CN104448366B - A kind of pipe lining high barrier TPU film and preparation method thereof - Google Patents

A kind of pipe lining high barrier TPU film and preparation method thereof Download PDF

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CN104448366B
CN104448366B CN201410780087.9A CN201410780087A CN104448366B CN 104448366 B CN104448366 B CN 104448366B CN 201410780087 A CN201410780087 A CN 201410780087A CN 104448366 B CN104448366 B CN 104448366B
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tpu
mwcnts
gonrs
film
cnts
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CN104448366A (en
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郑玉婴
曹宁宁
林锦贤
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Fuzhou University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/008—Additives improving gas barrier properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a kind of pipe lining high barrier TPU film and preparation method thereof, using MWCNTs, TPU as raw material, using longitudinally cutting MWCNTs methods are aoxidized, by controlling MWCNTs and KMnO4Mass ratio, is made GONRs CNTs nano composite material synthesises, then using TPU resins as matrix, GONRs CNTs/TPU composite material films are made using solution coating film-forming process.Composite material film produced by the present invention, on the one hand the solubility of gas in the polymer is reduced, on the other hand also causing the scattering and permeating path of gas becomes tortuous roundabout, extend diffusion path, improve the small-molecule substances such as gas penetrates difficulty, so that the barrier property of material has obtained the raising of high degree, it is particularly suitable for use in and prepares the unconventional gaseous energy conveyance conduit liner such as shale gas, with extensive society and economic benefit.

Description

A kind of pipe lining high barrier TPU film and preparation method thereof
Technical field
The invention belongs to macromolecule laminated film preparing technical field, and in particular to a kind of pipe lining high barrier TPU film and preparation method thereof.
Background technology
Thermoplastic polyurethane（TPU）It is the widely used elastic block copolymer of a class, is collectively constituted by soft segment and hard section, This special structure causes TPU to remain to keep elastic and preferable wearability well, extension in wider hardness range Property and processability.Meanwhile, with PVC, EVA, butyl rubber（IIR）Compared Deng traditional plastic material, TPU has high-tension, tough It is a kind of ripe ep-type material with the characteristic such as ageing-resistant.Current TPU is widely used to medical device, automobile industry, built The fields such as industry and sporting articles are built, become the functional material of the new period great development prospect.
But some specific areas have very high requirement, such as TPU medical mattress, TPU biogas storages to the barrier property of material The unconventional gaseous energy conveyance conduit liner such as bag, shale gas is paddled class product etc. with TPU membrane material, TPU, and oxygen and vapor It is easy to penetrate through TPU film Deng small-molecule substance, so as to significantly limit application of the TPU film in terms of barrier.Together When TPU because modulus it is low, during as functional material matrix, its mechanical property can not be not fully exerted, it is therefore desirable to other Inorganic or organic material is compound, prepares multi-element composite material, reaches the mesh for improving TPU material blocks performance and mechanical property 's.Current existing such composite typically just by adding the filler of single dimension, such as organic clay, nanometer fento, Nano-calcium carbonate, nm-class boron nitride, or reach that raising TPU is thin using the method being blended with other high-barrier polymer meltings Film obstruct and mechanical property purpose, but to reach required modified effect, there is that addition is big, filler in the base can not The problems such as being completely dispersed, easily cause stress concentration, limits its extensive use.
Multi-walled carbon nanotube（MWCNTs）With larger draw ratio, excellent mechanical characteristic, good chemical stability And heat endurance, there is very big development prospect in composite application field.The performance of functionalization composite mainly depends on The key factors such as the dispersed and orientation of interface interaction, filler in the base between filler and matrix, and there is carbon in MWCNTs Reunion, the defect such as bad dispersibility in polymeric matrix easily occur for pipe, therefore it is multiple in polymer to have limited to single dimension MWCNTs Application in condensation material field.Stannic oxide/graphene nano band（GONRs）It is a kind of main thin list structure being made up of carbon atom Material, its preparation method simplicity, good mechanical performance, surface have abundant oxygen-containing functional group.Reactivity is high, meanwhile, phase Than there is bigger specific surface area in MWCNTs, GONRs, it is more beneficial for carrying out polymer high-barrier, high intensity modification.But The same with MWCNTs, be present easily accumulation, in the organic solvent of part in GONRs, limit to a certain extent Its use in the composite.In order to give full play to the two combination property in terms of polymer modification, find a kind of The new structural material that MWCNTs is combined with GONRs different dimensions, to TPU carry out functionalization be one highly significant Work.
The present invention is proposed by the simultaneously compound thought of the nano material of different dimensions, using the longitudinally cutting MWCNTs of oxidation Legal system obtains stannic oxide/graphene nano band-CNT（GONRs-CNTs）Nano composite material synthesis, to by growing and entangling Tie the CNTs grids of winding to prevent GONRs accumulation, give full play to the two combination property in polymer application field；Again with TPU is matrix, and GONRs-CNTs/TPU composite material films are obtained by solution pouring forming technology, and to its barrier property and Mechanical property is determined.In current domestic and foreign literature, the new structure material being combined with GONRs-CNTs different dimensions Material, which is modified TPU composites, to be also rarely reported, and the present invention is successfully to prepare novel integrated TPU nano composite materials There is provided new approach, while also providing new thinking and spy for Future Development novel high-performance polymer nanocomposites Rope so that the present invention academicly there is innovation research to be worth, in actual applications with extensive economic results in society and war Slightly it is worth.
The content of the invention
It is an object of the invention to for deficiency of the prior art, there is provided a kind of pipe lining high barrier with defect TPU film and preparation method thereof.The thin-film material prepared through the inventive method has excellent barrier property, its safety and environmental protection and Mechanical property has obtained further raising, is particularly suitable for use in and prepares the unconventional gaseous energy conveyance conduit liner such as shale gas, tool There are extensive economic results in society and strategic value.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of pipe lining high barrier TPU film, its preparation method is, using the longitudinally cutting MWCNTs methods of oxidation, to lead to Cross MWCNTs and KMnO in control reaction system4Mass ratio, stannic oxide/graphene nano band-CNT is made（GONRs- CNTs）Nano composite material synthesis, then using TPU resins as matrix, GONRs-CNTs/ is made using solution coating film-forming process TPU composite material films.
The caliber of the MWCNTs is 40 ~ 80 nm, and preferred scope is 40 ~ 60 nm.
Its preparation method specifically includes following steps：
1）The preparation of GONRs-CNTs nano composite material synthesises：By the dense H that 180mL mass fractions are 98%2SO4 In the round-bottomed flask for entering 250mL, the H that 20mL mass fractions are 85.5% is then slowly added to3PO4, 100 ~ 120 r/min's Stirred under rotating speed；1g MWCNTs are subsequently added into, 1 ~ 2h is stirred, after MWCNTs is uniformly dispersed, is slowly added to KMnO4 （KMnO4Addition speed control in 1g/h）, stir 1 ~ 2h and obtain mixed liquor；The mixed liquor stirred is moved to 45 ~ 50 DEG C Oil bath pan in react 20 ~ 24h, then gained mixed system is poured slowly into 500mL mixture of ice and water, condenses and added after 1 ~ 2h 10 ~ 15mL mass fractions are 30% H2O21 ~ 2h is stirred, then gained mixed system is placed in 100W ultrasonic cleaner 0.5 ~ 1h of ultrasonic disperse, on teflon membrane filter, is filtered with HCl and deionized water, washs multiple, with removing system Simultaneously gained GONRs-CNTs nano composite materials synthesis, to neutrality, is finally freeze-dried trace impurity by regulation system；
2）Mix the preparation of liquid/paste：By step 1）The GONRs-CNTs nano composite material synthesises of preparation, are added Into 60 ~ 90mL DMF solutions, 1 ~ 2h of ultrasonic disperse in 100W ultrasonic cleaner is placed in, add 10 after it is stable ~ The TPU particles that 15g is dried in advance, are then placed in 60 ~ 80 DEG C of air dry ovens and are swelled 6 ~ 8h, then are stirred on machine mixer 3 ~ 5h, until after TPU is completely dissolved, being placed in 1 ~ 2h of ultrasonic disperse in 100W ultrasonic cleaner, then mixing pasty liquid Body is poured into the low capacity bottle with suction pipe, is extracted the air in liquid/paste out on suction filtration machine and is stood 1 ~ 2h；
3）Film：The clean and tidy glass plate in surface is positioned on film applicator and carries out film, control film thickness 0.06 ~ 0.08mm, obtains GONRs-CNTs/TPU composite material films after solvent fully volatilizees.
The beneficial effects of the present invention are：
（1）In gained GONRs-CNTs synthesises of the invention, linked between GONRs by CNTs, existing between the two has by force The pi-pi bond of power, can make this combining form more secure rigid, while CNTs presence also plays the effect of support frame, GONRs sliding and reunion is prevented, it is more beneficial for dispersed in polymeric matrix.
（2）GONRs-CNTs synthesises are added in TPU matrixes by the present invention, are obtained by solution pouring forming technology GONRs-CNTs/TPU composite material films.It has been investigated that, GONRs-CNTs and TPU matrix compatibilities in composite material film Very well, and GONRs-CNTs realize in the base it is good scattered.This multilayer, firm and equally distributed special construction And combining closely between GONRs-CNTs intercalations and TPU matrixes, the solubility of gas in the polymer is on the one hand reduced, separately On the one hand also causing the scattering and permeating path of gas becomes tortuous roundabout, extends diffusion path, improves the small molecules such as gas Material penetrates difficulty, so that the barrier property of material has obtained the raising of high degree, also obtains its mechanical property Further raising.
（3）TPU composite material film safety and environmental protections prepared by the present invention, are particularly suitable for use in and prepare the non-conventional gas such as shale gas State energy conveyance conduit liner；Meanwhile, the present invention adapts to the demand in current market, and preparation method is scientific and reasonable, process is simple, behaviour The property made is strong, drastically increases TPU value-added contents of product, and extends its application, with extensive market prospects and Significant social benefit.
Brief description of the drawings
Fig. 1 is the XRD spectra of the GONRs-CNTs nano composite materials of MWCNTs and different content ratio.
Fig. 2 is the TEM spectrograms of the GONRs-CNTs nano composite materials of MWCNTs and different content ratio.
The OTR oxygen transmission rate signal of TPU composite material films when Fig. 3 is pure TPU film and adds different Nano fillings Figure, wherein, 1 is pure TPU, and 2 be MWCNTs-TPU, and 3 be 1:2-TPU, 4 be 1:3-TPU, 5 be 1:4-TPU, 6 be 1:5-TPU, 7 For 1:6-TPU.
Embodiment
In order that content of the present invention easily facilitates understanding, with reference to embodiment to of the present invention Technical scheme is described further, but the present invention is not limited only to this.
Embodiment 1
The 15 g TPU particles dried in advance are poured slowly into 80mL DMF solutions, in the air dry oven for being placed in 80 DEG C 1h is swelled, the mixed system is and then stirred into 3.5h on machine mixer, until after TPU is completely dissolved, being placed in 100W's Ultrasonic disperse 2h in ultrasonic cleaner, will then mix liquid/paste and pours into the low capacity bottle with suction pipe, in suction filtration machine Air in upper extraction liquid/paste simultaneously stands 1.5h.The clean and tidy glass plate in surface is positioned on film applicator and carries out film, is controlled Thickness 0.08mm is film-made, after the completion of coating, sheet glass is hung to 24 h at room temperature with abundant solvent flashing, pure TPU is obtained Material film.
Embodiment 2
A kind of pipe lining high barrier TPU film, its preparation method is, using the longitudinally cutting MWCNTs methods of oxidation, to lead to Cross MWCNTs and KMnO in control reaction system4Mass ratio, be made different content than stannic oxide/graphene nano band-carbon nanometer Pipe（GONRs-CNTs）Nano composite material synthesis, then using TPU resins as matrix, be made using solution coating film-forming process GONRs-CNTs/TPU composite material films.
The caliber of the MWCNTs is 60 nm.
Its preparation method specifically includes following steps：
1）The preparation of GONRs-CNTs nano composite material synthesises：By the dense H that 180mL mass fractions are 98%2SO4 In the round-bottomed flask for entering 250mL, the H that 20mL mass fractions are 85.5% is then slowly added to3PO4, in 100 r/min rotating speed Under stir；1g MWCNTs are subsequently added into, 1.5h is stirred, after MWCNTs is uniformly dispersed, is slowly added to 2g KMnO4 （KMnO4Addition speed control in 1g/h）, 1h is stirred, it is 1 to obtain content ratio:2 mixed liquor；By the mixed liquor stirred 20h is reacted in the oil bath pan for moving to 50 DEG C, then gained mixed system is poured slowly into 500mL mixture of ice and water, is condensed after 2h Add the H that 10mL mass fractions are 30%2O2, 1.5h is stirred, then gained mixed system is placed in 100W ultrasonic cleaner Middle ultrasonic disperse 30min, on teflon membrane filter, is filtered with HCl and deionized water, washs multiple, with removing system Trace impurity and regulation system to neutrality, it is finally that gained GONRs-CNTs nano composite material synthesises is freeze-dried, Products therefrom is abbreviated as 1:2；
2）Mix the preparation of liquid/paste：By 0.075g steps 1）1 prepared:The GONRs-CNTs of 2 contents is nano combined Material synthesis is added in 80mL DMF solutions, and the ultrasonic disperse 6h in 100W ultrasonic cleaner, after it is stable The TPU particles that 15g is dried in advance are added, is then placed in 80 DEG C of air dry ovens and is swelled 1h, then are stirred on machine mixer 3.5h, until after TPU is completely dissolved, being placed in ultrasonic disperse 2h in 100W ultrasonic cleaner, then mixing liquid/paste Pour into the low capacity bottle with suction pipe, extract the air in liquid/paste out on suction filtration machine and stand 1.5h；
3）Film：The clean and tidy glass plate in surface is positioned on film applicator and carries out film, film thickness 0.08mm is controlled, works as painting After the completion of applying, sheet glass is hung to 24 h at room temperature with abundant solvent flashing, it is 1 to obtain 0.075g contents:2 GONRs- CNTs/TPU composite material films（Labeled as 1:2-TPU）.
Embodiment 3
Step 1）Middle KMnO4Addition be 3g, other conditions parameter is same as Example 2, finally gives 0.075g and contains Measure as 1:3 GONRs-CNTs/TPU composite material films（Labeled as 1:3-TPU）.
Embodiment 4
Step 1）Middle KMnO4Addition be 4g, other conditions parameter is same as Example 2, finally gives 0.075g and contains Measure as 1:4 GONRs-CNTs/TPU composite material films（Labeled as 1:4-TPU）.
Embodiment 5
Step 1）Middle KMnO4Addition be 5g, other conditions parameter is same as Example 2, finally gives 0.075g and contains Measure as 1:5 GONRs-CNTs/TPU composite material films（Labeled as 1:5-TPU）.
Embodiment 6
Step 1）Middle KMnO4Addition be 6g, other conditions parameter is same as Example 2, finally gives 0.075g and contains Measure as 1:6 GONRs-CNTs/TPU composite material films（Labeled as 1:6-TPU）.
Fig. 1 is the XRD spectra of the GONRs-CNTs nano composite materials of MWCNTs and different content ratio, and Fig. 2 is MWCNTs With the TEM spectrograms of the GONRs-CNTs nano composite materials of different content ratio.
It can be clearly seen that by Fig. 1 and Fig. 2, with MWCNTs and KMnO in reaction system4Content ratio is by 1:2 changes To 1:During 6, GONRs contents are more and more in gained GONRs-CNTs synthesises, and as MWCNTs and KMnO4Content Than for 1:When 6, do not observe CNTs presence in gained synthesis substantially, now in system MWCNTs substantially completely by oxygen It is GONRs to change longitudinally cutting；Simultaneously by Fig. 2 (d) it will be clear that its width of the GONRs of banded structure is about 160nm, but the obvious agglomerations of GONRs are can also see that from figure, limit further applying for its.Need to particularly point out , such as shown in Fig. 2 (b) and Fig. 2 (c), as MWCNTs and KMnO4Content ratio is 1:2 and 1:When 4, gained GONRs-CNTs is comprehensive In zoarium, linked between GONRs by CNTs, there is strong pi-pi bond between the two, this combining form can be made more firm Closely, while CNTs presence also plays the effect of support frame, it is therefore prevented that GONRs sliding and reunion, it is more beneficial for it It is dispersed in polymeric matrix.
The OTR oxygen transmission rate signal of TPU composite material films when Fig. 3 is pure TPU film and adds different Nano fillings Figure, wherein, 1 is pure TPU, and 2 be MWCNTs-TPU, and 3 be 1:2-TPU, 4 be 1:3-TPU, 5 be 1:4-TPU, 6 be 1:5-TPU, 7 For 1:6-TPU.
As seen in Figure 3, the OTR oxygen transmission rate of pure TPU film made from embodiment 1 is 460.335 cm3/ m2.d.Pa, hence it is evident that the compound TPU film standby higher than GONRs-CNTs combined systems obtained by embodiment 2-6；While it may be noted that It is, as shown in figure 3, as MWCNTs and KMnO in reaction system4Content ratio is 1:When 4, its OTR oxygen transmission rate reaches minimum 224.172cm3/m2.d.Pa, compared to pure TPU, its OTR oxygen transmission rate have dropped 51.3%, and barrier property is improved significantly.
Composite material film provided by the present invention is applied to prepare TPU medical mattress, TPU biogas storage-bags, shale gas Etc. unconventional gaseous energy conveyance conduit liner paddled with TPU membrane material, TPU class product etc. have to the barrier property of material it is higher will The field asked.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, should all belong to the covering scope of the present invention.

Claims (4)

1. a kind of pipe lining high barrier TPU film, it is characterised in that：Using longitudinally cutting MWCNTs methods are aoxidized, pass through Control MWCNTs and KMnO in reaction system4Mass ratio, GONRs-CNTs nano composite material synthesises are made, then with TPU Resin is matrix, and the TPU film is made using solution coating film-forming process；
Its preparation method specifically includes following steps：
1）The preparation of GONRs-CNTs nano composite material synthesises：By the H that mass fraction is 85.5%3PO4It is slowly added into matter Measure the dense H that fraction is 98%2SO4In, stirred under 100 ~ 120 r/min rotating speed；It is subsequently added into MWCNTs and stirs 1 ~ 2h, After MWCNTs is uniformly dispersed, by MWCNTs and KMnO4Mass ratio be 1:4 are slowly added to KMnO4, it is mixed that 1 ~ 2h of stirring is obtained Close liquid；Mixed liquor after stirring is moved to 20 ~ 24h of reaction in 45 ~ 50 DEG C of oil bath pan, then gained mixed system is slow Pour into mixture of ice and water, condense the H for adding that mass fraction is 30% after 1 ~ 2h2O2Stir 1 ~ 2h, then by mixed system in Scattered 0.5 ~ 1h under 100W ultrasounds, is filtered with deionized water with HCl on teflon membrane filter, washs multiple, to remove body Trace impurity and regulation system in system finally freeze gained GONRs-CNTs nano composite materials synthesis dry to neutrality It is dry；
2）Mix the preparation of liquid/paste：By step 1）The GONRs-CNTs nano composite material synthesises of preparation are added to DMF In solution, and 1 ~ 2h of ultrasonic disperse under 100W, the TPU particles dried in advance are added after it is stable, 60 ~ 80 DEG C are then placed in 6 ~ 8 h are swelled in drying box, 3 ~ 5h is stirred for, until after TPU is completely dissolved, then will be mixed in 1 ~ 2h of ultrasonic disperse under 100W Close liquid/paste to pour into the low capacity bottle with suction pipe, extract the air in liquid/paste out on suction filtration machine and stand 1 ~ 2h；
3）Film：The clean and tidy glass plate in surface is positioned on film applicator and carries out film, 0.06 ~ 0.08mm of film thickness is controlled, treats Solvent obtains GONRs-CNTs/TPU composite material films after fully volatilizing.
2. pipe lining high barrier TPU film according to claim 1, it is characterised in that：The caliber of the MWCNTs For 40 ~ 80 nm.
3. pipe lining high barrier TPU film according to claim 1, it is characterised in that：Step 1）Middle KMnO4Plus Enter speed control in 1g/h.
4. pipe lining high barrier TPU film according to claim 1, it is characterised in that：Step 2）TPU particles used Mass volume ratio with DMF solution is 1:6.
CN201410780087.9A 2014-12-17 2014-12-17 A kind of pipe lining high barrier TPU film and preparation method thereof Active CN104448366B (en)

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CN105968777B (en) * 2016-05-24 2018-09-18 福州大学 A kind of antistatic composite nano materials film and preparation method thereof
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CN107629440B (en) * 2017-09-29 2020-04-10 安徽嘉明新材料科技有限公司 Preparation method of high-barrier TPU film
CN109438968A (en) * 2018-09-11 2019-03-08 苏州市雄林新材料科技有限公司 A kind of automotive headrest high-barrier TPU film and preparation method thereof
CN109367183A (en) * 2018-09-11 2019-02-22 东莞市雄林新材料科技股份有限公司 One kind having antiforge function TPU composite membrane and preparation method thereof
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CN103834051A (en) * 2014-03-21 2014-06-04 福州大学 Barrier anti-static TPU (Thermoplastic Polyurethane) composite material film and preparation method thereof
CN104072979A (en) * 2014-07-18 2014-10-01 福州大学 Oxidized graphene nano-ribbon/polymer composite film and preparation method thereof

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