CN107556492A - A kind of aqueous epoxy resin emulsion of graphene-containing and preparation method thereof - Google Patents
A kind of aqueous epoxy resin emulsion of graphene-containing and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of aqueous epoxy resin emulsion of graphene-containing and preparation method thereof, the specific preparation process of the aqueous epoxy resin emulsion includes：The preparation of polyethylene glycol/graphene composite material, the preparation of aqueous epoxy resins emulsifying agent, the preparation of aqueous epoxy resin emulsion.Wherein polyethylene glycol/graphene composite material is prepared by situ aggregation method, it can be uniformly dispersed graphene and is anchored in polyethylene glycol matrix, when preparing emulsifying agent, hydroxyl on polyethylene glycol surface reacts under catalyst action with epoxy resin, realize the triangular connection of polyethylene glycol, graphene, epoxy resin, during emulsion is prepared, graphene enters in emulsion with emulsifying agent, solve graphene and the problems such as difficult scattered and poor compatibility, obtain the dispersed aqueous epoxy resin emulsion containing graphene in emulsion.The aqueous epoxy resin emulsion for the graphene-containing that the present invention is prepared has that centrifugation, dilution and storage stability are good, and relative to traditional epoxy resin, cost is relatively low, safety and environmental protection and nontoxic；Applied in anticorrosive paint, anticorrosive property and adhesive force are stronger, good impact resistance, are easy to construct.
Description
Technical field
The invention belongs to epoxy resin technical field of aqueous paint, and in particular to a kind of aqueous epoxy resins of graphene-containing
Emulsion and preparation method thereof.
Background technology
Epoxy resin has good physics, chemical property, and its surface to metal and nonmetallic materials has excellent
Adhesive strength, dielectric properties are good, and solidification post-shrinkage ratio is small, and hardness is high, is that coating industry disappears to alkali and most of solvent-stable
One of larger synthetic resin kind of consumption.With enhancing of the society to environmental protection consciousness, coating industry is from traditional
The environment-friendly type coating directions such as solvent based coating hydrotropism coating, high solid coating, powdery paints and photocureable coating are developed, often
Epoxy resin is not soluble in water to be dissolved only in organic solvent, and this is greatly limited the application of epoxy resin, also makes water-based
Epoxy resin obtains application and development.Existing aqueous epoxy emulsion antiseptic power is low, and stability of emulsion is poor, and dryness is slow, VOC content
The shortcomings of high, this also limits its application in anticorrosive paint.
Polyethylene glycol is that the molecule amount as obtained from oxirane with water or ethylene glycol progressively addition polymerization is relatively low
Water soluble polyether, there are the more good hydrophilic properties of ehter bond, water can be dissolved at room temperature but do not dissolve in non-polar solven, be often used as nonionic
Surfactant.Interfacial energy obtains larger raising after its terminal hydroxy group is substituted by hydrophobic groupings such as ester groups, in addition normal temperature and pressure
Lower polyethylene glycol is chemically inert material, ensure that its unique chemical moieties does not change easily.Utilize the excellent of polyethylene glycol
Good characteristic prepares aqueous epoxy resins emulsifying agent with epoxy resin reaction, and coating surface emulsifying agent precipitation when in use can be avoided to ask
Topic, and the emulsion with preferable stability is made.
Graphene be one kind by single layer of carbon atom with sp2The New Type of Carbon of the bi-dimensional cellular shape lattice structure of hybridized orbit composition
Nano material, its great specific surface area and replaces random alignment in the coating, can effectively extend the diffusion of corrosive medium
Path, strengthen the shielding properties of coating, can also greatly improve the corrosion resistance of coating as additive, but its lamella knot
Strong interaction between structure, causes graphene easily to be reunited, thus limits its scale application in coating.
At present, the aqueous epoxide resin paint that graphene is modified mostly is blended using aqueous epoxy resin emulsion and graphene
Or it is blended again with aqueous epoxy resin emulsion after being modified to graphenic surface.China Patent No. CN106085133A is disclosed
A kind of novel aqueous graphite-epoxy alkene anticorrosive paint, the water-based anticorrosive paint are two-component anticorrosive paint, and component A is does not contain
Aqueous epoxy emulsion and the defoamer composition of any cosolvent；B component is the aqueous epoxy curing agent with self-emulsifying function, stone
Black alkene, trbasic zinc phosphate, titanium dioxide, levelling agent, water composition；A, B component exists after being well mixed according to a certain ratio according to working viscosity
It is diluted with water, obtained water-base epoxy graphene anticorrosive paint is only available for spraying, but is not suitable for brushing.China Patent No.
CN106928810A disclose a kind of polypyrrole/graphene/epoxy emulsion tri compound water-based anticorrosive paint and preparation method and
Using the coating is dual-component coating, and component A includes aqueous epoxy resin emulsion, polypyrrole@graphenes composite assistant, divided
Agent, deionized water are killed in powder, polyphosphate, titanium dioxide, defoamer, thickener, levelling agent, microorganism suppression；B component is water-based ring
Oxygen curing agent；During using the coating, component A and B component are well mixed, and are coated on the treated substrate surface in surface,
Coating is made after solidification.
So far, the report in the starting synthesis phase addition graphene for preparing aqueous epoxy resin emulsion is had no, this
A new path is opened for graphene modified epoxy resin emulsion.
The content of the invention
The purpose of the present invention is to prepare polyethylene glycol/graphene composite material using situ aggregation method, enables graphene equal
Even to disperse and be anchored in polyethylene glycol matrix, when preparing emulsifying agent, the hydroxyl on polyethylene glycol surface is in catalyst action
It is lower to be reacted with epoxy resin, the triangular connection of polyethylene glycol, graphene, epoxy resin is realized, is preparing emulsion process
In, graphene enters in emulsion with emulsifying agent, solves graphene and the problems such as difficult scattered and poor compatibility, is obtained in emulsion
The dispersed aqueous epoxy resin emulsion containing graphene.
To achieve these goals, solution of the invention is：
A kind of preparation method of the aqueous epoxy resin emulsion of graphene-containing, comprises the following steps：
（1）The preparation of polyethylene glycol/graphene composite material：Ethylene glycol, graphene, catalyst A are passed through in autoclave,
Be mixed evenly, be passed through high pure nitrogen replace 3 ~ 5 times, then negative pressure is evacuated to -0.1MPa, is warming up to 110 ~ 115 DEG C, slowly to
Reactor is passed through oxirane, keeps 130 ~ 140 DEG C of reactor temperature, 0.2 ~ 0.5MPa of reaction pressure is controlled, by epoxy second
Alkane has all led to.Keep reaction temperature to carry out decompression curing, carry out degassing process after curing, neutralized, inhaled with citric acid after degassing
Attached, dehydration, filtering, dry polyethylene glycol/graphene composite material；（2）The preparation of aqueous epoxy resins emulsifying agent：By step
（1）Polyethylene glycol/graphene composite material and the epoxy resin mixing of gained, are well mixed at 70 ~ 80 DEG C, add catalyst
B, 2 ~ 4h of isothermal reaction after being warming up to 170 ~ 180 DEG C, obtain the aqueous epoxy resins emulsifying agent of graphene-containing；（3）Water-base epoxy
The preparation of resin emulsion：By step（2）Aqueous epoxy resins emulsifying agent and the epoxy resin mixing of obtained graphene-containing, 50
0.5h is stirred at ~ 60 DEG C, deionized water, 0.1 ~ 0.5h of high-speed stirred, the water of obtained graphene-containing are slowly added to after stirring
Property epoxy resin latex.
Step（1）Described in the ratio between the amount of material of ethylene glycol and oxirane be 1:90 ~ 470, the use of the graphene
Amount is the 0.5 ~ 10% of ethylene glycol weight, and the dosage of the catalyst A is the 10 ~ 20% of the amount of ethylene glycol material.
Step（1）Described in graphene could alternatively be functionalization graphene or graphene oxide, the catalyst A is hydrogen
One kind in sodium oxide molybdena, potassium hydroxide.
The graphene includes functionalization graphene.It is preferred that can well dispersed functionalization graphene in a solvent, tool
Body is grafted polar group such as hydroxyl, amino, carboxyl, sulfydryl, sulfonic group, fluorin radical, cl radical, bromine group；Further preferably
It is grafted the trim of carbon-carbon double bonds.
Step（1）Described in the molecular weight of polyethylene glycol that is prepared be 4000 ~ 20000.
Step（2）Described in the weight of polyethylene glycol/graphene composite material and epoxy resin ratio be 1:1 ~ 5, it is described to urge
Agent B dosage is the 0.5 ~ 2% of weight epoxy.
Step（3）Described in graphene-containing aqueous epoxy resins emulsifying agent and epoxy resin weight ratio be 1:2 ~ 6, institute
The mass fraction for stating deionized water is 40 ~ 60%.
The trade mark of the epoxy resin for bisphenol A-type E-12, E-20, E-44, E-51, E-54, E-55 in one kind, institute
It is any one in potassium peroxydisulfate, BFEE, alchlor, triphenyl phosphorus to state catalyst B.
The present invention has the characteristics that compared with prior art and beneficial effect：
（1）Polyethylene glycol is the conventional raw material for preparing aqueous epoxy resins emulsifying agent, and the present invention is in polyethylene glycol preparation process
Graphene is introduced, it is advantageous that：First, polyethylene glycol/graphene composite material is prepared using situ aggregation method, makes graphene
It can be uniformly dispersed and is anchored in polyethylene glycol matrix；Second, when preparing emulsifying agent, the hydroxyl on polyethylene glycol surface is being urged
Reacted in the presence of agent with epoxy resin, epoxy resin open loop, hydroxyl is incorporated into epoxy molecule up, realized
The triangular connection of polyethylene glycol, graphene, epoxy resin, obtain the dispersed emulsifying agent containing graphene；3rd, making
During standby aqueous epoxy resin emulsion, graphene enters in emulsion with emulsifying agent, and it is difficult scattered and compatible to avoid graphene
The problems such as property difference, seamless combination is realized with epoxy resin.
（2）Compared to dispersed graphite alkene direct in aqueous epoxy resin emulsion, preparation method advantage of the present invention is：The
One, because graphene is easily reunited, generally requiring long-time high shear treatment can just scatter, and emulsion pole under these conditions
Easily cause demulsification and fail, inventive process avoids this technical barrier；Second, because graphene is neither hydrophilic nor close
Oil, directly in emulsion during dispersed graphite alkene, graphene dispersion is identical with the probability of aqueous phase in asphalt mixtures modified by epoxy resin lipid phase, causes actually to enter
The problem of graphene amount entered in epoxy resin is uncontrollable, and graphene wastes in aqueous phase, the inventive method graphene is advance
Disperse and be coated in polyethylene glycol, it can be ensured that fully enter in epoxy resin；3rd, because graphenic surface is inert,
Water-based emulsion viscosity is relatively low, and dispersed graphite alkene is needed now with the current directly in emulsion, and otherwise graphene is easily settled and rolled into a ball
Poly-, the inventive method graphene is combined with emulsifying agent, the problem of can avoiding settling and reuniting.
（3）It is many that preparation method of the present invention not only overcomes difficult, the scattered uneven, dust pollution of graphene powder charging etc.
Problem, and the aqueous epoxy resin emulsion for the graphene-containing being prepared is good with centrifugation, dilution and storage stability, relatively
In traditional epoxy resin, cost is relatively low, safety and environmental protection and nontoxic；Applied in anticorrosive paint, anticorrosive property and adhesive force
It is stronger, good impact resistance, it is easy to construct.
Embodiment
In order to be better understood from the present invention, with reference to the embodiment content that the present invention is furture elucidated, but in the present invention
Appearance is not limited solely to the following examples.
Embodiment 1
（1）The preparation of polyethylene glycol/graphene composite material
0.1mol ethylene glycol, 0.2g graphene powders, 0.02mol sodium hydroxides are passed through in autoclave, mixed equal
It is even, it is passed through high pure nitrogen and replaces 3 ~ 5 times, then negative pressure is evacuated to -0.1MPa, is warming up to 110 DEG C, is slowly passed through 9mol to reactor
Oxirane, 130 DEG C of reactor temperature is kept, control reaction pressure 0.35MPa, oxirane has all been led to.Keep anti-
Answer temperature to carry out decompression curing, degassing process is carried out after curing, neutralized, adsorbed with citric acid after degassing, is dehydrated, filtered, dried
Obtain polyethylene glycol/graphene composite material that molecular weight is about 4000；
（2）The preparation of aqueous epoxy resins emulsifying agent
400g polyethylene glycol/graphene composite material and 400g epoxy resin E-44s are well mixed at 70 DEG C, add 2g mistakes
Potassium sulfate, isothermal reaction 4h after being warming up to 170 DEG C, obtain the aqueous epoxy resins emulsifying agent of graphene-containing；
（3）The preparation of aqueous epoxy resin emulsion
Aqueous epoxy resins emulsifying agent and the mixing of 200g epoxy resin of 100g graphene-containings are taken, 0.5h is stirred at 50 DEG C, stirs
200g deionized waters, high-speed stirred 0.5h, the aqueous epoxy resin emulsion of obtained graphene-containing are slowly added to after mixing uniformly.
Embodiment 2
（1）The preparation of polyethylene glycol/graphene composite material
0.1mol ethylene glycol, 0.2g graphene oxide powders, 0.02mol sodium hydroxides are passed through in autoclave, mixing is stirred
Mix uniformly, be passed through high pure nitrogen and replace 3 ~ 5 times, then negative pressure is evacuated to -0.1MPa, is warming up to 110 DEG C, is slowly passed through to reactor
9mol oxirane, 130 DEG C of reactor temperature is kept, control reaction pressure 0.35MPa, oxirane has all been led to.Protect
Hold reaction temperature and carry out decompression curing, degassing process is carried out after curing, neutralized, adsorbed with citric acid after degassing, is dehydrated, filtered,
Polyethylene glycol/graphene oxide composite material that dry molecular weight is about 4000；
（2）The preparation of aqueous epoxy resins emulsifying agent
400g polyethylene glycol/graphene oxide composite material and 400g epoxy resin E-44s are well mixed at 70 DEG C, added
2g potassium peroxydisulfates, isothermal reaction 4h after being warming up to 170 DEG C, obtain the aqueous epoxy resins emulsifying agent containing graphene oxide；
（3）The preparation of aqueous epoxy resin emulsion
Aqueous epoxy resins emulsifying agent and 200g epoxy resin mixing of the 100g containing graphene oxide are taken, is stirred at 50 DEG C
0.5h, 200g deionized waters are slowly added to after stirring, high-speed stirred 0.5h, the water-base epoxy tree containing graphene oxide are made
Fat liquor.
Embodiment 3
（1）The preparation of polyethylene glycol/graphene composite material
0.1mol ethylene glycol, 0.2g functionalization graphenes powder, 0.02mol sodium hydroxides are passed through in autoclave, mixed
Stir, be passed through high pure nitrogen and replace 3 ~ 5 times, then negative pressure is evacuated to -0.1MPa, is warming up to 110 DEG C, slowly leads to reactor
Enter 9mol oxirane, keep 130 DEG C of reactor temperature, control reaction pressure 0.35MPa, oxirane has all been led to.
Keep reaction temperature to carry out decompression curing, carry out degassing process after curing, neutralized, adsorbed with citric acid after degassing, is dehydrated, mistake
Polyethylene glycol/functionalization graphene composite that filter, dry molecular weight are about 4000；
（2）The preparation of aqueous epoxy resins emulsifying agent
400g polyethylene glycol/functionalization graphene composite and 400g epoxy resin E-44s are well mixed at 70 DEG C, added
Enter 2g potassium peroxydisulfates, isothermal reaction 4h after being warming up to 170 DEG C, obtain the aqueous epoxy resins emulsifying agent containing functionalization graphene；
（3）The preparation of aqueous epoxy resin emulsion
Aqueous epoxy resins emulsifying agent and 200g epoxy resin mixing of the 100g containing graphene oxide are taken, is stirred at 50 DEG C
0.5h, 200g deionized waters are slowly added to after stirring, high-speed stirred 0.5h, the water-base epoxy containing functionalization graphene are made
Resin emulsion.
Embodiment 4
（1）The preparation of polyethylene glycol/graphene composite material
0.1mol ethylene glycol, 0.05g graphene powders, 0.01mol sodium hydroxides are passed through in autoclave, mixed equal
It is even, it is passed through high pure nitrogen and replaces 3 ~ 5 times, then negative pressure is evacuated to -0.1MPa, is warming up to 110 DEG C, is slowly passed through to reactor
13.5mol oxirane, 130 DEG C of reactor temperature is kept, control reaction pressure 0.35MPa, oxirane has all been led to.
Keep reaction temperature to carry out decompression curing, carry out degassing process after curing, neutralized, adsorbed with citric acid after degassing, is dehydrated, mistake
Polyethylene glycol/graphene composite material that filter, dry molecular weight are about 6000；
（2）The preparation of aqueous epoxy resins emulsifying agent
500g polyethylene glycol/graphene composite material and 1000g epoxy resin E-51 are well mixed at 80 DEG C, add 5g tri-
Borate ether is fluorinated, isothermal reaction 2h after being warming up to 180 DEG C, obtains the aqueous epoxy resins emulsifying agent of graphene-containing；
（3）The preparation of aqueous epoxy resin emulsion
Aqueous epoxy resins emulsifying agent and the mixing of 400g epoxy resin of 100g graphene-containings are taken, 0.5h is stirred at 60 DEG C, stirs
500g deionized waters, high-speed stirred 0.4h, the aqueous epoxy resin emulsion of obtained graphene-containing are slowly added to after mixing uniformly.
Embodiment 5
（1）The preparation of polyethylene glycol/graphene composite material
0.1mol ethylene glycol, 0.3g graphene powders, 0.02mol sodium hydroxides are passed through in autoclave, mixed equal
It is even, it is passed through high pure nitrogen and replaces 3 ~ 5 times, then negative pressure is evacuated to -0.1MPa, is warming up to 110 DEG C, is slowly passed through to reactor
22.5mol oxirane, 130 DEG C of reactor temperature is kept, control reaction pressure 0.35MPa, oxirane has all been led to.
Keep reaction temperature to carry out decompression curing, carry out degassing process after curing, neutralized, adsorbed with citric acid after degassing, is dehydrated, mistake
Polyethylene glycol/graphene composite material that filter, dry molecular weight are about 10000；
（2）The preparation of aqueous epoxy resins emulsifying agent
100g polyethylene glycol/graphene composite material and 300g epoxy resin E-12 are well mixed at 80 DEG C, add 3g tri-
Phenyl phosphorus, isothermal reaction 2h after being warming up to 180 DEG C, obtain the aqueous epoxy resins emulsifying agent of graphene-containing；
（3）The preparation of aqueous epoxy resin emulsion
Aqueous epoxy resins emulsifying agent and the mixing of 600g epoxy resin of 100g graphene-containings are taken, 0.5h is stirred at 60 DEG C, stirs
1050g deionized waters, high-speed stirred 0.4h, the aqueous epoxy resin emulsion of obtained graphene-containing are slowly added to after mixing uniformly.
Embodiment 6
（1）The preparation of polyethylene glycol/graphene composite material
0.1mol ethylene glycol, 0.6g graphene powders, 0.15mol sodium hydroxides are passed through in autoclave, mixed equal
It is even, it is passed through high pure nitrogen and replaces 3 ~ 5 times, then negative pressure is evacuated to -0.1MPa, is warming up to 110 DEG C, is slowly passed through to reactor
45mol oxirane, 130 DEG C of reactor temperature is kept, control reaction pressure 0.35MPa, oxirane has all been led to.Protect
Hold reaction temperature and carry out decompression curing, degassing process is carried out after curing, neutralized, adsorbed with citric acid after degassing, is dehydrated, filtered,
Polyethylene glycol/graphene composite material that dry molecular weight is about 20000；
（2）The preparation of aqueous epoxy resins emulsifying agent
200g polyethylene glycol/graphene composite material and 600g epoxy resin E-55 are well mixed at 75 DEG C, add 6g tri-
Aluminium chloride, 175 isothermal reaction 3h are warming up to, obtain the aqueous epoxy resins emulsifying agent of graphene-containing；
（3）The preparation of aqueous epoxy resin emulsion
Aqueous epoxy resins emulsifying agent and the mixing of 800g epoxy resin of 200g graphene-containings are taken, 0.5h is stirred at 55 DEG C, stirs
1000g deionized waters, high-speed stirred 0.3h, the aqueous epoxy resin emulsion of obtained graphene-containing are slowly added to after mixing uniformly.
Embodiment selected by above is typical embodiments, and described above is only intended to help the method for understanding the present invention
And its core concept.It should be pointed out that for those skilled in the art, before the principle of the invention is not departed from
Put, some improvement and modification can also be carried out to the present invention, these are improved and modification also falls into the guarantor of the claims in the present invention
In the range of shield.
Claims (7)
1. a kind of preparation method of the aqueous epoxy resin emulsion of graphene-containing, it is characterised in that comprise the following steps：
（1）The preparation of polyethylene glycol/graphene composite material：Ethylene glycol, graphene, catalyst A are passed through in autoclave,
Be mixed evenly, be passed through high pure nitrogen replace 3 ~ 5 times, then negative pressure is evacuated to -0.1MPa, is warming up to 110 ~ 115 DEG C, slowly to
Reactor is passed through oxirane, keeps 130 ~ 140 DEG C of reactor temperature, 0.2 ~ 0.5MPa of reaction pressure is controlled, by epoxy second
Alkane has all led to, and keeps reaction temperature to carry out decompression curing, carries out degassing process after curing, neutralized, inhaled with citric acid after degassing
Attached, dehydration, filtering, dry polyethylene glycol/graphene composite material；
（2）The preparation of aqueous epoxy resins emulsifying agent：By step（1）Polyethylene glycol/the graphene composite material and epoxy of gained
Resin mixes, and is well mixed at 70 ~ 80 DEG C, adds catalyst B, 2 ~ 4h of isothermal reaction, is contained after being warming up to 170 ~ 180 DEG C
The aqueous epoxy resins emulsifying agent of graphene；
（3）The preparation of aqueous epoxy resin emulsion：By step（2）The aqueous epoxy resins emulsifying agent and ring of obtained graphene-containing
Oxygen tree fat is mixed, and 0.5h is stirred at 50 ~ 60 DEG C, and deionized water, 0.1 ~ 0.5h of high-speed stirred, system are slowly added to after stirring
Obtain the aqueous epoxy resin emulsion of graphene-containing.
A kind of 2. preparation method of the aqueous epoxy resin emulsion of graphene-containing as claimed in claim 1, it is characterised in that step
Suddenly（1）Described in the ratio between the amount of material of ethylene glycol and oxirane be 1:90 ~ 470, the dosage of the graphene is ethylene glycol
The 0.5 ~ 10% of weight, the addition of the catalyst A is the 10 ~ 20% of the amount of ethylene glycol material.
A kind of 3. preparation method of the aqueous epoxy resin emulsion of graphene-containing as claimed in claim 1, it is characterised in that step
Suddenly（1）Described in graphene could alternatively be functionalization graphene or graphene oxide, the catalyst A is sodium hydroxide, hydrogen
One kind in potassium oxide.
A kind of 4. preparation method of the aqueous epoxy resin emulsion of graphene-containing as claimed in claim 1, it is characterised in that step
Suddenly（1）Described in the molecular weight of polyethylene glycol that is prepared be 4000 ~ 20000.
A kind of 5. preparation method of the aqueous epoxy resin emulsion of graphene-containing as claimed in claim 1, it is characterised in that step
Suddenly（2）Described in the ratio between the amount of material of polyethylene glycol/graphene composite material and epoxy resin be 1:1 ~ 5, the catalyst B
Dosage be the 0.5 ~ 2% of weight epoxy.
A kind of 6. preparation method of the aqueous epoxy resin emulsion of graphene-containing as claimed in claim 1, it is characterised in that step
Suddenly（3）Described in graphene-containing aqueous epoxy resins emulsifying agent and epoxy resin weight ratio be 1:2 ~ 6, the deionized water
Mass fraction be 40 ~ 60%.
A kind of 7. preparation method of the aqueous epoxy resin emulsion of graphene-containing as claimed in claim 1, it is characterised in that institute
The trade mark for stating epoxy resin is one kind in E-12, E-20, E-44, E-51, E-54, E-55 of bisphenol A-type, the catalyst B
For any one in potassium peroxydisulfate, BFEE, alchlor, triphenyl phosphorus.
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