CN104448366A - High-barrier TPU (thermoplastic polyurethane) film for inner lining of pipe and preparation method thereof - Google Patents

High-barrier TPU (thermoplastic polyurethane) film for inner lining of pipe and preparation method thereof Download PDF

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CN104448366A
CN104448366A CN201410780087.9A CN201410780087A CN104448366A CN 104448366 A CN104448366 A CN 104448366A CN 201410780087 A CN201410780087 A CN 201410780087A CN 104448366 A CN104448366 A CN 104448366A
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tpu
gonrs
film
cnts
mwcnts
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CN104448366B (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 high-barrier TPU (thermoplastic polyurethane) film for the inner lining of a pipe and a preparation method thereof. A GONRs-CNTs (graphene oxide nanoribbons and carbon nanotubes) nanocomposite complex is prepared by cutting MWCNTs (multi-walled carbon nanotubes) longitudinally by oxidizing and controlling the mass ratio of MWCNTs to KMnO4, and a GONRs-CNTs/TPU composite film is prepared by adding the GONRs-CNTs nanocomposite complex into TPU resin by adopting a solution coating and film forming process, wherein the MWCNTs and the TPU serve as raw materials, and the TPU resin serves as a matrix. The composite film provided by the invention has the advantages that on the one hand, the solubility of gas in a polymer is reduced, on the other hand, the gas diffusion and penetration pathway is circuitous, the gas diffusion pathway is prolonged, the penetration of gases and other small-molecule substances is difficult, and the barrier of the material is improved greatly. The high-barrier TPU film disclosed by the invention is especially suitable for preparing the inner lining of pipelines for conveying shale gas and other unconventional gaseous energy and can achieve enormous social and economic benefits.

Description

A kind of pipe lining high barrier TPU film and preparation method thereof
Technical field
The invention belongs to polymer laminated film preparing technical field, be specifically related to a kind of pipe lining high barrier TPU film and preparation method thereof.
Background technology
Thermoplastic polyurethane (TPU) is the broad-spectrum elastic block copolymer of a class, jointly be made up of soft section and hard section, this special structure makes TPU in wider durometer level, still can keep good elasticity and good wear resistance, ductility and processibility.Meanwhile, compared with traditional plastic materials such as PVC, EVA, isoprene-isobutylene rubber (IIR), TPU has high tensile, the characteristic such as tough and ageing-resistant, is a kind of ep-type material of maturation.Current TPU has been widely used in the fields such as medical device, automobile industry, building trade and sporting articles, becomes the functional material that the new period has development prospect.
But the barrier property of some specific areas to material has very high requirement, as the unconventional gaseous energy transport pipe liner TPU membrane materials such as TPU medical mattress, TPU biogas storage-bag, shale gas, TPU paddle series products etc., and the small-molecule substance such as oxygen and water vapour is easy to penetrate through TPU film, thus significantly limit the application of TPU film in obstruct.TPU is because modulus is low simultaneously, and during as functional materials matrix, its mechanical property cannot be not fully exerted, and therefore needs or organic materials compound inorganic with other, prepares multi-element composite material, reaches the object improving TPU material block performance and mechanical property.The filler of this type of matrix material existing generally just by adding single dimension at present, as organic clay, nanometer fento, nano-calcium carbonate, nm-class boron nitride, or to adopt and the blended method of other high-barrier polymer melts reaches and improves TPU film and intercept and the object of mechanical property, but reach required modified effect, have that addition is large, filler cannot disperse completely in the base, easily cause the problems such as stress concentration, limit its widespread use.
Multi-walled carbon nano-tubes (MWCNTs) has larger length-to-diameter ratio, excellent mechanical characteristic, good chemical stability and thermostability, has very large development prospect in matrix material Application Areas.The performance of functionalization matrix material depends primarily on interface interaction, the filler key factor such as dispersiveness and orientation in the base between filler and matrix, and MWCNTs exists, and carbon pipe is easily reunited, the defect such as bad dispersibility in polymeric matrix, has therefore limited to the application of single dimension MWCNTs in polymer composites field.Stannic oxide/graphene nano band (GONRs) is a kind of sheet shape structured material formed primarily of carbon atom, and its preparation method is easy, good mechanical performance, surface have abundant oxygen-containing functional group.Reactive behavior is high, meanwhile, has larger specific surface area compared to MWCNTs, GONRs, is more conducive to carrying out high-barrier, high strength modification to polymkeric substance.But the same with MWCNTs, GONRs exist easily build up, the problem such as bad dispersibility in part organic solvent, limit its use in the composite to a certain extent.In order to give full play to the two over-all properties in polymer modification, find the new structural material that a kind of MWCNTs and GONRs different dimensions combines, carrying out functionalization to TPU is a job highly significant.
The present invention proposes the thought of compound while of the nano material of different dimensions, adopt oxidation longitudinally to cut MWCNTs legal system and obtain stannic oxide/graphene nano band-carbon nanotube (GONRs-CNTs) nano composite material synthesis, to being stoped the accumulation of GONRs by the long and CNTs grid of being entangled with winding, give full play to the two over-all properties in polymer application field; Be matrix again with TPU, obtain GONRs-CNTs/TPU composite material film by solution casting moulding process, and its barrier property and mechanical property are measured.In current domestic and foreign literature, the new structural material combined with GONRs-CNTs different dimensions is modified TPU matrix material also rarely has 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 pipe lining high barrier TPU film and preparation method thereof is provided.The thin-film material prepared through the inventive method has excellent barrier property, its safety and environmental protection and mechanical property obtains further raising, be particularly useful for preparing the unconventional gaseous energy transport pipe liners such as shale gas, there is economic results in society and strategic value widely.
For achieving the above object, the present invention adopts following technical scheme:
A kind of pipe lining high barrier TPU film, its preparation method adopts oxidation longitudinally cutting MWCNTs method, by controlling MWCNTs and KMnO in reaction system 4mass ratio, obtained stannic oxide/graphene nano band-carbon nanotube (GONRs-CNTs) nano composite material synthesis, then with TPU resin for matrix, adopt solution coating film-forming process to obtain GONRs-CNTs/TPU composite material film.
The caliber of described MWCNTs is 40 ~ 80 nm, and preferable range is 40 ~ 60 nm.
Its preparation method specifically comprises the steps:
1) preparation of GONRs-CNTs nano composite material synthesis: be the dense H of 98% by 180mL massfraction 2sO 4pour in the round-bottomed flask of 250mL, slowly add the H that 20mL massfraction is 85.5% subsequently 3pO 4, stir under the rotating speed of 100 ~ 120 r/min; Then add 1g MWCNTs, stir 1 ~ 2h, after MWCNTs is uniformly dispersed, slowly add KMnO 4(KMnO 4add speed control at 1g/h), stir 1 ~ 2h obtain mixed solution; The mixed solution stirred is moved in the oil bath pan of 45 ~ 50 DEG C and react 20 ~ 24h, then gained mixed system is slowly poured in 500mL mixture of ice and water, after condensation 1 ~ 2h, add the H that 10 ~ 15mL massfraction is 30% 2o 2stir 1 ~ 2h, then gained mixed system is placed in the ultrasonic cleaner ultrasonic disperse 0.5 ~ 1h of 100W, on teflon membrane filter, filter with HCl and deionized water, wash repeatedly, with the trace impurity in removing system and regulation system to neutral, finally by the lyophilize of gained GONRs-CNTs nano composite material synthesis;
2) preparation of liquid/paste is mixed: GONRs-CNTs nano composite material synthesis step 1) prepared, join in 60 ~ 90mL DMF solution, and be placed in the ultrasonic cleaner ultrasonic disperse 1 ~ 2h of 100W, the TPU particle that 10 ~ 15g is dried in advance is added after it is stable, then 60 ~ 80 DEG C of swelling 6 ~ 8h of air dry oven are put into, 3 ~ 5h is stirred again on machine mixer, until after TPU dissolves completely, be placed in the ultrasonic cleaner ultrasonic disperse 1 ~ 2h of 100W, subsequently mixing liquid/paste is poured in the low capacity bottle with suction pipe, suction filtration machine is extracted out the air in liquid/paste and leaves standstill 1 ~ 2h,
3) 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 GONRs-CNTs/TPU composite material film after solvent fully volatilizees.
beneficial effect of the present invention is:
(1) in gained GONRs-CNTs synthesis of the present invention, linked by CNTs between GONRs, strong pi-pi bond is there is between the two, this combining form secure rigid more can be made, the existence of CNTs simultaneously also serves the effect of support frame, prevent slippage and the reunion of GONRs, be more conducive to its dispersed in polymeric matrix.
(2) GONRs-CNTs synthesis joins in TPU matrix by the present invention, obtains GONRs-CNTs/TPU composite material film by solution casting moulding process.Find after deliberation, in composite material film, GONRs-CNTs and TPU matrix phase capacitive is fine, and GONRs-CNTs achieves good dispersion in the base.This multilayer, firm and equally distributed special construction and combining closely between GONRs-CNTs intercalation and TPU matrix, reduce gas solubility in the polymer on the one hand, also the scattering and permeating path of gas is made to become tortuous roundabout on the other hand, extend the evolving path, 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, 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 the unconventional gaseous energy transport pipe liners such as shale gas; 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 the GONRs-CNTs nano composite material of MWCNTs and different content ratio.
Fig. 2 is the TEM spectrogram of the GONRs-CNTs nano composite material of MWCNTs and different content ratio.
Fig. 3 be pure TPU film and add different Nano filling time TPU composite material film OTR oxygen transmission rate schematic diagram, wherein, 1 is pure TPU, and 2 is MWCNTs-TPU, and 3 is 1:2-TPU, and 4 is 1:3-TPU, and 5 is 1:4-TPU, and 6 is 1:5-TPU, and 7 is 1:6-TPU.
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
The TPU particle of being dried in advance by 15 g is slowly poured in 80mL DMF solution; be placed in the swelling 1h of air dry oven of 80 DEG C; and then this mixed system is stirred 3.5h on machine mixer; until after TPU dissolves completely; be placed in the ultrasonic cleaner ultrasonic disperse 2h of 100W; subsequently mixing liquid/paste is poured in the low capacity bottle with suction pipe, suction filtration machine is extracted out the air in liquid/paste and leaves standstill 1.5h.Sheet glass clean and tidy for surface is positioned on film applicator and carries out film, controlling diaphragm thickness 0.08mm, after coating completes, sheet glass is at room temperature hung 24 h with abundant solvent flashing, obtain pure TPU material film.
embodiment 2
A kind of pipe lining high barrier TPU film, its preparation method adopts oxidation longitudinally cutting MWCNTs method, by controlling MWCNTs and KMnO in reaction system 4mass ratio, stannic oxide/graphene nano band-carbon nanotube (GONRs-CNTs) the nano composite material synthesis of obtained different content ratio, then with TPU resin for matrix, adopt solution coating film-forming process to obtain GONRs-CNTs/TPU composite material film.
The caliber of described MWCNTs is 60 nm.
Its preparation method specifically comprises the steps:
1) preparation of GONRs-CNTs nano composite material synthesis: be the dense H of 98% by 180mL massfraction 2sO 4pour in the round-bottomed flask of 250mL, slowly add the H that 20mL massfraction is 85.5% subsequently 3pO 4, stir under the rotating speed of 100 r/min; Then add 1g MWCNTs, stir 1.5h, after MWCNTs is uniformly dispersed, slowly add 2g KMnO 4(KMnO 4add speed control at 1g/h), stirring 1h, obtaining content than being the mixed solution of 1:2; The mixed solution stirred is moved in the oil bath pan of 50 DEG C and react 20h, then gained mixed system is slowly poured in 500mL mixture of ice and water, after condensation 2h, add the H that 10mL massfraction is 30% 2o 2stir 1.5h, then gained mixed system is placed in the ultrasonic cleaner ultrasonic disperse 30min of 100W, on teflon membrane filter, filter with HCl and deionized water, wash repeatedly, with the trace impurity in removing system and regulation system to neutral, finally by gained GONRs-CNTs nano composite material synthesis through lyophilize, products therefrom is referred to as 1:2;
2) preparation of liquid/paste is mixed: the GONRs-CNTs nano composite material synthesis of 1:2 content 0.075g step 1) prepared joins in 80mL DMF solution, and in the ultrasonic cleaner of 100W ultrasonic disperse 6h, the TPU particle that 15g is dried in advance is added after it is stable, then 80 DEG C of swelling 1h of air dry oven are put into, 3.5h is stirred again on machine mixer, until after TPU dissolves completely, be placed in the ultrasonic cleaner ultrasonic disperse 2h of 100W, subsequently mixing liquid/paste is poured in the low capacity bottle with suction pipe, suction filtration machine is extracted out the air in liquid/paste and leaves standstill 1.5h,
3) film: sheet glass clean and tidy for surface is positioned on film applicator and carries out film, controlling diaphragm thickness 0.08mm, after coating completes, sheet glass is at room temperature hung 24 h with abundant solvent flashing, obtain the GONRs-CNTs/TPU composite material film (being labeled as 1:2-TPU) that 0.075g content is 1:2.
embodiment 3
KMnO in step 1) 4add-on be 3g, other conditional parameters are identical with embodiment 2, finally obtain the GONRs-CNTs/TPU composite material film (being labeled as 1:3-TPU) that 0.075g content is 1:3.
embodiment 4
KMnO in step 1) 4add-on be 4g, other conditional parameters are identical with embodiment 2, finally obtain the GONRs-CNTs/TPU composite material film (being labeled as 1:4-TPU) that 0.075g content is 1:4.
embodiment 5
KMnO in step 1) 4add-on be 5g, other conditional parameters are identical with embodiment 2, finally obtain the GONRs-CNTs/TPU composite material film (being labeled as 1:5-TPU) that 0.075g content is 1:5.
embodiment 6
KMnO in step 1) 4add-on be 6g, other conditional parameters are identical with embodiment 2, finally obtain the GONRs-CNTs/TPU composite material film (being labeled as 1:6-TPU) that 0.075g content is 1:6.
Fig. 1 is the XRD spectra of the GONRs-CNTs nano composite material of MWCNTs and different content ratio, and Fig. 2 is the TEM spectrogram of the GONRs-CNTs nano composite material of MWCNTs and different content ratio.
Can clearly be seen by Fig. 1 and Fig. 2, along with MWCNTs and KMnO in reaction system 4content is than being changed in the process of 1:6 by 1:2, and in gained GONRs-CNTs synthesis, GONRs content gets more and more, and as MWCNTs and KMnO 4content is than when being 1:6, and substantially do not observe the existence of CNTs in gained synthesis, now in system, the basic complete oxidized longitudinal direction of MWCNTs is cut into GONRs; Can be clear that by Fig. 2 (d), its width of the GONRs of zonal structure is about 160nm, but also can see the obvious agglomeration of GONRs from figure, limits its further application simultaneously.It is important to note that as shown in Fig. 2 (b) He Fig. 2 (c), as MWCNTs and KMnO 4content is than when being 1:2 and 1:4, in gained GONRs-CNTs synthesis, linked by CNTs between GONRs, strong pi-pi bond is there is between the two, this combining form secure rigid more can be made, the simultaneously existence of CNTs also serves the effect of support frame, prevents slippage and the reunion of GONRs, is more conducive to its dispersed in polymeric matrix.
Fig. 3 be pure TPU film and add different Nano filling time TPU composite material film OTR oxygen transmission rate schematic diagram, wherein, 1 is pure TPU, and 2 is MWCNTs-TPU, and 3 is 1:2-TPU, and 4 is 1:3-TPU, and 5 is 1:4-TPU, and 6 is 1:5-TPU, and 7 is 1:6-TPU.
As seen in Figure 3, the OTR oxygen transmission rate of the pure TPU film that embodiment 1 is obtained is 460.335 cm 3/ m 2.d.Pa, apparently higher than the compound TPU film that embodiment 2-6 gained GONRs-CNTs combined system is standby; It is pointed out that as shown in Figure 3, as MWCNTs and KMnO in reaction system simultaneously 4content is than when being 1:4, and its OTR oxygen transmission rate reaches Schwellenwert 224.172cm 3/ m 2.d.Pa, compare its OTR oxygen transmission rate of pure TPU and have dropped 51.3%, barrier property is improved significantly.
Composite material film provided by the present invention is applicable to the unconventional gaseous energy transport pipe liner TPU membrane materials such as preparation TPU medical mattress, TPU biogas storage-bag, shale gas, TPU paddles the field that series products etc. has higher requirements to the barrier 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 (6)

1. a pipe lining preparation method for high barrier TPU film, is characterized in that: adopt oxidation longitudinally cutting MWCNTs method, by controlling MWCNTs and KMnO in reaction system 4mass ratio, obtained GONRs-CNTs nano composite material synthesis, then with TPU resin for matrix, adopt solution coating film-forming process to obtain GONRs-CNTs/TPU composite material film.
2. the pipe lining preparation method of high barrier TPU film according to claim 1, is characterized in that: the caliber of described MWCNTs is 40 ~ 80 nm.
3. the pipe lining preparation method of high barrier TPU film according to claim 1, is characterized in that: specifically comprise the steps:
1) preparation of GONRs-CNTs nano composite material synthesis: be the H of 85.5% by massfraction 3pO 4slowly join the dense H that massfraction is 98% 2sO 4in, stir under the rotating speed of 100 ~ 120 r/min; Then add MWCNTs and stir 1 ~ 2h, after MWCNTs is uniformly dispersed, slowly add KMnO 4, stir the mixed solution that 1 ~ 2h obtains; Mixed solution after stirring is moved to reaction 20 ~ 24h in the oil bath pan of 45 ~ 50 DEG C, then gained mixed system is slowly poured in mixture of ice and water, after condensation 1 ~ 2h, add the H that massfraction is 30% 2o 2stir 1 ~ 2h, then by mixed system in the ultrasonic lower dispersion 0.5 ~ 1h of 100W, teflon membrane filter filters with HCl and deionized water, washs repeatedly, with the trace impurity in removing system and regulation system to neutral, finally by the lyophilize of gained GONRs-CNTs nano composite material synthesis;
2) preparation of liquid/paste is mixed: GONRs-CNTs nano composite material synthesis step 1) prepared joins in DMF solution, and under 100W ultrasonic disperse 1 ~ 2h, the TPU particle of drying in advance is added after it is stable, then 60 ~ 80 DEG C of swelling 6 ~ 8 h of loft drier are put into, stir 3 ~ 5h again, until after TPU dissolves completely, ultrasonic disperse 1 ~ 2h under 100W, subsequently mixing liquid/paste is poured in the low capacity bottle with suction pipe, suction filtration machine is extracted out the air in liquid/paste and leaves standstill 1 ~ 2h;
3) 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 GONRs-CNTs/TPU composite material film after solvent fully volatilizees.
4. the pipe lining preparation method of high barrier TPU film according to claim 1, is characterized in that: KMnO in step 1) 4add speed control at 1g/h.
5. the pipe lining preparation method of high barrier TPU film according to claim 1, is characterized in that: step 2) mass volume ratio of TPU particle used and DMF solution is 1:6.
6. the pipe lining high barrier GONRs-CNTs/TPU film that preparation method obtains as described in claim 1 or 3.
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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