CN105085835B - A kind of graphene modified polyvinyl acetate class film forming agent preparation method - Google Patents
A kind of graphene modified polyvinyl acetate class film forming agent preparation method Download PDFInfo
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Abstract
The invention provides a kind of graphene modified polyvinyl acetate class film forming agent preparation method, this method is by graphene, functionalization graphene is made in graphene oxide or amination graphene after ethylenically unsaturated monomer modified reaction, vinylacetate is distributed it to again, in the body or the aqueous solution of esters of acrylic acid or unsaturated acids anhydride monomer, through emulsion polymerization, graphene modified polyvinyl acetate class emulsion film forming agent is made, this method reaction temperature is low, technique is simple, cost is low, electrical efficiency is high, gained film forming agent can be used as antistatic or conductive film forming agent to use, for preparing glass fiber wire-drawing size, textile sizing agent, leather finishing agent, carbon fiber sizing agent, adhesive or coating etc., the film forming agent can effectively reduce material surface resistance, for antistatic or electromagnetic shielding material field.
Description
Technical field
The invention belongs to a kind of antistatic or conductive film forming agent technical field, specially a kind of graphene is modified poly-vinegar acid second
Alkene esters film forming agent preparation method.
Background technology：
Fiber glass reinforcement（FRP）With density is small, intensity is high, electric insulation, it is corrosion-resistant, the features such as being easily worked,
It is widely used in the hi-tech industries such as Aero-Space, communications and transportation, instrument and meter.But because glass fibre and resin all have
Higher surface resistivity and specific insulation, when frictional heat occurs between object, electronics transfer or electromagnetic induction is excited to cause
The uneven distribution of body surface electric charge, produces buildup of static electricity, if storeroom occurs also cause corona discharge during severe friction
Or spark discharge, cause inflammable, explosive material in surrounding environment to catch fire or explode, therefore with anti-static composite material with weight
Application value is wanted, anti-static composite material is mainly prepared using addition graphite or carbon black method at present, is difficult to be formed when the amount of filling out is low
Enough conductive networks, composite materials property can be caused to decline when the amount of filling out is too high, and add the anti-quiet of conductive fiber preparation
Composite is to eliminate electrostatic by electronics conduction and principle of corona discharge, and electrostatic can be eliminated within the extremely short time, and
And crisscross overlap joint forms continuous conduction network to fiberfill each other, and higher conductance can be obtained in low loading, is resisted quiet
Electric significant effect is lasting, and is avoided that influence of the powder antistatic filler to material mechanical performance, so the development of conductive fiber
As preparing the important channel of anti-static composite material, but numerous preparation methods are all difficult to the prepare with scale of conductive fiber
Or use, turn into the bottleneck of anti-static composite material development.
Electroconductive glass fibre packing material, glass fibre are a kind of new function material and knot in inorganic non-metallic material
Structure material.The cost of raw material is low, large-scale preparation method is ripe, composite material preparation process is various, and impact resistance is strong, acid resistance
Good, modified easy, glass fibre occupies 98% or so of reinforcing fiber used in composite at present.Led if glass fibre is additional
Electricity Functional, it will while reinforcing material, have antistatic or function of shielding concurrently, realize antistatic and enhancing performance unification.
If Rodolfo Cruz-Silva are by polyaniline（Specific insulation 10-2-102）Coated in fiberglass surfacing, asphalt mixtures modified by epoxy resin is filled
Fat, improving conductivity of composite material simultaneously, enhancing the mechanical performance of composite, sheet resistance reaches 0.33S/cm, such as
Using electroless plating technology, aluminize in fiberglass surfacing, nickel, silver, copper and alloy etc., but silver-plated cost is too high, copper facing, aluminum fiber
In placement a period of time or after heat treatment its electric conductivity drastically declines；Nickel coating easily aoxidizes unlike copper facing, aluminium lamination, but electric
Conductance is low；And the process of glass fibre metal-plated by the glass fibre of the type that has been processed into by complicated cleaning, activation,
, environmental issue be present in coating, the complicated technology cleaned again, the fiber surface coat of metal is rubbed and washing after be easier to peel off it is conductive
Material, wearability and washing fastness are poor, and various preparation methods can not all solve the scale system of electroconductive glass fibre in summary
Standby problem.
Day, eastern textile company succeeded in developing nickel plating electroconductive glass fibre, has started industrialness production already, has been added with this fiber
Work into yarn and cloth it is all conductive and good with the compatibility of plastics.Gifu Prefecture, Japan paper industry pilot plant is developed coated
The electroconductive glass fibre of tin oxide.This fiber may be used as eliminating the filler of electrostatic, MB companies of U.S. aluminium-coated glass-fibre
Reinforced resin do wing surface layer can the Ampere currents of loss 200,000 thunderbolt and it is free of surface defects.There is enterprise with conductive aluminium-coated glass-fibre
Production glass steel tile can apply to easily by the computer room construction of warehouse in thunder disaster environment with its light, cheap, high conductivity, and
The production of electroconductive glass fibre at home is still blank.
Core technology prepared by glass fibre is synthesis and the size compounded technology of film forming agent.The technology is directly connected to
All kinds of fiberglass product inherent qualities, it is one of core competitiveness that major glass manufacturing enterprise keeps sustainable development, independently grinds
Send out film forming agent high-end and be the only way which must be passed that glass big country makes the country prosperous to glass.In order to realize the prepare with scale of electroconductive glass fibre,
Wherein technological approaches the most feasible is the Online integration conducting function in glass fibre production process, realizes structure function one
Change, only introduce high conductivity component in glass fiber wire-drawing infiltration link, i.e., draw electro-conductive glass using highly conductive film forming agent
Fiber is ideal large-scale production approach.The firm two-dimension plane structure of graphene and SP2The electricity of hydridization conjugated path
Sub- mobility, excellent mechanical property, good conductive heat transfer property electromagnet shield effect are made it have, graphene is currently generation
On most thin, most hard nano material, absorptance 2.3%；Thermal conductivity factor is up to 5300 W/m K, and electron mobility surpasses under normal temperature
Cross 15000 cm2/V s, and resistivity only about 10-6Ω cm, good application prospect, this hair are shown in conductive field of heat transfer
It is bright to provide a kind of graphene modified polyvinyl acetate class film forming agent preparation method, for preparing antistatic glass fiber wire-drawing
Size, textile sizing agent, leather finishing agent, carbon fiber sizing agent, adhesive or coating etc..The film forming agent can be reduced effectively
Material surface resistance, for antistatic or electromagnetic shielding material field.
The content of the invention
The invention provides a kind of graphene modified polyvinyl acetate class film forming agent preparation method, this method is by graphite
Alkene, graphene oxide or amination graphene after ethylenically unsaturated monomer modified reaction be made functionalization graphene, then by its
It is distributed in vinylacetate, esters of acrylic acid or unsaturated acids anhydride monomer or the aqueous solution, through emulsion polymerization, graphite is made
Alkene modified polyvinyl acetate class emulsion film forming agent, this method reaction temperature is low, and technique is simple, and cost is low, and electrical efficiency is high, institute
Obtaining film forming agent can use as antistatic film forming agent, be applied for preparing glass fiber wire-drawing size, textile sizing agent, leather
Adorn agent, carbon fiber sizing agent, adhesive or coating etc..The film forming agent can effectively reduce material surface resistance, for antistatic
Or electromagnetic shielding material field.
The step and condition of the present invention is as follows：
A kind of graphene modified polyvinyl acetate class film forming agent preparation method, has following steps：
（1）Graphene, graphene oxide or amination graphene are distributed in the good solvent of ethylenically unsaturated monomer,
It is dispersed with stirring uniformly, after reacting 0.1-20 hours at 20-100 DEG C, functionalization graphene is made；
（2）In 1000 milliliters of there-necked flask, 300-600 ml deionized waters are added, then add emulsifying dispersant
6-50 grams, its dissolving is made under condition of heating and stirring, adds 200-600 grams of functionalization graphene, temperature control is in 50-100
DEG C, the vinyl monomer 200- such as esters of acrylic acid, vinyl acetate esters, unsaturated acid anhydride are then added under nitrogen protective condition
600 grams, it is small that free-radical emulsion polymerization reaction 2-8 is carried out under 0.2-10 grams of persulfuric acid salt or the effect of azo amidine class initiator
When, room temperature is then cooled to, graphene modified ethylene acetate class film forming agent is made；
Described graphene modified polyvinyl acetate class film forming agent preparation method in above-mentioned 1, it is characterised in that including such as
Lower step：The persulfuric acid salt of radical polymerization or azo amidine class initiator and surfactant are dissolved in aqueous solvent, institute
The volume ratio of initiator, surfactant and the aqueous solvent stated is 0.1:1:100-0.5:20:100, place into function graphite
Alkene, vinyl acetate esters, esters of acrylic acid or unsaturated acids anhydride are as polymerized monomer, by emulsion polymerisation process, in temperature
For stirring reaction 5-10 hours under 50-100 DEG C and nitrogen protective condition, vinyl acetate lipin polymer emulsion film forming agent is generated；
It is above-mentioned（1）In it is described:It is unsaturated single that graphene, graphene oxide or amination graphene are distributed to olefinic
In the good solvent of body, the ethylenically unsaturated monomer refer to γ-（Methacryloxypropyl）Propyl trimethoxy silicane, vinyl
Triethoxysilane, vinyltrimethoxy silane, maleic anhydride or glycidyl acrylate class monomer, it is contained in monomer
Alkoxy, epoxy radicals or anhydride group isoreactivity functional group and graphene oxide or the hydroxyl on amination graphene surface, carboxyl or
Amino is reacted, and functionalization graphene is made, wherein graphene or graphene oxide and unsaturated monomer mass ratio are 1:10-
10:1, the mass ratio of unsaturated monomer and solvent is 1:10-9:10.
It is above-mentioned（2）In it is described:In emulsion polymerization surfactant used can be anionic such as：It is stearic
Acid, dodecyl sodium sulfate (SBS), lauryl sodium sulfate (SDS), neopelex (SDBS) etc..Cationic
Such as：Cetyl trimethylammonium bromide (CTMAB), hexadecyltrimethylammonium chloride (CTMAC), trimethyl bromination
Ammonium, bromogeramine (bromogeramine), chlorohexidene etc..
Nonionic is such as：Octyl phenol polyoxyethylene (9) ether (Triton-100), Triton X-100 (emulsifying agent
OP), fatty acid sorbitan（Span）, polyoxyethylene sorbitan fatty acid ester（Tween）, polyvinyl alcohol（PVA）, poly- second two
Alcohol (PEG) etc..
It is above-mentioned（2）In it is described:In emulsion polymerization carry out radical polymerization initiator for persulfate (potassium,
Sodium or ammonium salt) or persulfuric acid salt redox system, azo-bis-isobutyrate hydrochloride（V-50）, azo diisopropylamidinateand azoles
Quinoline hydrochloride（VA-044）, the isobutyl imidazoline hydrochloride (AIBI, VAZO44) of azo two etc., selected solvent is water.
It is above-mentioned（2）In it is described：R in the architectural feature of the monomer of acrylic ester compound1, R2、R3Or R4Can be with
It is hydrogen atom, methyl, methoxyl group or aliphatic molecules chain.
It is above-mentioned（2）In it is described：Vinyl monomer can select vinylacetate, maleic anhydride, acrylamide, acryloyl-oxy
Ethyl front three（Second）Ammonium chloride, methylacryoyloxyethyl front three（Second）Ammonium chloride, acrylyl oxy-ethyl front three（Second）Base
Ammonium chloride, sodium allylsulfonate, methylpropene sodium sulfonate, styrene, SSS etc..
（2）The polymeric reaction temperature of the Raolical polymerizable of described progress is 40-100 DEG C；
（2）Described in functionalization graphene and unsaturated monomer can use the emulsion polymerisation process to feed jointly；Mend
Fill the seeded emulsion polymerization method of addition functionalization graphene and unsaturated monomer mixture；Or first functionalization graphite dispersion is existed
In the aqueous solution, then add the in-situ polymerization that unsaturated monomer is modified polymerization；
The graphene, graphene oxide or amination graphene can be mechanical milling method, chemistry redox method, change
Learn the stone that vapour deposition process, chemosynthesis reaction or surface made from coupling modifier reaction carry hydroxyl, carboxyl or amino structure
Black alkene；
The amination graphene can be that graphene is made by following reaction：By graphene, graphene oxide point
It is dispersed in the amino silicane coupling agents such as γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane or its solvent,
After 10-100 DEG C carries out coupling reaction, filtration washing or distillation remove excessive silane or solvent, obtain amination graphene；
The amination graphene can also be by graphene, graphene oxide according to 1-50% ratios be added to concentrated nitric acid,
In concentrated sulfuric acid mixture, after carrying out nitration reaction 1-24 hours at 20-100 DEG C, obtained after filtering, alkali cleaning, washing to neutrality
Nitro graphene, then by catalytic hydrogen reduction or tetra lithium aluminium hydride reduction or hydrazine hydrate reduction or metal（Tin,
Iron）Acid adding（Hydrochloric acid, sulfuric acid）Graphene of the obtained surface with amino or hydroxyl structure after solution reduction nitro；
Be used as antistatic or electroconductive glass fibre film forming agent, textile sizing agent, leather finishing agent, carbon fiber sizing agent,
Adhesive or coating use.
The invention provides a kind of graphene modified ethylene acetate class film forming agent preparation method, for preparing glass fibre
Wire drawing size, textile sizing agent, leather finishing agent, carbon fiber sizing agent, adhesive or coating etc..The film forming agent can be effective
Material surface resistance is reduced, for antistatic or electromagnetic shielding material field.The conduction prepared is produced or is modified through the film forming agent
Fiber can be used for enhancing polyimides, polyether-ether-ketone, polysulfones etc. to be used for the fields such as space flight, aviation, automobile, electronic instrument to light
The electrostatic dissipation functional requirement of matter Materials with High Strength, the conductive fiber can be additionally used in strengthen PC/ABS/PP/PE be used for automotive trim,
The civilian industries such as heat exchange pipeline, chemical industry equipment are to sports equipment and leisure goods etc..Therefore graphene modified polyvinyl acetate
Type conduction film forming agent has great economic benefit.
Embodiment
Embodiment 1：The preparation of graphene oxide
（1）Low-temp reaction, the 230mL concentrated sulfuric acid is sequentially added in dry beaker, be placed in low-temp reaction bath, treat dense
The temperature of sulfuric acid adds graphite 10g in 0 DEG C or so under strong mixing, add potassium permanganate 30g several times, controls reacting liquid temperature
In two hours of 10-15 DEG C of stirring reaction.
（2）Medium temperature is reacted, by step（1）Beaker be placed in 35 DEG C of waters bath with thermostatic control, when question response liquid temperature degree rises to 35 DEG C,
Continue to stir half an hour.
（3）Pyroreaction, deionized water is added under agitation, it is small to continue stirring half within 100 DEG C for controlling reaction temperature
When, with deionized water by reaction solution dilute 800 ~ 1000mL after, add 5% hydrogen peroxide, filter while hot, with 5% hydrochloric acid and go from
Sub- water washing dries 48h in 50 DEG C of baking ovens, graphene oxide is made to neutrality after filtering.
Embodiment 2：The preparation of graphene
It will be mixed after the ground sieving of gained graphite oxide of embodiment 1 with deionized water, it is in alkalescent to add a small amount of ammoniacal liquor,
Sonic oscillation one hour, the ratio for adding water is 1mg/1mL, obtains the molten colloidal suspensions of brown color, according to sodium borohydride with
The mass ratio of graphene oxide is 10:1 ratio, flow back 10h under 100 DEG C of oil baths, obtains black flocculent deposit, stood
Filter, is dried at room temperature.Obtain graphene.
Embodiment 3：It is prepared by MAH functionalization graphenes
5.0 grams of embodiment 1, the gained graphene oxide of embodiment 2 or graphene are dispersed in 2.0 grams of aminopropyl-triethoxies
In the 50mL tetrahydrofurans or ethanol solution of silane (KH550), after heating reflux reaction 4h, it is evaporated under reduced pressure and removes tetrahydrofuran
Or ethanol, surface amination graphene is obtained, then distribute it in DMAc solution and be made with maleic anhydride progress graft reaction
Maleic anhydride（MAH）Functionalization graphene.
Embodiment 4：It is prepared by KH570 functionalization graphenes
5.0 grams of embodiment 1, the gained graphene oxide of embodiment 2 or graphene are dispersed in 2.0 grams of second of acryloxy three
In the 50mL toluene solutions of TMOS (KH570), after heating reflux reaction 4h, it is evaporated under reduced pressure and removes toluene, obtain surface silicon
Alkane is coupled (KH570) functionalization graphene of vinyl monomer.
Embodiment 5：It is prepared by GMA functionalization graphenes
5.0 grams of embodiment 1, the gained graphene oxide of embodiment 2 or graphene are dispersed in 3.0 grams of Glycidyl methacrylates
Glyceride（GMA）50mL tetrahydrofuran solutions in, after heating reflux reaction 4h, be evaporated under reduced pressure remove tetrahydrofuran, obtain table
Face grafted epoxy monomer（GMA）Functionalization graphene.
Embodiment 6：It is prepared by MAH functionalization graphenes
5.0 grams of embodiment 1, the gained graphene oxide of embodiment 2 or graphene are distributed to the dense sulphur of 18mL concentrated nitric acids 10mL
In sour mixed solution, after being stirred and heated to 70 DEG C of back flow reaction 4h, filtering, 10% sodium carbonate liquor washing, be washed to neutrality again after
Obtain nitro graphene；
5.0g tin grains are placed in the reactor（Or iron powder）, 4.0 grams of nitro graphene, reflux is loaded onto, measures 20ml
Concentrated hydrochloric acid, fraction time add flask from the condensation mouth of pipe and constantly shake reactant mixture.After all hydrochloric acid adds, by flask
As for 30min is heated in the hot bath of boiling, reduction is tended to be complete, reactant is cooled to room temperature, it is filtered, add
The washing of 50%NaOH solution, be washed to neutrality, surface amination graphene be made, then distribute it in DMAc solution with Malaysia
Acid anhydrides carries out graft reaction and maleic anhydride functional graphene is made.
Embodiment 7：It is prepared by graphene modified polyvinyl acetate class film forming agent
First by methyl methacrylate（MMA）, butyl acrylate（BA）, GMA（GMA）With
Vinylacetate（VAc）.Adding 0.5% respectively（Mass ratio）Under the conditions of hydroquinones, it is evaporated under reduced pressure, removes polymerization inhibitor, it is low
Temperature is kept in dark place；Silane resin acceptor kh-550 and KH-570 are evaporated under reduced pressure, be put into refrigerator be sealed it is standby（Example below
Also need equally to handle, slightly）.
120 mL distilled water, 1.0 grams of tween, 1.0 grams of polyoxyethylene nonylphenol ether, polyvinyl alcohol are added in 250 mL there-necked flask
1.0 grams, 2.5 g are put into neopelex, 5.0 grams of maleic anhydride functional graphenes, are warming up to 90 DEG C, stirring
By temperature to 50 DEG C after making solution fully emulsified, 0.3g potassium peroxydisulfates are added, stirring makes it fully dissolve, then measures respectively
VAC10.0 grams, BA, GMA, each 1.0 grams of maleic anhydride, add in small beaker and be uniformly mixed, it is slow with constant pressure addition funnel
It is added drop-wise in reaction bulb, monomer slowly heating simultaneously is added dropwise, temperature rises to 80 DEG C in half an hour, and reaction about needs 3 h, to not having
Stop reaction after having the min of monomers flow back 15, be down to room temperature, save backup.
Embodiment 8：It is prepared by graphene modified polyvinyl acetate class film forming agent
240 mL distilled water are added in 250 mL there-necked flask, 4.5 g is put into neopelex, tells
1.0 grams of temperature, NP1.0 grams of emulsifying agent, 1.0 grams of polyvinyl alcohol, 5.0 grams of KH570 functionalization graphenes, 5.0 grams of GMA function graphites
Alkene, 90 DEG C are warming up to, stirred temperature after making solution fully emulsified to 50 DEG C, add 0.3g potassium peroxydisulfates, stirring makes its abundant
Dissolving, then measures 20.0 grams, BA of VAC respectively, each 1.0 grams of styrene monomer, adds in small beaker and is uniformly mixed, with normal
Pressure dropping funel is slowly dropped in reaction bulb, monomer slowly heating simultaneously is added dropwise, temperature rises to 80 DEG C in half an hour, reaction
About need 3 h, to no min of monomers flow back 15 after stop reaction, be down to room temperature, save backup.
Embodiment 9：It is prepared by graphene modified polyvinyl acetate class film forming agent
120 mL distilled water are added in 250 mL there-necked flask, 2.5 g is put into neopelex, tells
2.0 grams of temperature, 1.0 grams of polyoxyethylene nonylphenol ether, 1.0 grams of polyvinyl alcohol, 5.0 grams of GMA functionalization graphenes, 90 DEG C are warming up to, stirring makes molten
By temperature to 50 DEG C after liquid is fully emulsified, 0.3g potassium peroxydisulfates are added, stirring makes it fully dissolve, then measures VAC10.0 respectively
Gram, BA, sodium allylsulfonate is each 1.0 grams, 5.0 grams of GMA functionalization graphenes, adds in small beaker and is uniformly mixed, uses normal pressure
Dropping funel is slowly dropped in reaction bulb, monomer slowly heating simultaneously is added dropwise, temperature rises to 80 DEG C in half an hour, and reaction is about
Need 3 h, to no min of monomers flow back 15 after stop reaction, be down to room temperature, save backup.
Embodiment 10：It is prepared by graphene modified polyvinyl acetate class film forming agent
120 mL distilled water are added in 250 mL there-necked flask, 2.5 g is put into neopelex, tells
1.0 grams of temperature, 1.0 grams of polyoxyethylene nonylphenol ether, 1.0 grams of polyvinyl alcohol, 5.0 grams of KH570 functionalization graphenes, are warming up to 90 DEG C, stirring makes
By temperature to 50 DEG C after solution is fully emulsified, 0.3g potassium peroxydisulfates are added, stirring makes it fully dissolve, then measures respectively
VAC10.0 grams, BA, GMA, SSS, 5.0 grams of KH570 functionalization graphenes, add in small beaker and be stirred
It is even, it is slowly dropped to constant pressure addition funnel in reaction bulb, monomer slowly heating simultaneously is added dropwise, temperature rises to 80 in half an hour
DEG C, reaction about need 3 h, to no min of monomers flow back 15 after stop reaction, be down to room temperature, save backup.
Embodiment 11：The preparation of graphene modified polyvinyl acetate class electroconductive glass fibre
120 mL distilled water are added in 250 mL there-necked flask, 2.5 g is put into neopelex, tells
1.0 grams of temperature, 1.0 grams of polyoxyethylene nonylphenol ether, 1.0 grams of polyethylene glycol, 5.0 grams of VTES functionalization graphenes, heating
To 90 DEG C, to stir temperature after making solution fully emulsified to 50 DEG C, add 0.3g potassium peroxydisulfates, stirring makes it fully dissolve, then
VAC10.0 grams, BA is measured respectively, sodium allylsulfonate, each 1.0 grams of maleic anhydride, adds in small beaker and is uniformly mixed, and is used
Constant pressure addition funnel is slowly dropped in reaction bulb, monomer slowly heating simultaneously is added dropwise, temperature rises to 80 DEG C in half an hour, instead
3 h should about be needed, to no min of monomers flow back 15 after stop reaction, be down to room temperature, measure gained graphene be modified poly-vinegar acid
10 grams of vinyl esters film forming agent, coating infiltrate in 100 grams of fiberglass surfacings, are put into blanket of nitrogen high temperature furnace and are heated to 400
Degree, room temperature is cooled to after 3 hours, and graphene denatured conductive glass fibre is made.
Embodiment 12：The preparation of graphene modified polyvinyl acetate class electroconductive glass fibre
200 mL distilled water are added in 250 mL there-necked flask, 5.0 g is put into neopelex, tells
1.0 grams of temperature, NP1.0 grams of emulsifying agent, 1.0 grams of polyvinyl alcohol, 10.0 grams of maleic anhydride functional graphenes, are warming up to 90 DEG C, stir
Mix temperature after making solution fully emulsified to 50 DEG C, add 0.5g potassium peroxydisulfates, stirring makes it fully dissolve, then measures respectively
VAC20.0 grams, BA, methylpropene sodium sulfonate, each 1.0 grams of SSS, maleic anhydride functional graphene, add small
It is uniformly mixed in beaker, is slowly dropped to constant pressure addition funnel in reaction bulb, monomer is added dropwise and slowly heats up simultaneously, half
Temperature rises to 80 DEG C in hour, and reaction about needs 3 h, to no min of monomers flow back 15 after stop reaction, be down to room temperature, measure
10 grams of gained graphene modified polyvinyl acetate class film forming agent is taken, coating is infiltrated in 100 grams of fiberglass surfacings, is put into nitrogen
400 degree are heated in atmosphere high temperature furnace, room temperature is cooled to after 3 hours, graphene denatured conductive glass fibre is made.
Embodiment 13：The preparation of graphene modified polyvinyl acetate class conductive polyester fiber
120 mL distilled water, 1.0 grams of tween, 1.0 grams of polyoxyethylene nonylphenol ether, polyethylene glycol are added in 250 mL there-necked flask
1.0 grams, 2.5 g are put into neopelex, 5.0 grams of GMA functionalization graphenes, are warming up to 90 DEG C, stirring makes solution
By temperature to 50 DEG C after fully emulsified, 0.3g potassium peroxydisulfates are added, stirring makes it fully dissolve, then measures VAC10.0 respectively
Gram, sodium allylsulfonate, each 1.0 grams of acrylic acid, add in small beaker and be uniformly mixed, be slowly added dropwise with constant pressure addition funnel
Into reaction bulb, monomer slowly heating simultaneously is added dropwise, temperature rises to 80 DEG C in half an hour, and reaction about needs 3 h, to no list
Stop reaction after 15 min of body backflow, be down to room temperature, measure 10 grams of gained graphene modified polyvinyl acetate class film forming agent,
Coating is infiltrated in 100 grams of polyester fibre surfaces, is put into vacuum drying chamber and is heated to 120 degree, room temperature is cooled to after 3 hours, is made
Graphene denatured conductive nylon fiber.
Embodiment 14：The preparation of graphene modified polyvinyl acetate class electroconductive glass fibre
120 mL distilled water are added in 250 mL there-necked flask, are put into 2.5 g cetyl trimethylammonium bromides
(CTMAB), 2.5 g DTABs, 1.0 grams of tween, 1.0 grams of polyoxyethylene nonylphenol ether, 1.0 grams of polyvinyl alcohol, 5.0 grams
KH570 functionalization graphenes, 90 DEG C are warming up to, stir temperature after making solution fully emulsified to 50 DEG C, add 0.3g azos two
Isopropyl amidine oxazoline hydrochloride（VA-044）, stirring makes it fully dissolve, then measures VAC10.0 grams respectively, acrylyl oxy-ethyl
Each 1.0 grams of trimethyl ammonium chloride, methylacryoyloxyethyl triethyl ammonium chloride, add in small beaker and be uniformly mixed, use
Constant pressure addition funnel is slowly dropped in reaction bulb, monomer slowly heating simultaneously is added dropwise, temperature rises to 80 DEG C in half an hour, instead
3 h should about be needed, to no min of monomers flow back 15 after stop reaction, be down to room temperature, measure gained graphene be modified poly-vinegar acid
10 grams of vinyl esters film forming agent, 10 grams of water is added, 3.0 grams of hydrazine hydrate, coating infiltration is in 100 grams of glass fibres after being well mixed
Surface, it is put into vacuum drying chamber and is heated to 120 degree, room temperature is cooled to after 3 hours, graphene denatured conductive glass fibre is made.
Embodiment 15：The preparation of graphene modified polyvinyl acetate class electroconductive glass fibre
200 mL distilled water are added in 250 mL there-necked flask, are put into 2.5 g cetyl trimethylammonium bromides
(CTMAB), 2.0 grams, 5.0 grams 2.5 g DTABs, 1.0 grams of tween, polyvinyl alcohol GMA function graphites
Alkene, 5.0 grams of KH570 functionalization graphenes, 90 DEG C are warming up to, stir temperature after making solution fully emulsified to 50 DEG C, add
0.5g azo-bis-isobutyrate hydrochlorides（V-50）, stirring makes it fully dissolve, then measures VAC20.0 grams respectively, acryloyl-oxy second
Each 3.0 grams of base trimethyl ammonium chloride, methylacryoyloxyethyl triethyl ammonium chloride, add in small beaker and be uniformly mixed,
It is slowly dropped to constant pressure addition funnel in reaction bulb, monomer slowly heating simultaneously is added dropwise, temperature rises to 80 DEG C in half an hour,
Reaction about need 3 h, to no min of monomers flow back 15 after stop reaction, be down to room temperature, measure gained graphene be modified poly-vinegar
10 grams of vinyl acetate class film forming agent, 10 grams of water is added, 3.0 grams of hydrazine hydrate, coating infiltration is in 100 grams of glass fibers after being well mixed
Dimension table face, it is put into vacuum drying chamber and is heated to 120 degree, room temperature is cooled to after 3 hours, graphene denatured conductive glass fibers is made
Dimension.
Claims (2)
1. a kind of graphene modified polyvinyl acetate class film forming agent preparation method, it is characterised in that prepared according to following steps：
（1）It is prepared by γ-methacryloxypropyl trimethoxy silane functionalization graphene
5.0 grams of graphene oxide or graphene are dispersed in 2.0 grams of γ-methacryloxypropyl trimethoxy silanes
In 50mL toluene solutions, after heating reflux reaction 4h, it is evaporated under reduced pressure and removes toluene, obtain γ-methacryloxypropyl three
Methoxy silane functionalization graphene；
（2）It is prepared by GMA functionalization graphene
The 50mL tetrahydrofurans that 5.0 grams of graphene oxide or graphene are dispersed in 3.0 grams of GMAs are molten
In liquid, after heating reflux reaction 4h, it is evaporated under reduced pressure and removes tetrahydrofuran, obtain GMA function graphite
Alkene；
（3）It is prepared by graphene modified polyvinyl acetate class film forming agent
240mL distilled water is added in 250mL there-necked flask, is put into 4.5 grams to neopelex, 1.0 grams of tween,
1.0 grams of emulsifying agent NPE, 1.0 grams of polyvinyl alcohol, 5.0 grams of γ-methacryloxypropyl trimethoxy
Silane-functionalized graphene, 5.0 grams of GMA functionalization graphenes, 90 DEG C are warming up to, stirring makes solution
50 DEG C are cooled to after fully emulsified, adds 0.3 gram of potassium peroxydisulfate, stirring makes it fully dissolve, then measures vinyl acetate respectively
20.0 grams of ester, butyl acrylate, each 1.0 grams of styrene monomer, add in small beaker and be uniformly mixed, leaked with constant pressure addition
Bucket is added drop-wise in reaction bulb, and monomer is added dropwise and heats up simultaneously, and temperature rises to 80 DEG C in half an hour, and reaction needs 3 h, to no list
Stop reaction after body backflow 15min, be down to room temperature, save backup.
2. a kind of graphene modified polyvinyl acetate class film forming agent preparation method, it is characterised in that prepared according to following steps：
（1）It is prepared by GMA functionalization graphene
The 50mL tetrahydrofurans that 5.0 grams of graphene oxide or graphene are dispersed in 3.0 grams of GMAs are molten
In liquid, after heating reflux reaction 4h, it is evaporated under reduced pressure and removes tetrahydrofuran, obtain GMA function graphite
Alkene；
（2）It is prepared by graphene modified polyvinyl acetate class film forming agent
120mL distilled water is added in 250mL there-necked flask, is put into 2.5 grams to neopelex, 2.0 grams of tween,
1.0 grams of emulsifying agent OPEO, 1.0 grams of polyvinyl alcohol, 5.0 grams of GMA function graphites
Alkene, 90 DEG C are warming up to, stirring makes to be cooled to 50 DEG C after solution is fully emulsified, adds 0.3 gram of potassium peroxydisulfate, and stirring makes its abundant
Dissolving, then 10.0 grams of vinylacetate is measured respectively, butyl acrylate, sodium allylsulfonate is each 1.0 grams, 5.0 grams of methacrylic acids
Ethylene oxidic ester functionalization graphene, add in small beaker and be uniformly mixed, be added drop-wise to constant pressure addition funnel in reaction bulb,
Monomer is added dropwise to heat up simultaneously, temperature rises to 80 DEG C in half an hour, reaction 3 h of needs, to no min of monomers flow back 15 after stop
Only react, be down to room temperature, save backup.
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