CN104945659A - Novel CNT (carbon nanotube) surface treatment method and application thereof in preparing polymer/CNT nano composite material - Google Patents
Novel CNT (carbon nanotube) surface treatment method and application thereof in preparing polymer/CNT nano composite material Download PDFInfo
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Abstract
The invention relates to a novel CNT (carbon nanotube) surface treatment method which comprises the following steps: 1) proportionally dispersing CNT and a polymer in a solvent, or previously proportionally mixing the CNT and polymer uniformly; 2) grafting a matrix polymer of the target composite material by treating the mixture obtained in the step 1) by a high-energy physical means: the polymer molecular chain and CNT wall are broken to generate free radicals, and the polymer molecular chain is grafted onto the CNT surface through the coupling reaction of the free radicals; and separating to remove the solvent and unreacted polymers to obtain the surface-treated novel CNT. The method only uses a certain amount of solvent in certain cases, and can complete the CNT modification without any other reagent. The CNT surface grafting is performed on the polymer matrix, so the compatibility between the modified CNT and matrix is excellent.
Description
Technical field
The invention belongs to field of surface treatment and field of compound material, especially relate to a kind of novel CNT surface treatment process and preparing the application in polymkeric substance/CNT nano composite material.
Background technology
In recent years, in order to improve the performance such as mechanics, electrical property of polymkeric substance, a lot of scientific research institution and company attempt preparing polymkeric substance/CNT nano composite material.CNT lamella itself has high modulus and the excellent specific property such as intensity, very large specific surface area.It is added with suitable process the use properties that significantly can improve products obtained therefrom in polymkeric substance, expand its use field.
Generally speaking, prepare polymkeric substance/CNT nano composite material and have following three kinds of modes: solution method, situ aggregation method and melt-blending process.Solution method needs polymkeric substance and filler CNT to dissolve simultaneously or stable is scattered in certain suitable solvent, and except desolventizing after the two Homogeneous phase mixing, drying and moulding, obtains matrix material.This method restricted application.First, polymkeric substance must have good solvent, and the extremely insoluble polymkeric substance of such as high density polyethylene(HDPE) one class can not use this method.Secondly, solution method needs to use a large amount of solvent, and organic solvent poisonous often, extremely unfavorable and increase production cost to environmental protection.Therefore solution method generally uses in the scientific research of laboratory, few suitability for industrialized production.Situ aggregation method principle is then that polymerizing catalyst is carried on CNT tube wall, then mixes with polymer monomer and trigger polyreaction, while polymerization, prepare matrix material.Situ aggregation method is applicable to that fusing point is higher, processing degradation comparatively significantly polymkeric substance.But, because needs carry out redesigning and synthesize to polymerisation catalysts, whole conversion unit parameter is adjusted, adds into product difficulty and cost, be unfavorable for popularization.
Melt-blending process is current the most widely used Nano-composite materials method.When this method utilizes blended, the CNT of aggregating state is dispersed among polymer melt by the shearing force of screw rod, and multiple method prepares the finished product can to use injection moulding, extrude etc., and the scope of application is the most extensive, early investment and production cost lower.But CNT surface can be high, lack functional group, bad with main polymer chain consistency; And between CNT carbon pipe and carbon pipe, be often in the aggregating state mutually tangled, be therefore difficult to make it enter polymeric matrix with the dispersion of single state, thus make the modified effect of CNT can not get fully playing.In order to solve an above difficult problem, way general at present uses chemical oxidation method to carry out modification to CNT.Chemical oxidation can introduce functional group in CNT surface, and breaks the aggregate structure of CNT to a certain extent, thus improves CNT dispersion in the polymer.In recent years, also many reports are had by conjugation reaction (as " Click Chemistry " etc.) modification CNT, general thought is all by chemical reaction in CNT surface grafted functional group, then improves CNT dispersiveness by the interaction of these functional groups and polymeric matrix.
Although aforesaid method improves the dispersiveness of CNT, really also there is inevitable side effect.First, although chemical oxidization method modification CNT is effective, but to uses the strong oxidizer such as the vitriol oil, concentrated nitric acid in a large number, operator and environment are worked the mischief, and very easily etching apparatus.The more important thing is the chemical oxidization method havoc structural integrity of CNT, cause CNT self performance significantly to reduce, thus weaken the enhancement of CNT.Although some other method can keep the structural integrity of CNT relatively preferably, be faced with reaction reagent costliness, raw material needs the difficulties such as laboratory synthesis.The same with acid oxidase, conjugation reaction method also needs complicated subsequent purification, is separated the steps such as unreacting reagent, significantly increases complicacy and the cost of CNT surface process, causes CNT matrix material to be difficult to suitability for industrialized production.
Summary of the invention
In order to overcome the deficiency in background technology, the invention discloses a kind of novel CNT surface treatment process and preparing the application in polymkeric substance/CNT nano composite material.
In order to realize described goal of the invention, the present invention adopts following technical scheme: a kind of novel C NT surface treatment method, comprise the following steps: 1) by CNT and polymkeric substance proportionally 1:2 ~ 100:1 (w/w) be scattered in solvent, or by CNT and polymkeric substance proportionally 1:2 ~ 100:1 (w/w) be pre-mixed evenly; 2) matrix polymer of grafting target matrix material: use high-energy physical means to step 1) in the mixture that obtains process: interrupt polymer molecular chain and break CNT tube wall producing free radical, polymer molecular chain is made to graft on CNT surface by the coupling reaction of free radical, be separated except desolventizing and unreacted polymkeric substance, obtain surface treated novel C NT, be designated as product A.
Described high-energy physical means is the means producing the phenomenon of energy concentration of high temperature, high pressure, high speed shear or ultrasonic cavitation at processed material or its local, utilizes the energy in High-speed machining means to produce free radical or active group for physically; Described high-energy physical means comprises large power supersonic, ball milling, emulsification means.
Described CNT is multi-walled carbon nano-tubes (MWCNT), Single Walled Carbon Nanotube (SWCNT), or the one in double-walled carbon nano-tube.
Described CNT is radius is 1nm-200nm, CNT length 50nm-500 μm.
Described polymkeric substance is the one in PP, polyethylene (PE), nylon 12 (PA12), PVC, PMMA or PVDF.But type of polymer is not limited to mention above-mentioned several, and polyolefine effect is best, to polyolefin derivative thing, as the effects such as PVDF, PVC, PMMA are taken second place, more weak for the effect such as polyester, polymeric amide.
A kind of preparation method of polymkeric substance/CNT nano composite material, mixes product A with fluoropolymer resin, and by melt blending or solution blending mode, preparation draws polymkeric substance/CNT nano composite material.
In described polymkeric substance/CNT nano composite material, the content of CNT is 0.01 ~ 20wt%.
CNT in described step (1) can use the one in Graphene, carbon fiber or carbon nanofiber to substitute.
Owing to have employed technique scheme, the present invention has following beneficial effect: novel CNT surface treatment process of the present invention, and the energy provided by high-energy physical method, at the matrix polymer of CNT surface grafting target matrix material.The method only needs to use a certain amount of solvent in some cases, without the need to other any reagent, can complete CNT modification.Owing to being polymeric matrix itself in CNT surface grafting, therefore modification CNT and matrix phase capacitive splendid.CNT structure obtains better protecting simultaneously, and without the need to subsequent purification steps, is extremely conducive to suitability for industrialized production.
In the present invention, CNT first with a small amount of mixed with polymers, then by the process of the methods such as high-power ball mill, ultrasonic, mulser, at CNT surface graftomer molecular chain (needing in some cases to use a small amount of solvent).After solvent removal (if needing this step), treated CNT is mixed with fluoropolymer resin, use the method for melt blending or solution blending to prepare polymkeric substance CNT nano composite material.
Accompanying drawing explanation
Fig. 1: the FTIR spectrogram of CNT before and after process;
Fig. 2: the TEM photo (arrow indication place is PE) of CNT after process;
Fig. 3: the TGA curve of CNT before and after process;
The FESEM photo (arrow indication place is CNT) of Fig. 4: sample G section.
In figure: 1, the FTIR spectrogram of the treated CNT of product A in embodiment 1; 2, the FTIR spectrogram of undressed CNT; 3, the TGA curve of undressed CNT; 4, the TGA curve of the CNT that product A is treated in embodiment 1.
Embodiment
By explanation the present invention that the following examples can be detailed, disclose object of the present invention and be intended to protect all technological improvements in the scope of the invention.
In following examples, mechanic property test method is as follows:
Instron 5567 mechanical property tester, 50KN sensor, draw speed 50mm/min, probe temperature is 25 DEG C, and specimen shape meets ASTM D638V standard.
Embodiment 1
1 gram of multi-walled carbon nano-tubes (MWCNT) is scattered in 1000 grams of p-Xylol with 0.2 gram of PE, uses ultrasonic (1Kw) to process 4 hours.Except desolventizing and unreacted PE, obtain product A.
Then 0.2 gram of product A is mixed with 9.8 grams of PE, use twin screw extruder to prepare PE/CNT nano composite material G.Wherein blending temperature: 190 DEG C, screw rod L/D:40, screw speed: 80rpm.
Embodiment 2
1 gram of MWCNT is mixed with 0.01 gram of nylon 12 (PA12), process 16 hours in high speed ball mill (1000rpm).The MWCNT be disposed is separated with unreacted nylon 12, obtains product B.
1 gram of product B mixes with 99 grams of nylon 12, uses twin screw extruder to prepare PA12/CNT nano composite material I.Blending temperature: 195 DEG C, screw rod L/D:40, screw speed: 50rpm.
Embodiment 3
1 gram of MWCNT and 2 gram PMMA is scattered in 100 grams of chloroforms, uses high-speed emulsifying machine (30000rpm) to process 12 hours, except desolventizing and unreacted PMMA, obtain product C.
0.5 gram of product C mixes with 9.5 grams of PMMA, uses twin screw extruder to prepare PMMA/CNT nano composite material J.Blending temperature: 175 DEG C, screw rod L/D:40, screw speed: 30rpm.
Embodiment 4
1 gram of Single Walled Carbon Nanotube (SWCNT) is mixed with 0.5 gram of PE, process 12 hours in high speed ball mill (1000rpm).The SWCNT be disposed is separated with unreacted PE, obtains product D.
0.001 gram of product D mixes with 9.999 grams of PE, uses twin screw extruder to prepare PE/CNT nano composite material K.Blending temperature: 200 DEG C, screw rod L/D:40, screw speed: 100rpm.
Embodiment 5
1 gram of MWCNT and 1 gram PVDF is scattered in 100 grams of tetrahydrofuran (THF)s, uses ultrasonic (1Kw) to process 8 hours.Except desolventizing and unreacted PVDF, obtain product E.
1 gram of product E mixes with 4 grams of PVDF, uses twin screw extruder to prepare PVDF/CNT nano composite material L.Blending temperature: 210 DEG C, screw rod L/D:40, screw speed: 120rpm.
Comparative example
1 gram of MWCNT uses the concentrated acid oxidative treatment of bibliographical information, obtains product F.Then 0.2 gram of product F is mixed with 9.8 grams of PE, use twin screw extruder to prepare PE/CNT nano composite material H.Wherein blending temperature: 190 DEG C, screw rod L/D:40, screw speed: 80rpm.
Composite property contrast is done to embodiment and comparative example, as shown in Table 1:
Table one composite property contrasts
| Sample | Modulus (GPa) | Tensile strength (MPa) | Elongation at break (%) |
| G | 1.65 | 32 | 550 |
| H | 1.15 | 27 | 320 |
| I | 1.93 | 63 | 269 |
| J | 4.91 | 89 | / |
| K | 1.22 | 27 | 650 |
| L | 1.98 | 67 | 59 |
As a comparison, the performance of the straight polymer of CNT is not added as shown in Table 2:
Table two does not add the contrast of the straight polymer of CNT
| Sample | Modulus (GPa) | Tensile strength (MPa) | Elongation at break (%) |
| PE | 1.0 | 24 | 700 |
| PVDF | 1.1 | 43 | 200 |
| PMMA | 2.7 | 65 | 3 |
| PA12 | 1.1 | 46 | 450 |
As apparent from mechanical experimental results can, use modification CNT prepared by method provided by the present invention, the mechanical property of polymkeric substance can be increased substantially.Such as, for PE (sample G), the only addition of 0.2%, its modulus and intensity can improve 65% and 33% respectively, and keep splendid toughness.The major cause that composite materials property promotes is the dispersed of CNT and the interaction between filler CNT and polymkeric substance.As can be seen from FESEM (Fig. 4) photo of sample G section, CNT is the dispersion of single state, and under low multiple, see that distribution is very even.Relative, use CNT prepared by traditional acidifying oxidation style, it is to the reinforced effects of polymkeric substance very not obvious (comparative sample G and H).And acidifying oxidation style operating process is complicated and dangerous, method advantage provided by the invention is fairly obvious.
In addition, mixed with 1 gram of polyethylene (PE) by 1 gram of CNT, in high speed ball mill, (1000rpm) processes 6 hours.The CNT be disposed is separated with unreacted PE, and is characterized by means such as FTIR, TEM, TGA.Concrete outcome is shown in Figure of description.As can be seen from FTIR result (accompanying drawing 1), after process CNT FTIR collection of illustrative plates in there is the absorption peak of PE near wave number 2900/cm; After TEM photo (accompanying drawing 2) shows to process, CNT caliber becomes large, and can observe the existence of PE; The CNT that TGA analyzes after (accompanying drawing 3) shows to process simultaneously starts thermal destruction at about 400 DEG C, and basically identical with PE heat decomposition temperature, PE is about 27% in the grafting amount of CNT surface.As can be seen from the above results obviously, use method of the present invention can simple and effective at CNT surface graftomer.
Part not in the detailed description of the invention is prior art.
Claims (8)
1. a novel C NT surface treatment method, comprises the following steps: 1) by CNT and polymkeric substance proportionally 1:2 ~ 100:1(w/w) be scattered in solvent, or by CNT and polymkeric substance proportionally 1:2 ~ 100:1(w/w) be pre-mixed evenly;
2) matrix polymer of grafting target matrix material: use high-energy physical means to process the mixture obtained in step 1): interrupt polymer molecular chain and break CNT tube wall producing free radical, polymer molecular chain is made to graft on CNT surface by the coupling reaction of free radical, be separated except desolventizing and unreacted polymkeric substance, obtain surface treated novel C NT, be designated as product A.
2. novel C NT surface treatment method as claimed in claim 1, it is characterized in that: described high-energy physical means is the means producing the phenomenon of energy concentration of high temperature, high pressure, high speed shear or ultrasonic cavitation at processed material or its local, utilizes the energy in High-speed machining means to produce free radical or active group for physically; Described high-energy physical means comprises large power supersonic, ball milling, emulsification means.
3. novel C NT surface treatment method as claimed in claim 1, is characterized in that: described CN T is multi-walled carbon nano-tubes (MWCNT), Single Walled Carbon Nanotube (SWCNT), or the one in double-walled carbon nano-tube.
4. novel C NT surface treatment method as claimed in claim 2, is characterized in that: described CNT is radius is 1nm-200nm, CNT length 50nm-500 μm.
5. novel C NT surface treatment method as claimed in claim 1, is characterized in that: described polymkeric substance is PP, polyethylene (PE), nylon 12(PA12), one in PVC, PMMA or PVDF.
6. a preparation method for polymkeric substance/CNT nano composite material, is characterized in that: product A described in claim 1 mixed with fluoropolymer resin, and by melt blending or solution blending mode, preparation draws polymkeric substance/CNT nano composite material.
7. the preparation method of polymkeric substance/CNT nano composite material as claimed in claim 5, is characterized in that: in described polymkeric substance/CNT nano composite material, the content of CNT is 0.01 ~ 20wt%.
8. the preparation method of polymkeric substance/CNT nano composite material as claimed in claim 5, is characterized in that: the CNT in described step (1) can use the one in Graphene, carbon fiber or carbon nanofiber to substitute.
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Cited By (13)
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| CN105885397A (en) * | 2016-05-10 | 2016-08-24 | 扬州众成纳米科技有限公司 | MWCNT (multi-walled carbon nano-tube) surface treatment method, and method for preparing polymer/ MWCNT nanocomposite material by using MWCNTs |
| CN106117602A (en) * | 2016-05-10 | 2016-11-16 | 扬州众成纳米科技有限公司 | A kind of SWCNT surface treatment method and the method utilizing this SWCNT to prepare polymer/SWCNT nano composite material |
| EP3513411A4 (en) * | 2016-07-22 | 2020-03-25 | Rutgers, The State University of New Jersey | In situ bonding of carbon fibers and nanotubes to polymer |
| CN111484676A (en) * | 2020-06-13 | 2020-08-04 | 厦门毅兴行塑胶原料有限公司 | Toughness-improved polypropylene and preparation method thereof |
| CN112625437A (en) * | 2020-12-16 | 2021-04-09 | 湖北洋田塑料制品有限公司 | Nylon 66 thermoplastic elastomer material and preparation method thereof |
| US11098175B2 (en) | 2012-10-19 | 2021-08-24 | Rutgers, The State University Of New Jersey | In situ exfoliation method to fabricate a graphene-reinforced polymer matrix composite |
| US11174366B2 (en) | 2013-04-18 | 2021-11-16 | Rutgers, The State University Of New Jersey | In situ exfoliation method to fabricate a graphene-reinforced polymer matrix composite |
| US11225558B2 (en) | 2014-07-30 | 2022-01-18 | Rutgers, The State University Of New Jersey | Graphene-reinforced polymer matrix composites |
| US11479653B2 (en) | 2018-01-16 | 2022-10-25 | Rutgers, The State University Of New Jersey | Use of graphene-polymer composites to improve barrier resistance of polymers to liquid and gas permeants |
| US11479652B2 (en) | 2012-10-19 | 2022-10-25 | Rutgers, The State University Of New Jersey | Covalent conjugates of graphene nanoparticles and polymer chains and composite materials formed therefrom |
| US11702518B2 (en) | 2016-07-22 | 2023-07-18 | Rutgers, The State University Of New Jersey | In situ bonding of carbon fibers and nanotubes to polymer matrices |
| US11760640B2 (en) | 2018-10-15 | 2023-09-19 | Rutgers, The State University Of New Jersey | Nano-graphitic sponges and methods for fabricating the same |
| US11807757B2 (en) | 2019-05-07 | 2023-11-07 | Rutgers, The State University Of New Jersey | Economical multi-scale reinforced composites |
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| US11479652B2 (en) | 2012-10-19 | 2022-10-25 | Rutgers, The State University Of New Jersey | Covalent conjugates of graphene nanoparticles and polymer chains and composite materials formed therefrom |
| US11098175B2 (en) | 2012-10-19 | 2021-08-24 | Rutgers, The State University Of New Jersey | In situ exfoliation method to fabricate a graphene-reinforced polymer matrix composite |
| US11174366B2 (en) | 2013-04-18 | 2021-11-16 | Rutgers, The State University Of New Jersey | In situ exfoliation method to fabricate a graphene-reinforced polymer matrix composite |
| US11225558B2 (en) | 2014-07-30 | 2022-01-18 | Rutgers, The State University Of New Jersey | Graphene-reinforced polymer matrix composites |
| CN105885397A (en) * | 2016-05-10 | 2016-08-24 | 扬州众成纳米科技有限公司 | MWCNT (multi-walled carbon nano-tube) surface treatment method, and method for preparing polymer/ MWCNT nanocomposite material by using MWCNTs |
| CN106117602A (en) * | 2016-05-10 | 2016-11-16 | 扬州众成纳米科技有限公司 | A kind of SWCNT surface treatment method and the method utilizing this SWCNT to prepare polymer/SWCNT nano composite material |
| EP3513411A4 (en) * | 2016-07-22 | 2020-03-25 | Rutgers, The State University of New Jersey | In situ bonding of carbon fibers and nanotubes to polymer |
| US11702518B2 (en) | 2016-07-22 | 2023-07-18 | Rutgers, The State University Of New Jersey | In situ bonding of carbon fibers and nanotubes to polymer matrices |
| US11059945B2 (en) | 2016-07-22 | 2021-07-13 | Rutgers, The State University Of New Jersey | In situ bonding of carbon fibers and nanotubes to polymer matrices |
| US11479653B2 (en) | 2018-01-16 | 2022-10-25 | Rutgers, The State University Of New Jersey | Use of graphene-polymer composites to improve barrier resistance of polymers to liquid and gas permeants |
| US11760640B2 (en) | 2018-10-15 | 2023-09-19 | Rutgers, The State University Of New Jersey | Nano-graphitic sponges and methods for fabricating the same |
| US11807757B2 (en) | 2019-05-07 | 2023-11-07 | Rutgers, The State University Of New Jersey | Economical multi-scale reinforced composites |
| CN111484676A (en) * | 2020-06-13 | 2020-08-04 | 厦门毅兴行塑胶原料有限公司 | Toughness-improved polypropylene and preparation method thereof |
| CN112625437A (en) * | 2020-12-16 | 2021-04-09 | 湖北洋田塑料制品有限公司 | Nylon 66 thermoplastic elastomer material and preparation method thereof |
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Application publication date: 20150930 |