CN101407587A - Preparation of polyurethane / carbon nano-tube composite material - Google Patents
Preparation of polyurethane / carbon nano-tube composite material Download PDFInfo
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- CN101407587A CN101407587A CNA2008100418229A CN200810041822A CN101407587A CN 101407587 A CN101407587 A CN 101407587A CN A2008100418229 A CNA2008100418229 A CN A2008100418229A CN 200810041822 A CN200810041822 A CN 200810041822A CN 101407587 A CN101407587 A CN 101407587A
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Abstract
The invention relates to a preparation method of a polyurethane/carbon nanotube composite material, which is characterized in that carbon nanotubes which are subjected to mechanically ball grinding treatment of strong alkaline are dispersed in a solvent uniformly, polyurethane is dissolved in the solvent containing the carbon nanotubes and stirred for mixing uniformly; and finally, the solvent in the mixed solution is removed and the polyurethane/carbon nanotube composite material is prepared. The electric conductivity of the polyurethane/carbon nanotube composite material prepared by the method is greatly improved and the composite material can be used as an antistatic material; and simultaneously, mechanical properties are greatly enhanced. The composite material is prepared by using a solution stirring method, and the preparation method is simple in process, convenient in operation and suitable for large-scale industrializing production.
Description
Technical field
The invention belongs to the material technology field, be specifically related to a kind of preparation method of polyurethane/carbon nano-tube composite material.
Background technology
Carbon nanotube be Japanese Iijima in 1991 (Nature, 1991,354:56-58) producing C
60Experiment in find that the caliber size is nano level.The similar graphite of its structural pipe wall, good conductivity, specific surface area is big, has excellent mechanics, electricity, thermal property.More priorly be, the molecular structure of carbon nanotube and polymer chain structural similitude, length-to-diameter ratio has fabulous snappiness up to 100-1000, has good consistency with polymkeric substance.Therefore, constitute matrix material in the polymeric matrix, can greatly improve its performance if even carbon nanotube ground can be added to.
Polyurethane material is the superpolymer with unique processing characteristics that a class makes with polyisocyanates and polyol reaction, and it is widely used in departments such as electromechanics, boats and ships, aviation, vehicle, civil construction, light industry, weaving with its good performance.But poor performance such as its intensity is not high, and is antistatic, thereby limit its further application.Therefore, the preparation polyurethane/carbon nano-tube composite material can combine the performance of two kinds of materials, thereby can make it have purposes more widely.
At present, the report of existing preparation polyurethane/carbon nano-tube composite material.For example, people such as analogy radiance (use by engineering plastics, 2005,33:11-14) prepared polyurethane/carbon nano-tube composite material by situ aggregation method, people (Composites Science and Technology such as Korea S Nanda Gopal Sahoo, 2007,67:1920-1929) by Prepared by Solution Mixing Method polyurethane/carbon nano-tube composite material.The mechanical property of these matrix materials and conductivity have all had raising to a certain degree.But in above-mentioned prior art, for improving carbon nanotube uniformly dispersed in matrices of composite material, they adopt the strong acid method for oxidation that carbon nanotube is carried out surface modification.Because carbon nanotube itself has great length-to-diameter ratio, be easy to be intertwined, when especially adopting solution blending process, the volatilization of solvent can make carbon nanotube produce very serious reunion, thereby the improvement of composite property is restricted.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polyurethane/carbon nano-tube composite material of excellent performance.Carbon nanotube blocked become to have best length-to-diameter ratio, and make it be added with hydroxyl isoreactivity group, this not only helps further improving the performance of the uniformly dispersed and excellent properties of carbon nanotube in matrices of composite material, and can overcome in the prior art because carbon nanotube itself has great length-to-diameter ratio, be easy to be intertwined, especially when solvent evaporates, make carbon nanotube produce serious drawbacks such as agglomeration, prepare the excellent more polyurethane/carbon nano-tube composite material of performance.
The preparation method of a kind of polyurethane/carbon nano-tube composite material that the present invention proposes, it is characterized in that: will be dispersed in the solvent through highly basic mechanical ball milling processed carbon nanotubes, urethane is dissolved in the solvent that contains carbon nanotube, mixes; At last the solvent in the mixing solutions is removed and made polyurethane/carbon nano-tube composite material.
Described highly basic mechanical ball milling to carbon nanotube adopts the wet-milling mode, and the ball milling time was controlled at 3-40 hour, and the highly basic of selecting for use is KOH, and additive is that ethanol carries out wet-milling.
Described solvent is selected from toluene, acetone, dimethyl formamide, N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone.
The content of urethane accounts for 80-99.5wt% in the described matrix material, and the content of carbon nanotube accounts for 20-0.5wt%.
Described urethane is the urethane that can be dissolved in organic solvent that polyvalent alcohol, isocyanic ester and chainextender form, polyvalent alcohol is selected from polyether glycol or polyester polyol, isocyanic ester select oneself vulcabond, tolylene diisocyanate, 4,4, other derivatives of-diphenylmethanediisocyanate or isocyanic ester, chainextender is selected from C
2-C
6Glycol or diamines.
The present invention compares with existing preparation method, and its advantage is: carbon nanotube is uniformly dispersed in polymeric matrix, and the mechanical property and the conductivity of the polyurethane/carbon nano-tube composite material of preparation are significantly improved.Composite material by adopting solution stirring method preparation of the present invention, technology is simple, the easy to operate large-scale industrial production that is applicable to.
Embodiment
Further specify the present invention below by specific embodiment, but present embodiment is not limited to the present invention, every employing similarity method of the present invention and similar variation thereof all should be listed protection scope of the present invention in.
Embodiment 1: the preparation of polyurethane/carbon nano-tube composite material 1 (carbon nanotube is through the highly basic ball-milling processing, and content is the 0.5wt% of matrix material)
(1) processing of carbon nanotube: the carbon nanotube of 0.05g is mixed with 1gKOH, add a certain amount of ethanol, carry out ball milling, rotational speed of ball-mill is 250r/min, and the ball milling time is 3 hours, uses the distilled water repetitive scrubbing to neutral at last, dries stand-by.
(2) preparation of pure polyurethane material: earlier with polyether glycol (number-average molecular weight is 1816) and 4,4 ,-diphenylmethanediisocyanate prepares performed polymer at 90 ℃ of reaction 1h, and then with 1, the 4-butyleneglycol carries out chain extension.Add N,N-dimethylacetamide and dissolve, removing desolvates makes pure polyurethane material.Wherein, polyether glycol, 4,4 ,-diphenylmethanediisocyanate and 1, the mol ratio of 4-butyleneglycol is 1/3/2.
(3) preparation of matrix material: the treated carbon nanotube of 0.02g is put into 30mlN, in the N-N,N-DIMETHYLACETAMIDE, ultra-sonic dispersion 1h.The pure polyurethane material of 3.98g is put into above-mentioned solution, heating for dissolving, and after stirring, removing desolvates makes polyurethane/carbon nano-tube composite material.
Pure polyurethane material and matrix material mechanical property and conducting performance test have been carried out.The result shows that polyurethane/carbon nano-tube composite material 1 has improved 25% than the breaking tenacity of pure polyurethane material, and conductivity has improved 2 orders of magnitude.
Embodiment 2: the preparation of polyurethane/carbon nano-tube composite material 2 (carbon nanotube is through the highly basic ball-milling processing, and content is the 5wt% of matrix material)
(1) processing of carbon nanotube: the carbon nanotube of 0.4g is mixed with 6gKOH, add a certain amount of ethanol with the mixture submergence, carry out ball milling, rotational speed of ball-mill is 250r/min, and the ball milling time is 20 hours, uses the distilled water repetitive scrubbing to neutral at last, dries stand-by.
(2) preparation of pure polyurethane material: the preparation method is identical with method among the embodiment 1.
(3) preparation of matrix material: the treated carbon nanotube of 0.2g is put into the 30ml N,N-dimethylacetamide, ultra-sonic dispersion 2h.The pure polyurethane material of 3.8g is put into above-mentioned solution, heating for dissolving, and after stirring, removing desolvates makes polyurethane/carbon nano-tube composite material.
The performance test results shows that polyurethane/carbon nano-tube composite material 2 has improved 81% than the breaking tenacity of pure polyurethane material, and conductivity has improved 3 orders of magnitude.
Embodiment 3: the preparation of polyurethane/carbon nano-tube composite material 3 (carbon nanotube is through the highly basic ball-milling processing, and content is the 10wt% of matrix material)
(1) processing of carbon nanotube: the carbon nanotube of 0.6g is mixed with 12gKOH, add a certain amount of ethanol, add the laggard capable ball milling of goal with the mixture submergence, rotational speed of ball-mill is 250r/min, the ball milling time is 30 hours, uses the distilled water repetitive scrubbing to neutral at last, dries stand-by.
(2) preparation of pure polyurethane material: the preparation method is identical with method among the embodiment 1.
(3) preparation of matrix material: the treated carbon nanotube of 0.4g is put into the 30ml N,N-dimethylacetamide, ultra-sonic dispersion 5h.The pure polyurethane material of 3.6g is put into above-mentioned solution, heating for dissolving, and after stirring, removing desolvates makes polyurethane/carbon nano-tube composite material.
The performance test results shows that polyurethane/carbon nano-tube composite material 3 has improved 117% than the breaking tenacity of pure polyurethane material, and conductivity has improved 5 orders of magnitude.
Embodiment 4: the preparation of polyurethane/carbon nano-tube composite material 4 (carbon nanotube is through the highly basic ball-milling processing, and content is the 20wt% of matrix material)
(1) processing of carbon nanotube: the carbon nanotube of 1g is mixed with 16gKOH, add a certain amount of ethanol, add the laggard capable ball milling of goal with the mixture submergence, rotational speed of ball-mill is 250r/min, the ball milling time is 40 hours, uses the distilled water repetitive scrubbing to neutral at last, dries stand-by.
(2) preparation of pure polyurethane material: the preparation method is identical with method among the embodiment 1.
(3) preparation of matrix material: the treated carbon nanotube of 0.8g is put into the 30ml N,N-dimethylacetamide, ultra-sonic dispersion 10h.The pure polyurethane material of 3.2g is put into above-mentioned solution, heating for dissolving, and after stirring, removing desolvates makes polyurethane/carbon nano-tube composite material.
The performance test results shows that polyurethane/carbon nano-tube composite material 4 has improved 80% than the breaking tenacity of pure polyurethane material, and conductivity has improved 6 orders of magnitude.
Comparative example 1: the preparation of polyurethane/carbon nano-tube composite material 5 (carbon nanotube is through the strong acid oxide treatment, and content is 5wt%)
(1) processing of carbon nanotube: the 2g carbon nanotube is joined in the mixed solution of 60ml concentrated nitric acid and 20ml concentrated nitric acid, reflux in 90 ℃ and stirred 20 minutes, stop heating, remove acid solution, be washed with distilled water to neutrality repeatedly, oven dry.
(2) preparation of pure polyurethane material: the preparation method is identical with method among the embodiment 1.。
(3) preparation of matrix material: 0.2g is put into the 30ml N,N-dimethylacetamide, ultra-sonic dispersion 2h through acid-treated carbon nanotube.The pure polyurethane material of 3.8g is put into above-mentioned solution, heating for dissolving, and after stirring, removing desolvates makes polyurethane/carbon nano-tube composite material.
The performance test results shows that polyurethane/carbon nano-tube composite material 5 has only improved 8.8% than the breaking tenacity of pure polyurethane material, and conductivity has only improved 1 order of magnitude.
Comparative example 2: the preparation of polyurethane/carbon nano-tube composite material 6 (carbon nanotube is through the strong acid oxide treatment, and content is 10wt%)
Press the method in the comparative example 1,0.4g is put into the 30ml N,N-dimethylacetamide, ultra-sonic dispersion 2h through acid-treated carbon nanotube.The pure polyurethane material of 3.6g is put into above-mentioned solution, heating for dissolving, and after stirring, removing desolvates makes polyurethane/carbon nano-tube composite material.
The performance test results shows that polyurethane/carbon nano-tube composite material 6 has improved 15.2% than the breaking tenacity of pure polyurethane material, and conductivity has improved 2 orders of magnitude.
Claims (5)
1. the preparation method of a polyurethane/carbon nano-tube composite material is characterized in that: will be dispersed in the solvent through highly basic mechanical ball milling processed carbon nanotubes, urethane is dissolved in the solvent that contains carbon nanotube, and mix; At last the solvent in the mixing solutions is removed and made polyurethane/carbon nano-tube composite material.
2. the preparation method of a kind of polyurethane/carbon nano-tube composite material according to claim 1, it is characterized in that: described highly basic mechanical ball milling to carbon nanotube is to adopt the wet-milling mode, the ball milling time was controlled at 3-40 hour, and the highly basic of selecting for use is KOH, and additive is an ethanol.
3. the preparation method of a kind of polyurethane/carbon nano-tube composite material according to claim 1, it is characterized in that: described solvent is selected from toluene, acetone, dimethyl formamide, N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone.
4. the preparation method of a kind of polyurethane/carbon nano-tube composite material according to claim 1, it is characterized in that: the content of urethane accounts for 80-99.5wt% in the described matrix material, and the content of carbon nanotube accounts for 20-0.5wt%.
5. the preparation method of a kind of polyurethane/carbon nano-tube composite material according to claim 1, it is characterized in that: described urethane is the urethane that can be dissolved in organic solvent that polyvalent alcohol, isocyanic ester and chainextender form, polyvalent alcohol is selected from polyether glycol or polyester polyol, isocyanic ester select oneself vulcabond, tolylene diisocyanate, 4,4, other derivatives of-diphenylmethanediisocyanate or isocyanic ester, chainextender is selected from C
2-C
6Glycol or diamines.
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| CNA2008100418229A CN101407587A (en) | 2008-08-18 | 2008-08-18 | Preparation of polyurethane / carbon nano-tube composite material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627847A (en) * | 2012-04-11 | 2012-08-08 | 东华大学 | Bendable unsupported carbon nanotube gas-sensitive film and preparation method thereof |
| 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 |
| CN104592754A (en) * | 2015-01-14 | 2015-05-06 | 黑龙江大学 | Preparation method of polyaniline-coated carbon nanotube-supported copper and nickel solid solution material |
| US9506194B2 (en) | 2012-09-04 | 2016-11-29 | Ocv Intellectual Capital, Llc | Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media |
| CN115612283A (en) * | 2022-12-20 | 2023-01-17 | 山东一诺威聚氨酯股份有限公司 | Easily-conductive high-resilience TPU/EVA composite foam material and preparation method thereof |
-
2008
- 2008-08-18 CN CNA2008100418229A patent/CN101407587A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627847A (en) * | 2012-04-11 | 2012-08-08 | 东华大学 | Bendable unsupported carbon nanotube gas-sensitive film and preparation method thereof |
| US9506194B2 (en) | 2012-09-04 | 2016-11-29 | Ocv Intellectual Capital, Llc | Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media |
| 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 |
| CN104592754A (en) * | 2015-01-14 | 2015-05-06 | 黑龙江大学 | Preparation method of polyaniline-coated carbon nanotube-supported copper and nickel solid solution material |
| CN115612283A (en) * | 2022-12-20 | 2023-01-17 | 山东一诺威聚氨酯股份有限公司 | Easily-conductive high-resilience TPU/EVA composite foam material and preparation method thereof |
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Open date: 20090415 |