CN111087651B - High-conductivity waterborne polyurethane/modified graphene composite emulsion and preparation method thereof - Google Patents
High-conductivity waterborne polyurethane/modified graphene composite emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-conductivity waterborne polyurethane/modified graphene composite emulsion and a preparation method thereof, belonging to the field of modification of high polymer materials. According to the invention, hyperbranched polymer Polyethyleneimine (PEI) is adopted to carry out interlayer modification on graphene oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide compound (EDC/NHS) are adopted to carry out edge modification on graphene oxide, PEI modified graphene oxide is introduced into a waterborne polyurethane system in situ, and reduction treatment is carried out to prepare the waterborne polyurethane/PEI modified graphene nano composite emulsion, the nano composite film and the nano composite coating, so that the dispersibility and compatibility of graphene in waterborne polyurethane are further improved, and the conductivity of the composite emulsion is greatly improved.
Description
Technical Field
The invention relates to a high-conductivity waterborne polyurethane/modified graphene composite emulsion and a preparation method thereof, belonging to the field of modification of high polymer materials.
Background
The Waterborne Polyurethane (WPU) has the advantages of safety, environmental protection, energy conservation and the like of waterborne coatings, and also retains the characteristics of excellent film forming property, wear resistance, flexibility and the like of solvent type polyurethane. However, the mechanical properties (strength and modulus) and solvent resistance of the latex film of the polyurethane are not comparable to those of the traditional solvent-based polyurethane, and the like, and the problems exist, so that the further wide application of the waterborne polyurethane is limited.
The aqueous polyurethane/inorganic nano composite system organically combines the characteristics of organic, inorganic and nano materials, and is a very promising method for preparing high-performance aqueous polyurethane functional materials, and graphene has a typical lamellar structure and excellent mechanical properties, electrical conductivity and thermal conductivity, but is easy to agglomerate and difficult to disperse in a polymer matrix.
Disclosure of Invention
In order to solve at least one problem, the invention provides a waterborne polyurethane/modified graphene nano composite emulsion and a preparation method thereof. The invention mainly adopts polyethyleneimine PEI modified graphene oxide, PEI is a hyperbranched polymer containing a large amount of amino, polyethyleneimine PEI is used for carrying out interlayer modification on Graphene Oxide (GO), on the basis, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and an N-hydroxysuccinimide compound are used for carrying out edge modification on the graphene oxide, PEI modified graphene oxide is introduced into a waterborne polyurethane system in situ, and reduction treatment is carried out to prepare a waterborne polyurethane/PEI modified graphene nano composite emulsion, a nano composite film and a nano composite coating, so that the dispersibility and compatibility of the graphene in the waterborne polyurethane are further improved.
The invention fully utilizes the characteristics of the polyethyleneimine PEI, enhances the dispersibility and compatibility between the graphene and the waterborne polyurethane so as to prepare the composite emulsion with excellent performance, and improves the modulus and the conductivity of the waterborne polyurethane emulsion film and the coating. The waterborne polyurethane/modified graphene nano composite emulsion has a good application prospect in the fields of coatings, adhesives, printing ink, surface treatment agents, elastomers, foaming materials, functional films and the like.
The first purpose of the invention is to provide a preparation method of modified graphene oxide, which specifically comprises the following steps:
adding the graphene oxide dispersion liquid into a stirrer, adding polyethyleneimine PEI (polyetherimide) under high-speed stirring, adjusting the pH to 14, and stirring to obtain a mixed liquid; then adjusting the pH value of the mixed solution to 5.5, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and an N-hydroxysuccinimide compound according to the proportion, and carrying out water bath ultrasound to obtain a mixture; and finally, stirring the mixture obtained in the last step in an ice water bath, and then carrying out centrifugal washing to obtain a solid, namely the modified graphene oxide.
In one embodiment, the concentration of the graphene oxide dispersion is 1-5 mg/mL.
In one embodiment, the mass ratio of the graphene oxide to the polyethyleneimine is 6: (4-8).
In one embodiment, the polyethyleneimine is a hyperbranched polymer and has a molecular weight of 1800 to 40000.
In one embodiment, the pH alkaline regulator is NaOH with the concentration of 1 mol/L; the acidity regulator is HCl with the concentration of 1 mol/L.
In one embodiment, the agitation is: stirring for 12 hours at room temperature, wherein the stirring speed is 200-400 rpm.
In one embodiment, the mass ratio of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide compound and graphene oxide is 1: (2-4): (20-40).
In one embodiment, the water bath ultrasound is specifically: the water bath temperature is 25 ℃, the ultrasonic power is 20kV, and the ultrasonic time is 0.5 h.
In one embodiment, the ice-water bath stirring is specifically: the stirring speed is 200rpm, and the stirring time is 24 hours;
in one embodiment, the centrifugal washing is specifically: the solution was washed by centrifugation with 1mol/L HCl, acetone and water, respectively.
In one embodiment, the graphene oxide dispersion is prepared by a modified Hummers method, and the specific preparation method is as follows: under the condition of ice-water bath, mixing the following components in a mass ratio of 5: 30, sequentially adding graphite and potassium permanganate into a sodium nitrate concentrated sulfuric acid solution with a certain concentration (0.05g/mL), uniformly mixing and reacting for 9-12h, subsequently slowly adding distilled water, stirring for 1-2h, adding 85% hydrogen peroxide until the solution becomes light yellow and does not generate bubbles any more, centrifugally washing the solution until the supernatant is neutral, dialyzing for one week, centrifugally dispersing the solution in water, and dispersing the solution by using an ultrasonic cell crusher in an ice water bath to obtain the graphene oxide dispersion liquid.
In one embodiment, the N-hydroxysuccinimide compound is one or more of N-hydroxysuccinimide and N-hydroxysuccinimide sulfonate.
The second object of the present invention is modified graphene oxide obtained by the method for preparing modified graphene oxide according to the present invention.
The third purpose of the invention is to provide a preparation method of the waterborne polyurethane/modified graphene nano composite emulsion, which comprises the following steps:
and (2) dripping the waterborne polyurethane prepolymer into the modified graphene oxide dispersion liquid, stirring at a high speed for emulsification, then adding a reducing agent for reaction, and obtaining the waterborne polyurethane/modified graphene nano composite emulsion after the reaction is finished.
In one embodiment, the concentration of the modified graphene oxide is 1-15 mg/mL.
In one embodiment, the preparation method of the modified graphene oxide comprises the following steps: the modified graphene oxide was dispersed in a mixed solution of water and N, N-dimethylpyrrolidone (NMP).
In one embodiment, the ratio of the mixed solution of water and N, N-dimethylpyrrolidone (NMP) is (1-10): 1.
in one embodiment, the preparation method of the aqueous polyurethane prepolymer comprises the following steps: and (2) dropwise adding oligomer polyol and a catalyst into a diisocyanate compound according to a ratio to react, after dropwise adding, adding a hydrophilic monomer, continuing to react, then measuring the content of the isocyanate group NCO of the generated prepolymer by a toluene-di-n-butylamine method, cooling when the NCO in the aqueous polyurethane prepolymer is close to a theoretical value, adding an amine compound to react, and obtaining the aqueous polyurethane prepolymer after the reaction is finished.
In one embodiment, the amine compound is one or more of triethylamine, ammonia water, triethanolamine, and dimethylethanolamine.
In one embodiment, the preparation method of the waterborne polyurethane prepolymer specifically comprises the following steps: dripping oligomer polyol and a catalyst into a diisocyanate compound according to a ratio, reacting at 50 ℃ for 1-2h after dripping is finished, gradually heating to 60 ℃, adding a hydrophilic monomer, reacting at the temperature for 6-8h, measuring the content of isocyanate (NCO) of the generated prepolymer by using a toluene-di-n-butylamine method, reducing the reaction temperature to 25 ℃ when the theoretical value of NCO is approached, adding triethylamine, and reacting at 60 ℃ for 1-2h to obtain the waterborne polyurethane prepolymer.
In one embodiment, the diisocyanate compound, the oligomer polyol, the catalyst, and the hydrophilic monomer are used in a ratio of (20-40): (30-50): (0.01-0.1): (3-7).
In one embodiment, the prepolymer has a theoretical NCO content of 3% to 6%.
In one embodiment, the viscosity of the aqueous polyurethane prepolymer is adjusted, then the aqueous polyurethane prepolymer is dropwise added into the modified graphene oxide dispersion liquid, the mixture is stirred at a high speed and emulsified for 1 hour, and finally a reducing agent is added to react for 1 hour at 95 ℃ to obtain the aqueous polyurethane/modified graphene nano composite emulsion.
In one embodiment, the catalyst is dibutyltin dilaurate (DBTDL).
In one embodiment, the diisocyanate compound is one or more selected from 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, isophorone diisocyanate, diphenylmethane 4, 4' -diisocyanate, methylcyclohexyl diisocyanate, and 2,2, 4-trimethylhexamethylene diisocyanate.
In one embodiment, the oligomer polyol is selected from one or more of polyethylene glycol, polypropylene glycol, polytetrahydrofuran glycol, polycaprolactone polyol, polycarbonate diol, polyoxyethylene-polyoxypropylene-polyoxyethylene glycol, polyethylene adipate diol, polybutylene adipate diol, polyethylene terephthalate diol, polybutylene terephthalate diol, alpha, omega-dihydroxy polydimethylsiloxane, dihydroxy polydiphenylsiloxane, dihydroxy polytrifluoropropylmethylsiloxane, and has a molecular weight of 400-.
In one embodiment, the hydrophilic monomer is one or more selected from dimethylolpropionic acid, dimethylolbutyric acid and sodium 1, 2-dihydroxy-3-propanesulfonate.
In one embodiment, the reducing agent is one or more of ascorbic acid, hydroiodic acid, hydrazine hydrate and phenylhydrazine.
In one embodiment, the solid content of the aqueous polyurethane/modified graphene nano composite emulsion is 5% -20%.
In one embodiment, the content of graphene in the aqueous polyurethane/graphene nano composite emulsion is 1 wt% to 50 wt% of the amount of the pure aqueous polyurethane polymer.
The fourth purpose of the invention is that the waterborne polyurethane/modified graphene nano composite emulsion is prepared by the preparation method of the waterborne polyurethane/modified graphene nano composite emulsion.
The fifth purpose of the invention is to prepare the waterborne polyurethane/modified graphene nano composite film or nano composite coating by using the waterborne polyurethane/modified graphene nano composite emulsion.
In one embodiment, the nanocomposite emulsion of the present invention is transferred to a glass mold and dried to form a nanocomposite film.
The sixth purpose of the invention is to apply the waterborne polyurethane/modified graphene nano composite emulsion in the fields of coatings, adhesives, printing ink, surface treatment agents, elastomers, foaming materials and functional films.
The invention has the beneficial effects that:
(1) the invention selects the aqueous dispersion of the graphene oxide modified by the Polyethyleneimine (PEI), 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the N-hydroxysuccinimide compound (EDC/NHS), wherein the PEI and the graphene oxide modified by the EDC/NHS have a good dispersion effect because of a plurality of hydrophilic polar groups. And the emulsion preparation method has simple process, easy control of reaction and good repeatability.
(2) According to the invention, polyethyleneimine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and an N-hydroxysuccinimide compound (EDC/NHS) are selected as modifiers to synergistically modify graphene oxide, groups among graphene oxide lamella and at the edges of the lamella are fully utilized, the interaction between waterborne polyurethane and modified graphene oxide is increased, a waterborne polyurethane chain segment is adsorbed on the graphene oxide through a chemical or physical effect, the stable and uniform dispersion of the reduced graphene in a polymer is promoted, and the dispersion concentration of the graphene in the waterborne polyurethane can be effectively improved. Since the graphene oxide has conductivity after being reduced, the electrical property of the aqueous polyurethane/modified graphene composite emulsion is improved by adding the finally modified graphene oxide.
(3) The addition of the modified graphene dispersion liquid effectively improves the conductivity of the aqueous polyurethane coating, and the addition of a certain amount of polyethyleneimine modified graphene oxide endows the aqueous polyurethane composite membrane with a certain modulus improvement.
(4) According to the invention, PEI and EDC/NHS are adopted to modify graphene oxide, polyethyleneimine is a hyperbranched polymer containing a large number of amino groups, and the Graphene Oxide (GO) is subjected to interlayer modification by utilizing Polyethyleneimine (PEI), and on the basis, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide compound (EDC/NHS) are utilized to carry out edge modification on the Graphene Oxide (GO), and the Graphene Oxide (GO) is introduced into a waterborne polyurethane system in the synthesis stage of Waterborne Polyurethane (WPU), and then the high-conductivity waterborne polyurethane/modified graphene nano composite emulsion is obtained after reduction.
Drawings
Fig. 1 is a SEM image of a cross section of the aqueous polyurethane of example 1 and a SEM image of the aqueous polyurethane/modified graphene nanocomposite film of example 4; a: WPU, b: WPU/RGO-PEI (7%), c: WPU/RGO-PEI (10%), d: WPU/RGO-PEI (15%).
FIG. 2 is a sectional SEM photograph of a composite film of PEI-modified graphene and WPU without EDC/NHS modification of comparative example 2.
Fig. 3 is a stress-strain curve of the composite films obtained in example 4 and comparative example 2.
Fig. 4 is a digital photograph of a composite emulsion of PEI modified graphene and WPU without EDC/NHS modification of comparative example 2 and a composite emulsion of PEI and EDC/NHS synergistically modified graphene and WPU of example 4.
Fig. 5 is a graph of the conductivity of WPU composite membranes of example 4 with different amounts of modified graphene added.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
Stress-strain test: the composite membrane is cut into dumbbell-shaped sample strips, the effective length is 50mm, the width is 4mm, the composite membrane is tested by a universal tester, the tensile rate is 100mm/min, the test temperature is 25 ℃, and the average value of more than three groups of parallel experiments is obtained by repeating.
And (3) testing the conductivity: the dried composite coating on the PET substrate was placed on a four-probe stage, the surface resistivity of the film was tested using a model KEITHLEY 2400, jeshley, usa, five times per sample, and the average was taken. Coating size: 2cm × 2cm, test temperature: at 25 ℃.
Example 1
The preparation method of the waterborne polyurethane emulsion and the film comprises the following steps:
adding 25.1g of isophorone diisocyanate (IPDI) into a 1000mL four-necked flask provided with a stirrer, a thermometer and a reflux condenser, dropwise adding 70.0g of polycarbonate polyol (PCDL2000) and 0.15g of catalyst dibutyltin dilaurate (DBTDL) into the flask at room temperature by using a dropping funnel while stirring, controlling the dropwise adding speed within 1.5h, and reacting at 50 ℃ for 2h after the dropwise adding is finished; then heating to 60 ℃, adding 4.96g of dimethylolpropionic acid (DMPA), reacting for 6h, and determining the reaction degree by a toluene-di-n-butylamine back titration method until the content of NCO groups reaches a theoretical value; then 2.10g of triethylamine is added into the polyurethane prepolymer for reaction for 1.5 h; dropwise adding deionized water into the system for emulsification to obtain emulsion; and transferring the nano composite emulsion into a glass mold, and drying to obtain the waterborne polyurethane film which is marked as WPU.
Example 2
Preparing a modified graphene oxide dispersion liquid:
adding the graphene oxide dispersion liquid (with the concentration of 5mg/mL) into a 2L three-neck flask, and stirring at a high speed according to the mass ratio of 6: 4 adding hyperbranched Polyethyleneimine (PEI), then adjusting the pH to 14 by using 1mol/L NaOH, and stirring for 12h at room temperature. The reaction mixture was poured into a 2L beaker, the pH was adjusted to 5.5 with 1mol/L HCl, then 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide compound were added in the ratio (1: 2: 20) and subjected to sonication in a water bath for 0.5 h. Finally, the prepared liquid in the beaker is poured back into a 2L three-neck flask and stirred for 24 hours under the ice-water bath. And (3) respectively centrifugally washing the reaction mixed solution obtained in the last step by using HCl, acetone and water with the concentration of 1mol/L for purification, finally taking out the solid in the centrifugal tube, and re-dispersing the solid in the centrifugal tube into a mixed solution of water and N, N-dimethyl pyrrolidone (NMP) (the volume ratio of the water to the N, N-dimethyl pyrrolidone (NMP) is 1: 1) to obtain a modified graphene oxide dispersion solution with the concentration of 5 mg/mL.
Example 3
The preparation method of the waterborne polyurethane/modified graphene oxide nano composite emulsion and the composite film comprises the following steps:
adding 25.1g of isophorone diisocyanate (IPDI) into a 1000mL four-necked flask provided with a stirrer, a thermometer and a reflux condenser, dropwise adding 70.0g of polycarbonate polyol (PCD2000) and 0.15g of catalyst dibutyltin dilaurate (DBTDL) into the flask at room temperature by using a dropping funnel while stirring, controlling the dropwise adding speed within 1.5h, and reacting at 50 ℃ for 2h after the dropwise adding is finished; then heating to 60 ℃, adding 4.96g of dimethylolpropionic acid (DMPA), reacting for 6h, and determining the reaction degree by a toluene-di-n-butylamine back titration method until the content of NCO groups reaches a theoretical value; then 2.10g of triethylamine is added into the polyurethane prepolymer for reaction for 1.5 h; the viscosity is properly adjusted and is dropwise added into modified graphene oxide dispersion liquid (water dispersion liquid, 2mg/mL) with different contents, and the mixture is stirred at a high speed for reaction for 1 hour; dropwise adding deionized water into the system for emulsification; obtaining aqueous polyurethane/modified graphene oxide nano composite emulsion; and (3) transferring the nano composite emulsion into a glass mold, and drying to obtain the waterborne polyurethane/modified graphene oxide nano composite film. According to the addition amount of the modified graphene oxide, marking the composite membrane as: and WPU/GO-PEI (X%), wherein X% respectively accounts for 7%, 10% and 15% according to different contents, and respectively corresponds to the mass fraction of the modified graphene oxide in the waterborne polyurethane.
Example 4
The preparation method of the waterborne polyurethane/modified graphene nano composite emulsion and the composite film comprises the following steps:
adding 25.1g of isophorone diisocyanate (IPDI) into a 1000mL four-necked flask provided with a stirrer, a thermometer and a reflux condenser, dropwise adding 70.0g of polycarbonate polyol (PCD2000) and 0.15g of catalyst dibutyltin dilaurate (DBTDL) into the flask at room temperature by using a dropping funnel while stirring, controlling the dropwise adding speed within 1.5h, and reacting at 50 ℃ for 2h after the dropwise adding is finished; then heating to 60 ℃, adding 4.96g of dimethylolpropionic acid (DMPA), reacting for 6h, and determining the reaction degree by a toluene-di-n-butylamine back titration method until the content of NCO groups reaches a theoretical value; then 2.10g of triethylamine is added into the polyurethane prepolymer for reaction for 1.5 h; the viscosity is properly adjusted and is dropwise added into modified graphene oxide dispersion liquid (water dispersion liquid, 2mg/mL) prepared in example 2 with different contents, and the mixture is stirred at a high speed for reaction for 1 hour; dropwise adding deionized water into the system for emulsification; and finally adding hydrazine hydrate (the mass fraction is 3%) in a certain ratio (the mass ratio of the graphene to the hydrazine hydrate is 1: 1) to react for one hour at 95 ℃ to obtain the waterborne polyurethane/modified graphene nano composite emulsion, transferring the nano composite emulsion into a glass mold, and drying to obtain the waterborne polyurethane/modified graphene nano composite film. According to the addition amount of the modified graphene, the composite membrane is marked as follows: and WPU/RGO-PEI (X%), wherein the X% respectively accounts for 3%, 5%, 7%, 10%, 15%, 20%, 25%, 30% and 35% according to different contents, and respectively corresponds to the mass fraction of the modified graphene oxide in the waterborne polyurethane.
Comparative example 1
The preparation method of the pure polyethyleneimine modified graphene oxide aqueous dispersion comprises the following specific steps:
preparing graphene oxide aqueous dispersion by improving a Hummers method: under the condition of ice-water bath, sequentially adding graphite and potassium permanganate into a sodium nitrate concentrated sulfuric acid solution with a certain ratio (the mass ratio of the graphite to the potassium permanganate is 5: 20) according to a ratio (the concentration of the sodium nitrate concentrated sulfuric acid solution is 1g/20mL), uniformly mixing and reacting for 12h, then slowly adding distilled water, stirring for 2h, adding 85% hydrogen peroxide until the solution becomes pale yellow and no bubbles are generated, centrifugally washing until the supernatant is neutral, centrifugally dispersing in water after dialysis for one week, and performing dispersion treatment by using an ultrasonic cell crusher under the ice-water bath to obtain a graphene oxide dispersion solution;
adding the graphene oxide dispersion liquid into a 2L three-neck flask, adding 6g of Polyethyleneimine (PEI) with the molecular weight of 1800 under high-speed stirring, adjusting the pH to 14 by using 1mol/L NaOH, and stirring at room temperature for 12 hours; and taking out the reaction mixed solution, respectively carrying out centrifugal washing by using HCl, acetone and water with the concentration of 1mol/L for purification, finally taking out the solid in the centrifugal tube, re-dispersing the solid in an ice water bath into the mixed solution of water and N-methylpyrrolidone NMP for solid content determination, and preparing the pure polyethyleneimine modified graphene oxide dispersion liquid.
Comparative example 2
The preparation method of the waterborne polyurethane/pure polyethyleneimine modified reduced graphene oxide nano composite emulsion comprises the following steps:
adding 25.1g of isophorone diisocyanate (IPDI) into a 1000mL four-necked flask provided with a stirrer, a thermometer and a reflux condenser, dropwise adding 70.0g of polycarbonate polyol (PCD2000) and 0.15g of catalyst dibutyltin dilaurate (DBTDL) into the flask at room temperature by using a dropping funnel while stirring, controlling the dropwise adding speed within 1.5h, and reacting at 50 ℃ for 2h after the dropwise adding is finished; then heating to 60 ℃, adding 4.96g of dimethylolpropionic acid (DMPA), reacting for 6h, and determining the reaction degree by a toluene-di-n-butylamine back titration method until the content of NCO groups reaches a theoretical value; then 2.10g of triethylamine is added into the polyurethane prepolymer for reaction for 1.5 h; the viscosity was appropriately adjusted and the mixture was added dropwise to the dispersion (2 mg/mL) of pure polyethyleneimine modified graphene oxide and pure polyethyleneimine modified graphene oxide prepared in comparative example 1, the addition of the modified graphene was controlled to be the same, and the reaction was carried out for 1 hour with high-speed stirring; dropwise adding deionized water into the system for emulsification; finally adding hydrazine hydrate (the mass fraction is 3%) in a certain proportion to react for one hour at 95 ℃ to obtain the waterborne polyurethane/pure polyethyleneimine modified reduced graphene oxide nano composite emulsion; and transferring the nano composite emulsion into a glass mold, and drying to obtain the waterborne polyurethane/pure polyethyleneimine modified reduced graphene oxide nano composite film. According to different modification methods, the composite membrane is marked as WPU/PRGO-PEI.
Table 1 shows the mechanical properties of the WPU composite membrane in which the modified graphene is added in different amounts in examples 3 and 4, and it is seen from the table that the modulus of the WPU composite membrane is greatly improved with the addition of the modified graphene, but the strain is reduced due to the introduction of the rigid graphene, so the modulus of the waterborne polyurethane is greatly improved with the addition of the modified graphene.
Table 1 mechanical properties of WPU composite membranes with different amounts of modified graphene added in example 5
| Sample (I) | Strain (%) | Stress (Mpa) | Modulus (Mpa) |
| WPU | 977 | 24.6 | 13 |
| WPU/RGO-PEI(7％) | 322 | 8.26 | 57 |
| WPU/GO-PEI(7％) | 213 | 18.21 | 81 |
| WPU/GO-PEI(10％) | 97 | 16.14 | 93 |
| WPU/GO-PEI(15％) | 34 | 23.17 | 144 |
WPU/RGO-PEI (X%): and a cross-section SEM image of the nano composite membrane obtained by introducing graphene obtained by synergistic modification of polyethyleneimine PEI and EDC/NHS into Waterborne Polyurethane (WPU) according to the mass ratio of X%.
Table 2 shows the composite films obtained in example 4 and comparative example 2. The film prepared in comparative example 2 was a film obtained by compositing PEI-modified graphene and WPU only. From table 2, it can be seen that the composite membrane obtained without using the synergistic modification of polyethyleneimine and EDC/NHS has poor performance, which indicates the importance of the synergistic modification of polyethyleneimine and EDC/NHS.
WPU/PRGO-PEI (7%): the composite membrane comprises pure polyethyleneimine modified graphene (PRGO-PEI) and WPU, wherein the PRGO-PEI accounts for 7 wt% of the WPU;
WPU/RGO-PEI (7%): PEI and EDC/NHS synergistically modify the composite membrane of graphene (RGO-PEI) and WPU, wherein the RGO-PEI accounts for 7 wt% of the WPU.
TABLE 2
| Sample (I) | Strain (%) | Stress (Mpa) | Modulus (Mpa) |
| WPU/PRGO-PEI(7％) | 501 | 2.45 | 13 |
| WPU/RGO-PEI(7％) | 322 | 8.26 | 57 |
Table 3 shows the different modified graphene additions in example 4The conductivity of the added WPU composite film can be seen from the table that: with the addition of the modified graphene, the conductivity of the waterborne polyurethane/modified graphene composite coating increases exponentially at the early stage, the use standard of the antistatic coating is reached when the addition amount is 3%, the antistatic coating is saturated when the addition amount is 25%, and the conductivity is 1.33 multiplied by 103(10-6s/cm), and the addition of the modified graphene is proved to greatly improve the electrical property of the waterborne polyurethane/modified graphene composite coating.
Table 3 conducting performance of WPU composite films with different addition amounts of modified graphene in example 4
| Addition amount (wt%) | Electrical conductivity (10)-6s/cm) |
| 0 | 1.1×10-5 |
| 3 | 7×101 |
| 5 | 5.7×102 |
| 10 | 9.5×102 |
| 15 | 1.18×102 |
| 20 | 1.32×103 |
| 25 | 1.33×103 |
| 30 | 1.31×103 |
| 35 | 1.32×103 |
Fig. 1 is a sectional SEM image (a) of a pure WPU film in example 1 and sectional SEM images (b-d) of WPU composite films in example 4 in which modified graphene was added at different contents. As can be seen from the figure: the section of the pure WPU is smooth and flat; FIGS. (b-d) are respectively: and (3) a cross-section SEM image of the aqueous polyurethane/modified graphene nano composite membrane with the addition amounts of 7 wt%, 10 wt% and 15 wt% of modified graphene. As can be seen from the figure, the addition of the modified graphene enables the cross section of the WPU membrane to be rough, the modified graphene is uniformly dispersed in the WPU matrix, the cross section of the composite membrane has a graphene lamellar structure, the graphene lamellar structure is arranged locally, the graphene lamellar structure is uniformly distributed, and the wrinkles and warps are dense. Sheet graphene structures can be seen from a high-power SEM sectional view of the composite membrane with the PEI-GO content of 7 wt%, and the dispersion is uniform, which shows that the PEI-GO and waterborne polyurethane have strong interfacial interaction force and good dispersion, and the improvement of material performance is facilitated.
FIG. 2 is a sectional SEM photograph of a composite film of PEI-modified graphene and WPU without EDC/NHS modification of comparative example 2. As can be seen from fig. 2, when PEI and EDC/NHS are not used for synergistic modification, pure PEI modified graphene has poor dispersibility in WPU, and obvious peeling and cavities occur, which are not favorable for charge conduction in the composite film.
Fig. 3 is a stress-strain curve of the composite films obtained in example 4 and comparative example 2. The addition amount of the modified graphene oxide in example 4 is 7%, and the film prepared in comparative example 2 is a composite film of PEI modified graphene and WPU without EDC/NHS modification, where the addition amount of PRGO-PEI is 7%, abbreviated as WPU/PRGO-PEI (7%). As can be seen from fig. 3: the composite membrane without using polyethyleneimine and EDC/NHS synergistic modification has poor performance, which shows the importance of polyethyleneimine and EDC/NHS synergistic modification.
FIG. 4 is a digital photograph of a composite emulsion of PEI modified graphene and WPU without EDC/NHS modification in comparative example 2 and a composite emulsion of PEI and EDC/NHS synergistically modified graphene and WPU in example 4, wherein the addition amount of both modified graphene is 35%, and it can be seen from the figure that the WPU composite emulsion without PEI and EDC/NHS synergistic modification is extremely unstable, a large amount of agglomeration occurs on the bottle wall, and the dispersibility is poor when the addition amount of modified graphene is high; the WPU composite emulsion synergistically modified by PEI and EDC/NHS has good compatibility and can stably exist for more than 4 weeks.
Fig. 5 is a graph of the conductivity of WPU composite membranes of example 4 with different amounts of modified graphene added. As can be seen from the figure, with the addition of the modified graphene, the conductivity of the waterborne polyurethane/modified graphene composite coating increases exponentially at the early stage, the use standard of the antistatic coating is achieved when the addition amount is 3%, the antistatic coating is saturated when the addition amount is 25%, and the conductivity is 1.33 multiplied by 103(10-6s/cm), and the addition of the modified graphene is proved to greatly improve the electrical property of the waterborne polyurethane/modified graphene composite coating.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. The preparation method for preparing the nano composite emulsion by compounding the modified graphene oxide and the waterborne polyurethane is characterized by comprising the following steps of:
dripping the waterborne polyurethane prepolymer into the modified graphene oxide dispersion liquid, stirring at a high speed for emulsification, then adding a reducing agent for reaction, and obtaining a waterborne polyurethane/modified graphene nano composite emulsion after the reaction is finished;
wherein the modified graphene oxide accounts for 3-35% of the mass of the waterborne polyurethane prepolymer;
the concentration of the modified graphene oxide dispersion liquid is 1-15 mg/mL;
the preparation method of the modified graphene oxide comprises the following steps:
adding the graphene oxide dispersion liquid into a stirrer, adding polyethyleneimine PEI (polyetherimide) under high-speed stirring, adjusting the pH to 14, and stirring to obtain a mixed liquid; then adjusting the pH value of the mixed solution to 5.5, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and an N-hydroxysuccinimide compound according to the proportion, and carrying out water bath ultrasound to obtain a mixture; finally, stirring the mixture obtained in the last step in an ice water bath, and then carrying out centrifugal washing to obtain a solid, namely the modified graphene oxide; the mass ratio of the graphene oxide to the polyethyleneimine is 6: (4-8); the polyethyleneimine is a hyperbranched polymer, and the molecular weight range of the polyethyleneimine is 1800-40000.
2. The preparation method according to claim 1, wherein the concentration of the modified graphene oxide is 1-15 mg/mL.
3. The preparation method of claim 1, wherein the theoretical range of-NCO content in the aqueous polyurethane prepolymer is 3% -6%.
4. The waterborne polyurethane/modified graphene nano composite emulsion obtained by the preparation method of any one of claims 1 to 3.
5. The waterborne polyurethane/modified graphene nanocomposite film or nanocomposite coating prepared from the waterborne polyurethane/modified graphene nanocomposite emulsion according to claim 4.
6. The application of the waterborne polyurethane/modified graphene nano composite emulsion disclosed by claim 4 in the fields of coatings, adhesives, printing inks, surface treatment agents, elastomers, foaming materials or functional films.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732027A (en) * | 2012-05-29 | 2012-10-17 | 东南大学 | Preparation method for graphene oxide-polyethyleneimine composite |
| CN103131728A (en) * | 2011-11-22 | 2013-06-05 | 刘遵峰 | Multifunctional graphene gene vector and gene transfection reagent based on gene vector and preparation method thereof |
| CN106744834A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of aqueous-dispersible conductive Graphene |
| CN107266711A (en) * | 2017-05-19 | 2017-10-20 | 浙江大学宁波理工学院 | Graphene oxide hybrid fire retardant and preparation method thereof |
| CN107383848A (en) * | 2017-08-10 | 2017-11-24 | 江南大学 | A kind of preparation method of aqueous polyurethane/graphene nano complex emulsions |
| CN109970050A (en) * | 2019-05-14 | 2019-07-05 | 广州特种承压设备检测研究院 | The preparation method of modified graphene and modified graphene slurry |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020057417A1 (en) * | 1999-02-19 | 2002-05-16 | Galin Miles A. | Polysaccharide coating of contact lenses |
-
2019
- 2019-12-31 CN CN201911415130.0A patent/CN111087651B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131728A (en) * | 2011-11-22 | 2013-06-05 | 刘遵峰 | Multifunctional graphene gene vector and gene transfection reagent based on gene vector and preparation method thereof |
| CN102732027A (en) * | 2012-05-29 | 2012-10-17 | 东南大学 | Preparation method for graphene oxide-polyethyleneimine composite |
| CN106744834A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of aqueous-dispersible conductive Graphene |
| CN107266711A (en) * | 2017-05-19 | 2017-10-20 | 浙江大学宁波理工学院 | Graphene oxide hybrid fire retardant and preparation method thereof |
| CN107383848A (en) * | 2017-08-10 | 2017-11-24 | 江南大学 | A kind of preparation method of aqueous polyurethane/graphene nano complex emulsions |
| CN109970050A (en) * | 2019-05-14 | 2019-07-05 | 广州特种承压设备检测研究院 | The preparation method of modified graphene and modified graphene slurry |
Non-Patent Citations (2)
| Title |
|---|
| Preparation of novel cross-linked graphene oxide membrane for desalination applications using (EDC and NHS)-activated graphene oxide and PEI;Parisa SadatParsamehr et al;《Desalination》;SCI;20190723;第468卷;第114079页 * |
| 功能化石墨烯改性水性聚氨酯及其性能;郑春森等;《复合材料学报》;20171231;第34卷(第12期);第2643-2652页 * |
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