CN104530686A - Functional graphene/TPU (thermoplastic polyurethane) film as well as preparation method and application thereof - Google Patents
Functional graphene/TPU (thermoplastic polyurethane) film as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a functional graphene/TPU (thermoplastic polyurethane) film as well as a preparation method and application thereof. The preparation method comprises the following steps: preparing graphene oxide by adopting an improved Hummers method; and performing intercalation modification by using didodecyl dimethyl ammonium bromide (DDAB) at first, then performing reduction by using ascorbic acid to prepare a DDAB-RGO nano composite material, and finally preparing a DDAB-RGO/TPU composite film by using TPU resin as a matrix and adopting a solution coating film-forming process. By adopting the composite film prepared by the method disclosed by the invention, on the one hand, a diffusion infiltration passage of a gas becomes winding, and the perforation difficulty of small-molecule substances of gases and the like is improved, so that the blocking performance of a material is greatly improved; and on the other hand, the DDAB-RGO forms a conductive network in TPU to improve the antistatic performance of the material, so that the composite film is suitable for film materials for water storage and oil storage bags and has wide social and economic benefits.
Description
Technical field
The invention belongs to the preparing technical field of polymer laminated film, be specifically related to a kind of functional graphene/TPU film 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, in chemical structure, TPU does not have or seldom has chemically crosslinked, its molecular weight is linear substantially, wherein A is soft section, is made up of, makes a part for TPU molecular chain keep elastomeric state at normal temperatures the polyester glycol of long flexible chain or polyether glycol.B is that hard section is in vitreous state or crystal form at normal temperatures, is made up of short chain glycol.The chemical structure that wherein AB chain is intersegmental connects with coupling agent vulcabond.
Due to the carbamate groups containing strong polarity in TPU molecule, be insoluble to non-polar group, there is good oil-proofness, toughness, wear resistance, ageing resistance and binding property.TPU material is again a kind of environment-friendly materials of maturation simultaneously, and it repeatedly can repeat recycling, the place that current every PVC can use, and TPU all can become its good substitute, and it also has superiority more more than PVC.TPU because of its superior performance and environmental protection concept day by day welcomed by the people.Have so many premium properties based on TPU, people can't help having 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.But due to the property of high molecular polymer, so there is certain requirement for the obstruct of TPU oil storage bag, the performance such as antistatic.
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.The finishing of Graphene is the key preparing polymer/graphene composite material.
When modified function Graphene with the formal distribution of sheet in TPU matrix time, gas and water vapour and some other small molecule organic compound by during TPU matrix because the obstruction and detouring being subject to layered nano-graphite alkene sheet is walked, so just, extend the distance of small-molecule substance by TPU matrix, thus improve the barrier property of TPU.Graphene forms conductive network in TPU matrix simultaneously, and the Electrostatic Electron that TPU is in use produced is got rid of by the graphene conductive passage formed in TPU matrix, reaches anlistatig effect.If modified graphene and TPU matrix phase capacitive are well, more single-layer graphene films just can be made to be evenly distributed in the matrix of TPU, barrier and antistatic property can be made like this to bring up to original more than several times.
The present invention proposes and after quaternary ammonium salt DDAB is intercalation into graphene oxide, to be reduced the Graphene of obtained DDAB modification again, to improving the problem that Graphene is reunited in organic matrix; Be matrix again with TPU, obtain DDAB-RGO/TPU composite material film by solution casting moulding process, and its barrier property and antistatic property are measured.In current domestic and foreign literature, with DDAB intercalation modifying Graphene TPU matrix material modified 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 functional graphene/TPU film and its preparation method and application is provided.The thin-film material prepared through the inventive method has excellent obstruct and antistatic property, its safety and environmental protection and mechanical property obtains further raising, is particularly useful for preparing water storage oil storage bag thin-film material, has economic results in society and strategic value widely.
For achieving the above object, the present invention adopts following technical scheme:
A kind of functional graphene/TPU film: adopt and improve Hummers legal system for graphene oxide, first carry out intercalation modifying with didodecyldimethylammbromide bromide, reduce with xitix again, obtained DDAB-RGO nano composite material, last with TPU resin for matrix, adopt solution coating film-forming process to obtain DDAB-RGO/TPU laminated film.This laminated film has obstruct and antistatic property.
Preparation method comprises the following steps:
1) Hummers legal system is improved for graphene oxide: in low-temp reaction bath, slowly while stirring the vitriol oil to be added in the graphite after cooling process, then in 1h, add potassium permanganate in batches, reaction system is heated to 50 DEG C after half an hour by low-temp reaction, add deionized water after sustained reaction 12h, continue stirring and drip hydrogen peroxide after 15 minutes, finally carry out pickling and be washed to neutrality, through frozen dried, obtained graphene oxide;
2) the DDAB intercalation modifying of graphene oxide: graphene oxide obtained for step 1) to be dissolved in deionized water and ultrasonic disperse 1 ~ 2h, add DDAB and continue ultrasonic half an hour, stir 3 ~ 6h, filter, wash, through freeze-drying, obtained DDAB-GO nano composite material;
3) reduction reaction of modified graphene: by step 2) obtained DDAB-GO nano composite material ultrasonic disperse in deionized water, add xitix, be heated to 80 ~ 95 DEG C, reaction 2 ~ 6h, filter, wash, through freeze-drying, obtained DDAB-RGO nano composite material;
4) preparation of liquid/paste is mixed: the DDAB-RGO nano composite material that step 3) is obtained to be joined in DMF and ultrasonic disperse 1 ~ 2h, add the TPU particle of drying in advance, 60 ~ 80 DEG C of swelling 6 ~ 8 h, stir 2 ~ 5h again, until after TPU dissolves completely, ultrasonic 1 ~ 2h gets rid of the air in liquid/paste, leaves standstill 1 ~ 2h;
5) film: carry out film on the sheet glass that surface is clean and tidy, controlling diaphragm thickness 0.06 ~ 0.08mm, obtains DDAB-RGO/TPU laminated film after solvent fully volatilizees.
Cooling process described in step 1) refers to that graphite is placed in low-temp reaction bath is cooled to 0 DEG C.
Low-temp reaction temperature described in step 1) controls below 5 DEG C.
Pickling described in step 1) refers to: adopt temperature to be the mass percent of 45 DEG C to be the dilute hydrochloric acid of 3% repeatedly to clean graphene oxide 3 times.
Step 2) or the freeze-drying described in step 3) refer to: freezing temp is-50 DEG C, vacuum-drying 48 ~ 72h.
The mass volume ratio of step 4) TPU particle used and DMF is 1g:6mL.
Described functional graphene/TPU film is as water storage, oil storage bag thin-film material.
beneficial effect of the present invention is:
(1) in the DDAB-GO nano material that the present invention obtains, DDAB is intercalation in aluminum oxide/graphite layer by electrostatic interaction, expand the interlamellar spacing of graphite oxide further, DDAB-RGO nano material after reduction still retains DDAB group, eliminate other oxy radicals simultaneously, make DDAB-RGO not only recover its good electric property, in organic matrix, keep again its good consistency simultaneously, prevent Graphene to reunite, be more conducive to its dispersed in polymeric matrix.
(2) DDAB-RGO nano composite material joins in TPU matrix by the present invention, obtains DDAB-RGO/TPU composite material film by solution casting moulding process.Find after deliberation, in composite material film, DDAB-RGO and TPU matrix phase capacitive is fine, and DDAB-RGO achieves good dispersion in the base.This DDAB-RGO is with firm and be evenly distributed in TPU matrix to be formed and combine closely, the scattering and permeating path of gas is made to become tortuous roundabout on the one hand, improve the difficulty that penetrates of the small-molecule substances such as gas, thus make the barrier property of material obtain the raising of high degree, DDAB-RGO forms conductive network in TPU matrix on the other hand, improve the antistatic property of material, also make its mechanical property obtain further raising.
(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 the XRD spectra of GO, DDAB-GO, RGO, DDAB-RGO nano composite material.
Fig. 2 is the infrared absorption spectra of GO, DDAB-GO, RGO, DDAB-RGO nano composite material.
Fig. 3 be pure TPU film and add different Nano filling time TPU composite material film OTR oxygen transmission rate change curve.
Fig. 4 be pure TPU film and add different Nano filling time TPU composite material film volume resistance change curve.
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) by 500mg by improve the standby graphite oxide of Hummers legal system to be dissolved in 500ml deionized water and under 100W ultrasonic disperse 2h, then in graphene oxide solution, add 500mgDDAB continue to move in water-bath and stir 3h ultrasonic half an hour, obtain brown color suspension liquid, then in suspension liquid, 1g xitix is added, 80 DEG C are heated in oil bath pan, filtration washing after reaction 2h, through Freeze Drying Equipment freeze-drying, obtained DDAB-RGO nano composite material (being labeled as 1-2DL);
2) 30mgDDAB-RGO nano composite material joins in 80mlDMF solution, and under 100W ultrasonic disperse 2h, the 15gTPU particle of drying in advance is added after it is stable, then 60 DEG C of swelling 6 h of loft drier are put into, stir 2h again, until after TPU dissolves completely, under 100W, ultrasonic disperse 2h gets rid of the air in liquid/paste and leaves standstill 2h;
3) sheet glass clean and tidy for surface is positioned on film applicator carries out film, controlling diaphragm thickness 0.06 ~ 0.08mm, after solvent fully volatilizees, obtain DDAB-RGO/TPU composite material film (being labeled as 0.2%TPU).
embodiment 2
1) by 500mg by improve the standby graphite oxide of Hummers legal system to be dissolved in 500ml deionized water and under 100W ultrasonic disperse 2h, then in graphene oxide solution, add 500mgDDAB continue to move in water-bath and stir 3h ultrasonic half an hour, obtain brown color suspension liquid, then in suspension liquid, 2.5g xitix is added, 80 DEG C are heated in oil bath pan, filtration washing after reaction 2h, through Freeze Drying Equipment freeze-drying, obtained DDAB-RGO nano composite material (being labeled as 1-5DL);
2) 75mgDDAB-RGO nano composite material joins in 80mlDMF solution, and under 100W ultrasonic disperse 2h, the 15gTPU particle of drying in advance is added after it is stable, then 60 DEG C of swelling 6 h of loft drier are put into, stir 2h again, until after TPU dissolves completely, under 100W, ultrasonic disperse 2h gets rid of the air in liquid/paste and leaves standstill 2h;
3) sheet glass clean and tidy for surface is positioned on film applicator carries out film, controlling diaphragm thickness 0.06 ~ 0.08mm, after solvent fully volatilizees, obtain DDAB-RGO/TPU composite material film (being labeled as 0.5%TPU).
embodiment 3
1) by 500mg by improve the standby graphite oxide of Hummers legal system to be dissolved in 500ml deionized water and under 100W ultrasonic disperse 2h, then in graphene oxide solution, add 1gDDAB continue to move in water-bath and stir 3h ultrasonic half an hour, obtain brown color suspension liquid, then in suspension liquid, 2.5g xitix is added, 80 DEG C are heated in oil bath pan, filtration washing after reaction 2h, through Freeze Drying Equipment freeze-drying, obtained DDAB-RGO nano composite material (being labeled as 2-5DL);
2) 150mgDDAB-RGO nano composite material joins in 80mlDMF solution, and under 100W ultrasonic disperse 2h, the 15gTPU particle of drying in advance is added after it is stable, then 60 DEG C of swelling 6 h of loft drier are put into, stir 2h again, until after TPU dissolves completely, under 100W, ultrasonic disperse 2h gets rid of the air in liquid/paste and leaves standstill 2h;
3) sheet glass clean and tidy for surface is positioned on film applicator carries out film, controlling diaphragm thickness 0.06 ~ 0.08mm, after solvent fully volatilizees, obtain DDAB-RGO/TPU composite material film (being labeled as 1%TPU).
embodiment 4
1) by 500mg by improve the standby graphite oxide of Hummers legal system to be dissolved in 500ml deionized water and under 100W ultrasonic disperse 2h, then in graphene oxide solution, add 1gDDAB continue to move in water-bath and stir 3h ultrasonic half an hour, obtain brown color suspension liquid, then in suspension liquid, 5g xitix is added, 80 DEG C are heated in oil bath pan, filtration washing after reaction 2h, through Freeze Drying Equipment freeze-drying, obtained DDAB-RGO nano composite material (being labeled as 2-10DL);
2) 300mgDDAB-RGO nano composite material joins in 80mlDMF solution, and under 100W ultrasonic disperse 2h, the 15gTPU particle of drying in advance is added after it is stable, then 60 DEG C of swelling 6 h of loft drier are put into, stir 2h again, until after TPU dissolves completely, under 100W, ultrasonic disperse 2h gets rid of the air in liquid/paste and leaves standstill 2h;
3) sheet glass clean and tidy for surface is positioned on film applicator carries out film, controlling diaphragm thickness 0.06 ~ 0.08mm, after solvent fully volatilizees, obtain DDAB-RGO/TPU composite material film (being labeled as 2%TPU).
Fig. 1 is the XRD spectra of GO, DDAB-GO, RGO, DDAB-RGO nano composite material.Fig. 2 is the infrared absorption spectra of GO, DDAB-GO, RGO, DDAB-RGO nano composite material.
As seen in Figure 1, GO and DDAB-GO has a peak at <10 °, and relative and GO, DDAB-GO diffraction peak obviously offsets to low angle.This is that its volume effect causes the increase of graphite oxide interlamellar spacing because large-sized quaternary ammonium salt cationic and electronegative graphite oxide structural sheet enter graphite oxide interlayer by electrostatic attraction.And RGO and DDAB-RGO is the diffraction peak disappearance of about 10 °, its reason is that graphene oxide is after xitix reduction, hydroxyl on its structural level, carboxyl and epoxide group are reduced and under the effect of hydrogen bond, cannot form aggregate along basal plane, thus form the flocculence Graphene of unordered accumulation, so occur without obvious diffraction peak in XRD figure spectrum.
Can clearly be seen by Fig. 2 a, in the infrared spectra of DDAB-GO, compared with GO infrared absorption band, at 2920 ± 3 cm
-1the absorption peak that neighbouring appearance is new, by-CH: antisymmetric stretching vibration causes; At 2851 ± 3 cm
-1there is absorption peak in position, is attributed to-CH: symmetrical stretching vibration, at 1464 ± 3 cm
-1there is absorption peak in position, is attributed to-CH
3unsymmetrically flexural vibration; Show that season defines new chemical bond by the functional group of salt and graphite oxide interlayer, season, oneself was successfully inserted into graphite oxide interlayer by salt.This is same as shown in Figure 1.Can be found out by Fig. 2 b, 2920 ± 3 cm in DDAB-RGO infrared absorption band
-1, 2851 ± 3 cm
-1the peak at two places also exists, and illustrate that modified graphene oxide is after xitix reduction, its quaternary ammonium salt group is not departed from; And the infrared absorption peak of RGO and DDAB-RGO comparatively GO and DDAB-GO all obviously weakens, illustrate its oxy radical major part all reduce by xitix.
By embodiment 1,2,3, the performance test results of the DDAB-RGO/TPU composite material film obtained by 4 compares, and embodiment 1 adds 0.2 wt%DDAB-RGO, embodiment 2 adds 0.5wt%DDAB-RGO, embodiment 3 adds 1 wt% DDAB-RGO, embodiment 4 adds 2wt%DDAB-RGO.
Along with the increase of DDAB-RGO number, network structure can be formed in TPU matrix, substantially increase the obstruct of TPU and antistatic mechanical property.As can be seen from Figure 3, when addition is 0.2 ~ 1wt%, when the more quick addition of OTR oxygen transmission rate decline continues to increase, OTR oxygen transmission rate decline degree slows down, illustrate when addition is 1wt%, functional graphene basically forms uniform network in TPU matrix, greatly extends water vapour and the gas small-molecule substance path by composite material film, thus reaches the object of obstruct.
The volume resistance change curve of TPU laminated film when Fig. 4 is DDAB-RGO Different adding amount, upper as can be seen from figure, when addition is 1%, volume resistance sharply declines nearly 8 orders of magnitude, reach antistatic effect, illustrate that DDAB-RGO has defined conductive network passage in TPU matrix, reaches antistatic effect when addition is 1%.And when continuing to increase DDAB-RGO, volume resistance is almost constant, illustrates that DDAB-RGO is substantially saturated in TPU matrix, so desirable addition is 1wt%.
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. functional graphene/TPU film, it is characterized in that: adopt and improve Hummers legal system for graphene oxide, first carry out intercalation modifying with didodecyldimethylammbromide bromide, reduce with xitix again, obtained DDAB-RGO nano composite material, last with TPU resin for matrix, adopt solution coating film-forming process to obtain DDAB-RGO/TPU laminated film.
2. functional graphene/TPU film according to claim 1, is characterized in that: DDAB-RGO/TPU laminated film has obstruct and antistatic property.
3. prepare a method for functional graphene/TPU film as claimed in claim 1, it is characterized in that: comprise the following steps:
1) Hummers legal system is improved for graphene oxide: in low-temp reaction bath, slowly while stirring the vitriol oil to be added in the graphite after cooling process, then in 1h, add potassium permanganate in batches, reaction system is heated to 50 DEG C after half an hour by low-temp reaction, add deionized water after sustained reaction 12h, continue stirring and drip hydrogen peroxide after 15 minutes, finally carry out pickling and be washed to neutrality, through frozen dried, obtained graphene oxide;
2) the DDAB intercalation modifying of graphene oxide: graphene oxide obtained for step 1) to be dissolved in deionized water and ultrasonic disperse 1 ~ 2h, add DDAB and continue ultrasonic half an hour, stir 3 ~ 6h, filter, wash, through freeze-drying, obtained DDAB-GO nano composite material;
3) reduction reaction of modified graphene: by step 2) obtained DDAB-GO nano composite material ultrasonic disperse in deionized water, add xitix, be heated to 80 ~ 95 DEG C, reaction 2 ~ 6h, filter, wash, through freeze-drying, obtained DDAB-RGO nano composite material;
4) preparation of liquid/paste is mixed: the DDAB-RGO nano composite material that step 3) is obtained to be joined in DMF and ultrasonic disperse 1 ~ 2h, add the TPU particle of drying in advance, 60 ~ 80 DEG C of swelling 6 ~ 8 h, stir 2 ~ 5h again, until after TPU dissolves completely, ultrasonic 1 ~ 2h gets rid of the air in liquid/paste, leaves standstill 1 ~ 2h;
5) film: carry out film on the sheet glass that surface is clean and tidy, controlling diaphragm thickness 0.06 ~ 0.08mm, obtains DDAB-RGO/TPU laminated film after solvent fully volatilizees.
4. method according to claim 3, is characterized in that: the cooling process described in step 1) refers to that graphite is placed in low-temp reaction bath is cooled to 0 DEG C.
5. method according to claim 3, is characterized in that: the low-temp reaction temperature described in step 1) controls below 5 DEG C.
6. method according to claim 3, is characterized in that: the pickling described in step 1) refers to: adopt temperature to be the mass percent of 45 DEG C to be the dilute hydrochloric acid of 3% repeatedly to clean graphene oxide 3 times.
7. method according to claim 3, is characterized in that: step 2) or the freeze-drying described in step 3) refer to: freezing temp is-50 DEG C, vacuum-drying 48 ~ 72h.
8. method according to claim 3, is characterized in that: the mass volume ratio of step 4) TPU particle used and DMF is 1g:6mL.
9. an application for functional graphene/TPU film as claimed in claim 1, is characterized in that: described functional graphene/TPU film is as water storage, oil storage bag thin-film material.
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