CN104804204A - Graphene/thermoplastic polyurethane composite and preparation method thereof - Google Patents
Graphene/thermoplastic polyurethane composite and preparation method thereof Download PDFInfo
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- CN104804204A CN104804204A CN201510194684.8A CN201510194684A CN104804204A CN 104804204 A CN104804204 A CN 104804204A CN 201510194684 A CN201510194684 A CN 201510194684A CN 104804204 A CN104804204 A CN 104804204A
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Abstract
The invention discloses a graphene/thermoplastic polyurethane composite and a preparation method and application thereof. The improved Hummers method is adopted to prepare graphene oxide which is dispersed in DMF to be subjected to ultrasonic treatment, TPU (Thermoplastic polyurethanes) swollen in DMF is poured in, and the solution coating film-forming process is adopted to prepare a GO (Graphene Oxide)/TPU composite film which is subjected to in-situ thermal recovery treatment for 2 h at 200 DEG C to prepare the graphene/thermoplastic polyurethane composite. The prepared graphene/thermoplastic polyurethane composite has the excellent electrical property, is uniform in filler dispersion, can be used for preparing TPU medical cushions, TPU biogas storage bags, TPU wading products and TPU water and oil storage bags, and can also be used in the field demanding relatively much on the obstructing and antistatic performance of materials.
Description
Technical field
The invention belongs to polymer laminated film preparing technical field, be specifically related to a kind of Graphene/Thermoplastic polyurethane composite material and its preparation method and application.
Background technology
A kind of heating that Polyurethane Thermoplastic Elastomer (TPU) is made up of vulcabond, polyvalent alcohol and short chain glycol can plastify, solvent can dissolve (AB)
ntype block linear polymer.Urethane is a kind of macromolecular material with extensive use, is mainly used in the aspects such as automobile, building, pavement material, mine, exploitation, electronics and space flight.In recent years, the urethane injecting paste material development as one of important chemical consolidation material is also very rapid, and people have turned one's attention to TPU water storage bag, the military oil storage bag of TPU, TPU paddle series products etc.
The ideal chose of following alternative hard tank as military oil storage bag using TPU.Software oil bag compared with metallic oil tank, have lightweight, volume is little, debit's advantage such as is just removed in not corrosion, handling transport and expansion, is widely used in battlefield storing bulk oil plant by U.S. army.In particular cases, also collapsible fuel tank can be placed in as fortune oil vessel on automobile, naval vessel and aircraft, some collapsible fuel tanks also can be used for air transport, air-drop, vertiplane handling, haul waterborne and fittings storage oil plant.Alternative traditional iron oil tank or fuel tank in the various fields such as processed oil storage, pipe first-aid, become the new way of a kind of storage and transport liquid.The same with other macromolecular material, polyurethane material itself has very high surface resistivity, in use easily produces static charge accumulation, is the important hidden danger causing the security incident such as fire, blast.
Graphene is by individual layer Sp
2hydbridized carbon atoms tightly packed one-tenth bi-dimensional cellular shape crystalline network carbon material.The monoatomic layer structures shape that Graphene the is special physical properties of its uniqueness, as high strength, high-modulus, high thermal conductivity, high electron mobility, high-ratio surface sum high obstructing performance etc.The unique electronic that Graphene shows and physical property, make it in polymer composites, have important application prospect.But the use of high toxicity reductive agent is related to owing to preparing reduced graphene technique, not only may bring potentially dangerous in laboratory and large-scale commercial production, and remain in the toxic reagent in goods and also can have a negative impact to the physicals of polymkeric substance.Therefore, find a kind of without the need to reductive agent, the complete processing that low cost prepares conductive graphene matrix material becomes a problem demanding prompt solution.
Graphite oxide is a large amount of shuttle base, the light oxygen-containing functional group such as base, epoxy because surface has, and is easy to realize in water and in DMF to peel off and dispersed after supersound process, and with single-layer oxidized graphite, i.e. graphene oxide (GO) form existence.And can be dispersed in uniformly in TPU matrix.In the present invention, take TPU as matrix, obtain graphene oxide compound polyurethane material film by solution casting moulding process, then by heating the technique of in-situ reducing, under without the need to the condition of reductive agent, prepare reduced graphene matrix material efficiently, and its conductivity has been measured.In current domestic and foreign literature, that carries out antistatic treatment to TPU mainly needs to add a large amount of additive based on carbon black and metal oxide etc., and also rarely have report, the present invention successfully provides new approach for preparing Novel integrated TPU nano composite material, also provide new thinking and exploration for Future Development novel high-performance polymer nanocomposites simultaneously, make the present invention academicly having innovation research value, there is economic results in society and strategic value in actual applications widely.
Summary of the invention
The object of the invention is to for deficiency of the prior art and defect, a kind of Graphene/Thermoplastic polyurethane composite material and its preparation method and application is provided, obtained thin-film material has good antistatic property, and without the need to any reductive agent, safety and environmental protection, has economic results in society and strategic value widely.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of Graphene/Thermoplastic polyurethane composite material, adopt and improve Hummers legal system for graphene oxide, be scattered in DMF, supersound process, pour the TPU swollen in DMF into, solution coating film-forming process is adopted to obtain GO/TPU composite material film, then through in-situ heat reduction treatment, obtained Graphene/Thermoplastic polyurethane composite material.
Concrete steps are as follows:
1) first graphite is carried out deepfreeze, put in low-temp reaction bath, slowly add the vitriol oil while stirring, and add potassium permanganate in batches in 1h, low-temp reaction half an hour, be heated to 50 DEG C, reaction 12h, adds deionized water, stir 15 minutes, drip hydrogen peroxide, pickling, be washed to neutrality, freeze-drying obtains graphene oxide;
2) joined by graphene oxide in DMF solution, 100W ultrasonic disperse 1 ~ 2h, pours the TPU swollen in DMF into, stirs 2 ~ 5h, 100W ultrasonic disperse, 1 ~ 2h, excluding air, leave standstill 1 ~ 2h under normal temperature;
3) film, controlling diaphragm thickness 0.06 ~ 0.08mm, obtains GO/TPU composite material film after solvent fully volatilizees;
4) GO/TPU composite material film is dried 2 h at 200 DEG C, obtained Graphene/Thermoplastic polyurethane composite material.
In step 1), deepfreeze graphite is placed in low-temp reaction bath to be cooled to 0 DEG C.
In step 1), low-temp reaction temperature is lower than 5 DEG C.
In step 1), pickling is employing 45 DEG C, 3wt.% dilute hydrochloric acid cleaning graphene oxide head product 3 times.
Parameters of freeze-drying process in step 1): temperature-50 DEG C, time 48 ~ 72h.
Step 2) in swelling time TPU and DMF mass volume ratio be 1g:6mL.
Described Graphene/Thermoplastic polyurethane composite material to be paddled series products and TPU water storage oil storage bag for the preparation of TPU medical mattress, TPU biogas storage-bag, TPU.
beneficial effect of the present invention is:
(1) the present invention to utilize on GO lamella containing a large amount of oxy radical, is dispersed in DMF uniformly, and in organic matrix, keeps again its good consistency, prevent Graphene to reunite through ultrasonic energy, is more conducive to its dispersed in polymeric matrix.Obtain graphene oxide compound polyurethane material film by solution casting moulding process, then by heating the technique of in-situ reducing, under without the need to the condition of reductive agent, prepare reduced graphene matrix material efficiently.
(2) the present invention is by the technique of heating in-situ reducing, reduced graphene matrix material has been prepared efficiently under without the need to the condition of reductive agent, make Graphene can with firm and be evenly distributed in TPU matrix to be formed and combine closely, in TPU collective, form three-dimensional conductive network, improve the antistatic property of material.
(3) the TPU composite material film safety and environmental protection prepared of the present invention, is particularly useful for preparing water storage, oil storage bag thin-film material; Meanwhile, the present invention adapts to the demand in current market, and preparation method is scientific and reasonable, operation is simple, strong operability, drastically increases TPU value-added content of product, and extends its range of application, has market outlook and significant social benefit widely.
Accompanying drawing explanation
Fig. 1 is graphite oxide thermogravimetric curve figure.
Fig. 2 is the thermogravimetric curve figure of TPU.
Fig. 3 is the SEM figure of pure TPU film and TPU composite material film.
Fig. 4 is the volume resistance change curve of the in-situ heat reduced graphene/compound polyurethane material of Different adding amount.
Embodiment
More being convenient to make content of the present invention understand, below in conjunction with embodiment, technical solutions according to the invention are described further, but the present invention being not limited only to this.
embodiment 1
1) GO of 150mg is joined in 20mlDMF solution form stable graphite oxide DMF dispersion liquid, and under 100W ultrasonic disperse 2h, swelling TPU solution in DMF is in advance poured into after it is stable, stir 2 ~ 5h under normal temperature, under 100W, ultrasonic disperse 1 ~ 2h gets rid of the air in liquid/paste and leaves standstill 1 ~ 2h;
2) film: be positioned over by sheet glass clean and tidy for surface on film applicator and carry out film, controlling diaphragm thickness 0.06 ~ 0.08mm, obtains graphene oxide/Thermoplastic polyurethane composite material after solvent fully volatilizees.
3) preparation of in-situ heat reduced graphene/compound polyurethane material: the graphene oxide/Thermoplastic polyurethane composite material obtained is put into 200 DEG C of baking ovens and dries 2 h, matrix material becomes grey black by dark-brown, obtained in-situ heat reduced graphene/compound polyurethane material (being labeled as 1#TPU).
embodiment 2
1) GO of 300mg is joined in 20mlDMF solution form stable graphite oxide DMF dispersion liquid, and under 100W ultrasonic disperse 2h, swelling TPU solution in DMF is in advance poured into after it is stable, stir 2 ~ 5h under normal temperature, under 100W, ultrasonic disperse 1 ~ 2h gets rid of the air in liquid/paste and leaves standstill 1 ~ 2h;
2) film: be positioned over by sheet glass clean and tidy for surface on film applicator and carry out film, controlling diaphragm thickness 0.06 ~ 0.08mm, obtains graphene oxide/Thermoplastic polyurethane composite material after solvent fully volatilizees.
3) preparation of in-situ heat reduced graphene/compound polyurethane material: the graphene oxide/Thermoplastic polyurethane composite material obtained is put into 200 DEG C of baking ovens and dries 2 h, matrix material becomes grey black by dark-brown, obtained in-situ heat reduced graphene/compound polyurethane material (being labeled as 2#TPU).
embodiment 3
1) GO of 450mg is joined in 20mlDMF solution form stable graphite oxide DMF dispersion liquid, and under 100W ultrasonic disperse 2h, swelling TPU solution in DMF is in advance poured into after it is stable, stir 2 ~ 5h under normal temperature, under 100W, ultrasonic disperse 1 ~ 2h gets rid of the air in liquid/paste and leaves standstill 1 ~ 2h;
2) film: be positioned over by sheet glass clean and tidy for surface on film applicator and carry out film, controlling diaphragm thickness 0.06 ~ 0.08mm, obtains graphene oxide/Thermoplastic polyurethane composite material after solvent fully volatilizees.
3) preparation of in-situ heat reduced graphene/compound polyurethane material: the graphene oxide/Thermoplastic polyurethane composite material obtained is put into 200 DEG C of baking ovens and dries 2 h, matrix material becomes grey black by dark-brown, obtained in-situ heat reduced graphene/compound polyurethane material (being labeled as 3#TPU).
embodiment 4
1) GO of 60mg is joined in 20mlDMF solution form stable graphite oxide DMF dispersion liquid, and under 100W ultrasonic disperse 2h, swelling TPU solution in DMF is in advance poured into after it is stable, stir 2 ~ 5h under normal temperature, under 100W, ultrasonic disperse 1 ~ 2h gets rid of the air in liquid/paste and leaves standstill 1 ~ 2h;
2) film: be positioned over by sheet glass clean and tidy for surface on film applicator and carry out film, controlling diaphragm thickness 0.06 ~ 0.08mm, obtains graphene oxide/Thermoplastic polyurethane composite material after solvent fully volatilizees.
3) preparation of in-situ heat reduced graphene/compound polyurethane material: the graphene oxide/Thermoplastic polyurethane composite material obtained is put into 200 DEG C of baking ovens and dries 2 h, matrix material becomes grey black by dark-brown, obtained in-situ heat reduced graphene/compound polyurethane material (being labeled as 4#TPU).
Fig. 1 is the TG figure of graphite oxide, Fig. 2 is that the TG of TPU schemes.Can observe graphite oxide by Fig. 1 and occur obviously mass loss at about 200 DEG C, when 300 DEG C, the residual mass of graphite oxide is 76%.Show that graphite oxide there occurs comparatively strong reduction reaction near 200 DEG C.The a large amount of organic group in graphite oxide surface is reduced at 200 DEG C, and the thermal reduction Graphene obtained has higher ordered structure.After 300 DEG C, curve becomes mild, shows graphite oxide at a higher temperature by the limitation reduced further.As seen from Figure 2, the weight loss of TPU occurs in after 300 DEG C, does not affect before 300 DEG C concerning TPU, so, 200 DEG C are decided to be the heat reduction temperature of redox graphene/Thermoplastic polyurethane composite material.
Fig. 3 is in-situ heat reduced graphene/compound polyurethane material SEM profile scanning figure.
As can be seen from Fig. 3 a, the surface of fracture of pure TPU is comparatively smooth, smooth, display brittle rupture, and Fig. 3 b situ thermal reduction graphene/polyurethane composite material surface of fracture is more coarse, observe Graphene to disperse uniformly in TPU matrix, and can find out that Graphene is coated by TPU matrix, lamella still keeps pleated structure, unordered is dispersed in TPU matrix, and being separated does not appear in matrix material, interface between two-phase is fringe, and the consistency of both explanations is better, and this is favourable to the over-all properties of raising matrix material.
The volume resistance change curve of TPU laminated film when Fig. 4 is GO Different adding amount, upper as can be seen from figure, when addition is 2.3%, volume resistance sharply declines nearly 7 orders of magnitude, reach antistatic effect, illustrate that GO has defined conductive network passage in TPU matrix, reaches antistatic effect when addition is 2.3%.And when continuing to increase GO, volume resistance is almost constant, illustrates that GO is substantially saturated in TPU matrix, so desirable addition is 2.3wt%.
Composite material film provided by the present invention is applicable to preparation TPU medical mattress, TPU biogas storage-bag, TPU paddle the field that series products, TPU water storage oil storage bag etc. have higher requirements to obstruct and the antistatic property of material.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (9)
1. the preparation method of Graphene/Thermoplastic polyurethane composite material, it is characterized in that: adopt and improve Hummers legal system for graphene oxide, be scattered in DMF, supersound process, pour the TPU swollen in DMF into, solution coating film-forming process is adopted to obtain GO/TPU composite material film, then through in-situ heat reduction treatment, obtained Graphene/Thermoplastic polyurethane composite material.
2. the preparation method of Graphene/Thermoplastic polyurethane composite material according to claim 1, is characterized in that: concrete steps are as follows:
1) first graphite is carried out deepfreeze, put in low-temp reaction bath, slowly add the vitriol oil while stirring, and add potassium permanganate in batches in 1h, low-temp reaction half an hour, be heated to 50 DEG C, reaction 12h, adds deionized water, stir 15 minutes, drip hydrogen peroxide, pickling, be washed to neutrality, freeze-drying obtains graphene oxide;
2) joined by graphene oxide in DMF solution, 100W ultrasonic disperse 1 ~ 2h, pours the TPU swollen in DMF into, stirs 2 ~ 5h, 100W ultrasonic disperse, 1 ~ 2h, excluding air, leave standstill 1 ~ 2h under normal temperature;
3) film, controlling diaphragm thickness 0.06 ~ 0.08mm, obtains GO/TPU composite material film after solvent fully volatilizees;
4) GO/TPU composite material film is dried 2 h at 200 DEG C, obtained Graphene/Thermoplastic polyurethane composite material.
3. the preparation method of Graphene/Thermoplastic polyurethane composite material according to claim 2, is characterized in that: in step 1), deepfreeze graphite is placed in low-temp reaction bath to be cooled to 0 DEG C.
4. the preparation method of Graphene/Thermoplastic polyurethane composite material according to claim 2, is characterized in that: in step 1), low-temp reaction temperature is lower than 5 DEG C.
5. the preparation method of Graphene/Thermoplastic polyurethane composite material according to claim 2, is characterized in that: in step 1), pickling is employing 45 DEG C, 3wt.% dilute hydrochloric acid cleaning graphene oxide head product 3 times.
6. the preparation method of Graphene/Thermoplastic polyurethane composite material according to claim 2, is characterized in that: parameters of freeze-drying process in step 1): temperature-50 DEG C, time 48 ~ 72h.
7. the preparation method of Graphene/Thermoplastic polyurethane composite material according to claim 2, is characterized in that: step 2) in swelling time TPU and DMF mass volume ratio be 1g:6mL.
8. Graphene/Thermoplastic polyurethane composite material that the method for claim 1 is obtained.
9. the application of Graphene/Thermoplastic polyurethane composite material that obtains of the method for claim 1, is characterized in that: described Graphene/Thermoplastic polyurethane composite material to be paddled series products and TPU water storage oil storage bag for the preparation of TPU medical mattress, TPU biogas storage-bag, TPU.
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| CN106147204A (en) * | 2016-08-30 | 2016-11-23 | 苏州佰锐生物科技有限公司 | A kind of preparation method of graphene/polyaniline/conductive polyurethane laminated film |
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