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| CN108795107A (en) * | 2018-03-24 | 2018-11-13 | 成都迪泰化工有限公司 | The method of modifying and its product and UV photocureable coating of a kind of graphene |
| CN108977056B (en) * | 2018-08-13 | 2020-06-23 | 南雄市瑞晟化学工业有限公司 | Ultra-wear-resistant ultraviolet curing coating |
| CN109148887B (en) * | 2018-08-30 | 2021-03-23 | 上海力信能源科技有限责任公司 | Preparation method of graphene-carbon nanofiber conductive agent |
| CN110083013B (en) * | 2019-04-19 | 2020-05-22 | 西安交通大学 | Light-curable graphene oxide and preparation method thereof |
| CN112158831A (en) * | 2020-09-28 | 2021-01-01 | 胥彩虹 | Photoactive modified graphene and preparation method and application thereof |
| CN112625533A (en) * | 2020-12-15 | 2021-04-09 | 桐乡市璟祥新材料科技有限公司 | Anticorrosive material of graphene grafted modified acrylic resin and preparation method thereof |
| CN114350229B (en) * | 2022-01-14 | 2022-07-01 | 深圳市朗迈新材料科技有限公司 | Graphene modified epoxy resin floor paint and preparation method thereof |
| CN114410193B (en) * | 2022-01-17 | 2022-10-11 | 深圳市姿彩科技有限公司 | Functionalized TiO 2 Modified light-cured epoxy acrylic resin and preparation method thereof |
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